CN106489100A - Photosensitive polymer combination, solidfied material, black matrix" and image display device - Google Patents

Photosensitive polymer combination, solidfied material, black matrix" and image display device Download PDF

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Publication number
CN106489100A
CN106489100A CN201580036578.5A CN201580036578A CN106489100A CN 106489100 A CN106489100 A CN 106489100A CN 201580036578 A CN201580036578 A CN 201580036578A CN 106489100 A CN106489100 A CN 106489100A
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group
optionally
compound
alkylidene
bond
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CN106489100B (en
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石井宏明
上村次郎
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Mitsubishi Rayon Co Ltd
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Mitsubishi Kasei Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)

Abstract

The present invention provide dispersibility excellent, the color material content ratio in photosensitive polymer combination can not relied on and forms the photosensitive polymer combination of the fine rule of fine.The photosensitive polymer combination of the present invention comprises：Color material (a), dispersant (b), Photoepolymerizationinitiater initiater (c), alkali soluble resin (d) and solvent (e), wherein, dispersant (b) comprises the polyurethane dispersant (b 1) with solvophilic group and adsorption group, this polyurethane dispersant (b 1) comprises the part-structure shown in following formula (i), and Photoepolymerizationinitiater initiater (c) comprises oxime ester Photoepolymerizationinitiater initiater (c 1).

Description

Photosensitive polymer combination, solidfied material, black matrix" and image display device
Technical field
The present invention relates to photosensitive polymer combination, solidfied material, black matrix" and image display device.Specifically, relate to And dispersibility, developability, excellent heat resistance, can be formed fine fine rule photosensitive polymer combination.The sense of the present invention Photosensitive resin composition be particularly suited for having high light-proofness, can be formed simultaneously fine fine rule black matrix" (Black Matrix, hereinafter also referred to as " BM ") use photosensitive polymer combination.Moreover, it relates to this photosensitive polymer combination Solidfied material and application thereof.
Background technology
Light filter typically the surface of the transparency carrier such as glass or plastics formed black black matrix" then successively with The pattern of striated or zyklopisch etc. forms the pixel of more than the 3 kinds different colours such as red, green or blue.Pattern dimension is because of filter The purposes of color chips and respective color and different, but usually 5～700 μm about.
As the representational manufacture method of light filter, it has been currently known pigment dispersion method.Using pigment dispersion method system In the case of making light filter, first, after by the coating on the transparent substrate of the photosensitive polymer combination containing black pigment So that it is dried, then, after image exposure, development, so that it is solidified by more than 200 DEG C of high-temperature process, thus Form BM.By repeating this operation for the shades of colour such as red, green or blue, thus forming light filter.
BM generally configures between the pixel such as red, green or blue with clathrate, striated or zyklopisch, by suppressing each pixel Between colour mixture and have and improve contrast or the effect that prevents light leak.Therefore, for BM it is desirable to high light-proofness.
Further, since the edge part of the pixel such as red, green or blue being formed after BM is formed can be overlapped with this BM, therefore can Affected by the thickness of BM and formed difference in height in lamination portion.In this lamination portion, the flatness of pixel is destroyed, meeting There is the not homogenizing of gap of liquid crystal cell or the unordered, thus causing the reduction of display capabilities of liquid crystal aligning.
For this reason, in recent years, particularly require to make the thickness of BM reach filming, and in order to display that when carrying out filming Go out sufficient light-proofness, developing direction is to make the pigment content ratio in photosensitive polymer combination become higher.
On the other hand, in order to realize the long lifetime of energy-saving and battery of mobile phone, developing direction is intended to reduce backlight Output, and show to also image be realized with high brightness in such a situa-tion, the graph thinning as the BM of light shielding part obtains To development.
In addition, in recent years, on the market of liquid crystal display, the miniaturization of panel computer etc. becomes main flow, and just large-scale For television set, high-resolution requirement just improves constantly, based on these reasons, for BM high graph thinning expectation increasingly High.In recent years, the live width of BM fine rule develops required up till now 6 μm from conventional 10 μm about.
In general, in order to manufacture the photosensitive polymer combination for pigment dispersion method, making first with bead etc. The compositionss comprising color material, dispersant or solvent etc. disperse to prepare dispersion liquid.Then, by this dispersion liquid and alkali soluble resin Or Photoepolymerizationinitiater initiater etc. is stirred mixing and prepares photosensitive polymer combination.
As light filter dispersant, be suggested has acrylic compounds, carbamatess, polyethyleneimine amine or poly- The all kinds such as esters, in addition, with regard to structure, also have been presented for all kinds such as random, block type or graft type (comb shape) (for example, patent documentation 1～3).
In the middle of these, carbamatess dispersant is due to can have hydroxyl using amino-formate bond in terminal addition The compound of base, primary/secondary amino group or mercapto, therefore, has been developed the material (example of various forms as dispersant As patent documentation 4～9).
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 2002-031713 publication
Patent documentation 2：No. 3509512 publications of Japanese Patent No.
Patent documentation 3：No. 3789965 publications of Japanese Patent No.
Patent documentation 4：Japanese Unexamined Patent Application 57-162723 publication
Patent documentation 5：Japanese Unexamined Patent Application Publication 2002-503746 publication
Patent documentation 6：Japanese Unexamined Patent Application Publication 2003-506538 publication
Patent documentation 7：Japanese Unexamined Patent Application Publication 2005-538192 publication
Patent documentation 8：Japanese Unexamined Patent Application Publication 2010-511752 publication
Patent documentation 9：Japanese Unexamined Patent Application Publication 2011-514411 publication
Content of the invention
Problems to be solved by the invention
The present inventor etc. it has been investigated that, for the dispersant described in regard to patent documentation 1～3, there is the kind because of pigment Class etc. is different and produce thickening after leading to not disperse or disperse, do not select suitable material or condition then cannot obtain fully Dispersion effect problem.In addition, during using these traditional dispersants, even if also cannot shape using highly sensitive initiator Become the higher fine fine rule currently requiring that.
In addition, for dispersant described in regard to patent documentation 4～9, under the conditions of the higher obscurity currently requiring that, It is exactly under conditions of pigment content ratio height, be insufficient for forming thinner fine rule.
Based on this, the problem of the present invention is that offer dispersibility is excellent, can not rely on color material content ratio and formed The photosensitive polymer combination of the fine rule of fine and employ the solidfied material of this photosensitive polymer combination, black matrix" And image display device.
The method of solve problem
The present inventor etc. have made intensive studies to solve above-mentioned problem, it was found that special by having certain The polyurethane dispersant of fixed structure is combined with highly sensitive Photoepolymerizationinitiater initiater, can not rely on photosensitive polymer combination In color material content ratio and form the fine fine rule of the height currently requiring that.
The present invention is based on such opinion and completes, and its main points is as follows.
1. a kind of photosensitive polymer combination, it comprises：Color material (a), dispersant (b), Photoepolymerizationinitiater initiater (c), alkali can Soluble resin (d) and solvent (e), wherein,
Dispersant (b) comprises the polyurethane dispersant (b-1) with solvophilic group and adsorption group,
This polyurethane dispersant (b-1) comprises the part-structure shown in following formula (i),
Photoepolymerizationinitiater initiater (c) comprises oxime ester Photoepolymerizationinitiater initiater (c-1).
[chemical formula 1]
[in formula (i), RaRepresent and optionally there is the alkylidene of carbon number 1～20 of substituent group, optionally there is substituent group The arlydene of carbon number 6～20 or the base of the carbon number 7～20 being linked by above-mentioned alkylidene and above-mentioned arlydene Group, * represents bonding position.]
2. the photosensitive polymer combination described in preceding paragraph 1, wherein, above-mentioned polyurethane dispersant (b-1) comprises：Containing above-mentioned The part-structure containing solvophilic group of solvophilic group and the part-structure containing adsorption group containing above-mentioned adsorption group,
The part-structure that this contains solvophilic group contains the part-structure of adsorption group by the portion shown in above-mentioned formula (i) with this Separation structure and link.
3. the photosensitive polymer combination described in preceding paragraph 1 or 2, wherein, above-mentioned polyurethane dispersant (b-1) has main chain, This main chain comprises the part-structure shown in above-mentioned formula (i).
4. the photosensitive polymer combination any one of preceding paragraph 1～3, wherein, above-mentioned solvophilic group comprises polyethers At least one of chain and polyester chain.
5. the photosensitive polymer combination any one of preceding paragraph 1～4, wherein, above-mentioned adsorption group is to be selected from the group In at least one：Tertiary amino, quaternary ammonium salt base and nitrogen atom heterocyclic radical.
6. the photosensitive polymer combination any one of preceding paragraph 2～5, wherein, the above-mentioned part knot containing adsorption group Structure has the part-structure shown in following formula (1).
[chemical formula 2]
[in formula (1), R1Represent the alkyl or aryl optionally with substituent group, R2And R3Represent independently of one another and optionally have The alkylidene of substituent group, arylidene alkylene or arlydene.
* represent bonding position.]
7. the photosensitive polymer combination any one of preceding paragraph 2～6, wherein, the above-mentioned part knot containing adsorption group Structure has at least one part-structure representing with following formula (2-1)～(2-3).
[chemical formula 3]
[in formula (2-1), RαAnd RβRepresent the alkyl or aryl optionally with substituent group independently of one another.
Rγ、RδAnd RεRepresent independently of one another the alkylidene optionally with substituent group, the arlydene optionally with substituent group, Or the group being linked by above-mentioned alkylidene and above-mentioned arlydene, wherein, RγFor optionally have substituent group alkylidene or by In the case of the group that above-mentioned alkylidene and above-mentioned arlydene link, constitute at least one of methylene of above-mentioned alkylidene Divide and be optionally selected from ester bond, ehter bond, amino-formate bond, urea bond, amido link, imide bond, thiocarbamate key, thioether At least one bonding in key and thioester bond replaces, in addition, RγAt least any with adjacent optionally via-NH- (C=O)-base One N atom is collectively forming urea bond or optionally forms amido link via carbonyl.
* represent bonding position.]
[chemical formula 4]
[in formula (2-2), RαAnd RβRepresent the alkyl or aryl optionally with substituent group independently of one another.
RγAnd RηRepresent independently of one another optionally have substituent group alkylidene, optionally have substituent group arlydene or The group being linked by above-mentioned alkylidene and above-mentioned arlydene, wherein, RγAnd RηIt is each independently and optionally there is substituent group Alkylidene or the group that linked by above-mentioned alkylidene and above-mentioned arlydene in the case of, constitute the Asia of above-mentioned alkylidene At least a portion of methyl is optionally selected from ester bond, ehter bond, amino-formate bond, urea bond, amido link, imide bond, thio ammonia At least one bonding in carbamate key, thioether bond and thioester bond replaces, in addition, RγAnd RηOptionally via-NH- (C=O)-base And be collectively forming urea bond with adjacent at least any one N atom or optionally form amido link via carbonyl.
* represent bonding position.]
[chemical formula 5]
[in formula (2-3), RαAnd RβRepresent the alkyl or aryl optionally with substituent group independently of one another.
Rγ’And RδRepresent independently of one another optionally have substituent group alkylidene, optionally have substituent group arlydene or The group being linked by above-mentioned alkylidene and above-mentioned arlydene, wherein, Rγ’For optionally have substituent group alkylidene or by In the case of the group that above-mentioned alkylidene and above-mentioned arlydene link, constitute at least one of methylene of above-mentioned alkylidene Divide and be optionally selected from ester bond, ehter bond, amino-formate bond, urea bond, amido link, imide bond, thiocarbamate key, thioether At least one bonding in key and thioester bond replaces, in addition, Rγ’Optionally common with adjacent N atom via-NH- (C=O)-base Form together urea bond or optionally form amido link via carbonyl.
Rε’Represent direct key, optionally there is the alkylidene of substituent group, optionally there is the arlydene of substituent group or by above-mentioned Asia The group that alkyl and above-mentioned arlydene link.
RζRepresent hydrogen atom, optionally there is the alkyl or aryl of substituent group.Wherein, RζFor abovementioned alkyl or above-mentioned aryl In the case of, at least one in its hydrogen atom is optionally replaced by tertiary amino or nitrogen atom heterocyclic radical.
* represent bonding position.]
8. the photosensitive polymer combination any one of preceding paragraph 1～7, wherein, oxime ester Photoepolymerizationinitiater initiater (c-1) has There is optionally substituted carbazyl.
9. the photosensitive polymer combination any one of preceding paragraph 1～8, wherein, alkali soluble resin (d) contain have The alkali soluble resin (d-1) of at least one of carboxyl and ethylenically unsaturated group.
10. wherein, alkali soluble resin (d-1) is epoxy (methyl) propylene to the photosensitive polymer combination described in preceding paragraph 9 Acid ester resin.
Photosensitive polymer combination described in 11. preceding paragraphes 10, wherein, above-mentioned epoxy (methyl) acrylate is following At least one of epoxy (methyl) acrylate (D1-1) and epoxy (methyl) acrylate (D1-2),
(1) epoxy (methyl) acrylate (D1-1), it is to make α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester and epoxy resin addition, then so that it is reacted with least one of polyprotic acid and its anhydride and obtain 's；
(2) epoxy (methyl) acrylate (D1-2), it is to make α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester and epoxy resin addition, then make itself and polyhydric alcohol and at least one of polyprotic acid and its anhydride Obtained from reaction.
Photosensitive polymer combination any one of 12. preceding paragraphes 1～11, wherein, the average primary particle diameter of color material (a) For 20～100nm.
Photosensitive polymer combination any one of 13. preceding paragraphes 1～12, wherein, color material (a) comprises white carbon black.
Photosensitive polymer combination described in 14. preceding paragraphes 13, its contain with respect to all solids composition be 40 mass % with On above-mentioned white carbon black.
A kind of 15. solidfied materials, it is so that the photosensitive polymer combination any one of preceding paragraph 1～14 is solidified Solidfied material.
A kind of 16. black matrix"s, it comprises the solidfied material described in preceding paragraph 15.
A kind of 17. image display devices, it possesses the black matrix" described in preceding paragraph 16.
The effect of invention
According to the present invention, it is possible to provide dispersibility is excellent, the color material that can not rely in photosensitive polymer combination contains Ratio and form the photosensitive polymer combination of the fine rule of fine.The photosensitive polymer combination of the present invention is especially as tool The black matrix" photosensitive polymer combination of fine rule that have high light-proofness, simultaneously can form fine is useful.
Brief description
[Fig. 1] Fig. 1 is the generalized section of of the organic EL element of the light filter illustrating to possess the present invention.
Symbol description
10 transparent support substrates
20 pixels
30 organic protection layers
40 inorganic oxide films
50 transparent anodes
51 hole injection layers
52 hole transmission layers
53 luminescent layers
54 electron injecting layers
55 negative electrodes
100 organic EL element
500 organic luminorphors
Specific embodiment
Hereinafter, embodiments of the present invention are specifically described, but the present invention are not limited to following embodiment, Implement after various changes can be carried out in the range of its main points.
It should be noted that in the present invention, described " (methyl) acrylic acid " expression " acrylic acid and/or metering system Acid ", with regard to described " (methyl) acrylate ", " (methyl) acryloyl group " similarly.In addition, described " sour (anhydride) ", " ... acid The implication of (acid anhydride) " includes both acid and its anhydride.
In addition, in the present invention, described " all solids composition " refers in photosensitive polymer combination or described below Whole compositions beyond contained solvent in ink.
In addition, in the present invention, described number-average molecular weight and weight average molecular weight refer to based on GPC (gel permeation chromatography) And obtain and be converted into the number-average molecular weight (Mn) of polystyrene, weight average molecular weight (Mw).
In addition, in the present invention, unless otherwise specified, described " amine number " represents the amine being converted into effective solid constituent Value, is to become, with the alkali number with every 1g solid constituent of dispersant, the value that the weight of the KOH of equivalent represents.It should be noted that closing In assay method, as hereinafter described.On the other hand, unless otherwise specified, described " acid number " expression is converted into effective solid The acid number of composition, can be calculated by acid-base titration.
In addition, in this manual, sometimes represent bonding position using " * ".
In addition, in this manual, concept described " polyurethane skeleton " not only includes the skeleton being made up of polyurethane, also Including the skeleton being made up of polyurethane-urea.Similarly, the concept of described " polyurethane dispersant " not only includes thering is more than 2 ammonia The dispersant of carbamate key, also includes the dispersant with more than 2 urea bonds, the dispersion with amino-formate bond and urea bond Agent.
[photosensitive polymer combination]
The photosensitive polymer combination of the present invention contains：
Color material (a),
Specific dispersant (b),
Specific Photoepolymerizationinitiater initiater (c),
Alkali soluble resin (d) and
Solvent (e).
The photosensitive polymer combination of the present invention preferably further contains photopolymerization monomer, and further as desired Comprise thio-alcohol, dispersing aid (pigment derivative), closely sealed improving agent, coating improving agent, development modifying agent, ultra-violet absorption Other gradation composition such as agent, antioxidant, surfactant, each gradation composition is generally to be dissolved or dispersed in the state of solvent (e) Used.
It is a feature of the present invention that containing specific polyurethane dispersant (b-1) conduct point in photosensitive polymer combination Powder and containing oxime ester Photoepolymerizationinitiater initiater (c-1) as Photoepolymerizationinitiater initiater (c).
[dispersant (b)]
The photosensitive polymer combination of the present invention is characterised by, as dispersant (b), comprises specific they Agent (b-1).
[polyurethane dispersant (b-1)]
Above-mentioned polyurethane dispersant (b-1) is to comprise following formula (i) with solvophilic group and adsorption group and further The dispersant of shown part-structure.
[chemical formula 6]
In above-mentioned formula (i), RaRepresent and optionally there is the alkylidene of carbon number 1～20 of substituent group, optionally there is replacement The arlydene of carbon number 6～20 of base or the carbon number 7～20 that linked by above-mentioned alkylidene and above-mentioned arlydene Group, * represents bonding position.
As long as the carbon number of the alkylidene optionally with substituent group in above-mentioned formula (i) does not just have in the range of 1～20 Have a particular determination, preferably more than 2, more preferably more than 3, additionally, it is preferred that for less than 15, more preferably less than 10, further It is preferably less than 7.More than for above-mentioned lower limit, there is the tendency that can make favorable dispersibility, in addition, by above-mentioned Below limit value, there is the tendency being prevented from high viscosity.
Alkylidene can also can be ring-type for chain, furthermore it is also possible to be the alkylene of alkylidene by chain and ring-type The group that base links.From the viewpoint of dispersibility, preferably at least there is the group of annulus.
As the concrete example of alkylidene, can enumerate：Trimethylene, tetramethylene, pentamethylene, hexa-methylene, eight methylenes Base, decamethylene, cyclohexylidene, cyclohexylidene methylene and cyclohexylidene methylene cyclohexylidene etc..From making favorable dispersibility From the viewpoint of, preferably tetramethylene, pentamethylene, hexa-methylene, cyclohexylidene or cyclohexylidene methylene Asia hexamethylene Base, more preferably pentamethylene, hexa-methylene, cyclohexylidene or cyclohexylidene methylene cyclohexylidene.
As the concrete example of the alkylidene optionally with substituent group, following group can be enumerated.
[chemical formula 7]
As long as the carbon number of the arlydene optionally with substituent group in above-mentioned formula (i) does not just have in the range of 6～20 There is a particular determination, preferably less than 15, more preferably less than 10, more preferably less than 8.By for above-mentioned lower limit with On, there is the tendency that can make favorable dispersibility, in addition, by below for above-mentioned higher limit, existing and being prevented from high viscosity Tendency.
As the concrete example of arlydene, following group can be enumerated.
[chemical formula 8]
In addition, as the concrete example of the arlydene with substituent group, following group can be enumerated.
[chemical formula 9]
Wherein, from the viewpoint of dispersibility, the group shown in preferably above-mentioned formula (0-3).
In above-mentioned formula (i) by the alkylidene optionally with substituent group and optionally there is the arlydene of substituent group link As long as the carbon number of group be just not particularly limited in the range of 7～20, more preferably more than 8, more preferably 9 More than, additionally, it is preferred that being less than 15, more preferably less than 14, more preferably less than 13.By for above-mentioned lower limit with On, there is the tendency that can make favorable dispersibility, in addition, by below for above-mentioned higher limit, existing and being prevented from high viscosity Tendency.
As long as the number of the arlydene being had by the group that above-mentioned alkylidene and above-mentioned arlydene link is more than 1 Just it is not particularly limited, from the viewpoint of dispersibility, preferably more than 2, more preferably less than 3.As long as in addition, alkylidene Number is just not particularly limited for more than 1, from the viewpoint of dispersibility, preferably less than 3.
Specifically can enumerate for example：By 1 arlydene optionally with substituent group and 1 alkylidene optionally with substituent group The group that links and by 2 arlydene optionally with substituent group via 1 alkylidene optionally with substituent group even The group of knot.
As the concrete example of the group being linked by above-mentioned alkylidene and above-mentioned arlydene, following group can be enumerated.
[chemical formula 10]
Wherein, from the viewpoint of dispersibility, the group shown in preferably above-mentioned formula (0-5).
As these alkylidenes, arlydene, the replacement optionally being had by the group that alkylidene and arlydene link Base, is not particularly limited, and can enumerate for example：Alkyl, aryl, aralkyl etc..
The carbon number of abovementioned alkyl is not particularly limited, preferably 1～20, more preferably 1～10, more preferably 1～5.Alkyl can be straight-chain, can also be branched, can also be ring-type.As concrete example, can enumerate methyl, ethyl, Cyclohexyl etc..
In addition, the carbon number of above-mentioned aryl is not particularly limited, preferably 6～20, more preferably 6～10.As tool Style, can enumerate phenyl, naphthyl etc..
In addition, the carbon number of above-mentioned aralkyl is not particularly limited, preferably 7～20, more preferably 7～10.As Concrete example, can enumerate benzyl etc..
In the middle of these, from the viewpoint of handling easiness or dispersibility, preferably methyl.
In the middle of these, from the viewpoint of dispersibility, further preferred RaGroup shown in above-mentioned formula (0-5), above-mentioned Group shown in formula (0-3) or the group shown in above-mentioned formula (0-1).
In addition, polyurethane dispersant (b-1) can also be the part-structure containing solvophilic group described below to each other Linked by the part-structure shown in above-mentioned formula (i).It is equally possible that being the portion containing adsorption group described below Separation structure is linked by the part-structure shown in above-mentioned formula (i) to each other.Furthermore it is also possible to be described below containing parent The part-structure of solvent group and the part-structure containing adsorption group described below are by the part-structure shown in above-mentioned formula (i) Link.
It is believed that polyurethane dispersant (b-1) passes through there is the part-structure shown in above-mentioned formula (i), energy like this Enough the part-structure containing solvophilic group and the part-structure containing adsorption group are configured on straight line, so that these parts knot The movable range of structure increases, and thus exists and can improve the intermiscibility to solvent and the tendency of the adsorptivity to pigment.
Additionally, it is preferred that polyurethane dispersant (b-1) has main chain, and this main chain comprises the part knot shown in above-mentioned formula (i) Structure.It is believed that by adopting the high part-structure of the rectilinearity shown in above-mentioned formula (i) like this as contained in main chain Part-structure, can configure the part-structure containing solvophilic group and the part-structure containing adsorption group on straight line, thus So that the movable range of these part-structures is increased, thus exist and improve inclining of the intermiscibility to solvent and the adsorptivity to pigment To.
It should be noted that in this manual, the main chain that polyurethane dispersant (b-1) has refers to by more than 2 ammonia Chain the longest in the chain that carbamate key links.
As preferred embodiment, the polyurethane skeleton that can enumerate main chain is the embodiment of linear chain structure.This situation Under, in main chain except with solvophilic group be bonded position, adsorption group and with adsorption group be bonded position in addition to, become Linear chain structure.In the case that polyurethane skeleton is straight chain like this, there is solvophilic group to the intermiscibility of solvent or absorption Group becomes good tendency to the absorption of pigment.Particularly, by making polyurethane skeleton be straight chain, can promote based on amino first , there is the tendency that dispersibility becomes good in the pigment adsorption of the nitrogen-atoms of acid esters key.
In addition, the content ratio of the part-structure shown in above-mentioned formula (i) in polyurethane dispersant (b-1) does not have special limit Fixed, from the viewpoint of dispersibility, preferably 5 moles more than %, more preferably 10 moles of more than %, additionally, it is preferred that rub for 90 You are below %, more preferably 80 moles of below %.
Similarly, the part knot shown in above-mentioned formula (i) from the viewpoint of dispersibility, in polyurethane dispersant (b-1) The content ratio of structure is preferably more than 5 mass %, more than more preferably 10 mass %, additionally, it is preferred that for below 90 mass %, more It is preferably below 80 mass %.
(adsorption group)
The adsorption group that polyurethane dispersant (b-1) has is not particularly limited, from the viewpoint of dispersibility, preferably It is at least one (hereinafter also referred to as " the specifically absorption base in tertiary amino, quaternary ammonium salt base and nitrogen atom heterocyclic radical Group ").
In addition, in the case that polyurethane dispersant (b-1) has main chain, from the viewpoint of dispersibility, adsorption group is excellent Elect at least one in tertiary amino, quaternary ammonium salt base and nitrogen atom heterocyclic radical that is in main chain or being bonded with main chain as.
Polyurethane dispersant (b-1) preferably comprises the part-structure containing adsorption group comprising above-mentioned adsorption group, such as front Described in face, from the viewpoint of dispersibility, the preferably part knot to each other or containing adsorption group for the part-structure containing adsorption group Linked by the part-structure shown in above-mentioned formula (i) between structure and the part-structure containing solvophilic group described below.
(part-structure 1 containing adsorption group)
Specific part-structure for the part-structure containing adsorption group is not particularly limited, preferably following formula (1) Shown part-structure.
[chemical formula 11]
In formula (1), R1Represent the alkyl or aryl optionally with substituent group, R2And R3Represent independently of one another and optionally have The alkylidene of substituent group, arylidene alkylene or arlydene.
* represent bonding position.
R1The carbon number of alkyl be not particularly limited, usually more than 1, be preferably more than 2, additionally, it is preferred that being 20 Below, more preferably less than 10, more preferably less than 6.When within the above range, there is dispersibility becomes good inclining To.Specifically can enumerate for example：Methyl, ethyl, propyl group, butyl, amyl group, hexyl, cyclopenta, cyclohexyl, suberyl and cyclooctyl Deng.From the viewpoint of dispersibility, preferably methyl, ethyl, propyl group, cyclopenta or cyclohexyl, more preferably methyl, ethyl Or cyclohexyl, more preferably methyl or cyclohexyl.
R1The carbon number of aryl be not particularly limited, usually more than 6, additionally, it is preferred that for less than 30, more preferably Less than 20, more preferably less than 15.When within the above range, there is the tendency that dispersibility becomes good.Specifically can enumerate Such as phenyl and naphthyl etc., from the viewpoint of dispersibility, preferably phenyl.
The substituent group optionally having as these alkyl, aryl, is not particularly limited, and can enumerate：Hydroxyl；Carboxyl；First The alkyl such as base, ethyl, propyl group, cyclohexyl；The aryl such as phenyl；Aralkyl such as benzyl etc..
The carbon number of abovementioned alkyl is not particularly limited, preferably 1～20, more preferably 1～10, more preferably 1～5.Alkyl can be straight-chain, can also be branched, can also be ring-type.As concrete example, can enumerate：Methyl, second Base, cyclohexyl etc..
In addition, the carbon number of above-mentioned aryl is not particularly limited, preferably 6～20, more preferably 6～10.As tool Style, can enumerate phenyl, naphthyl etc..
In addition, the carbon number of above-mentioned aralkyl is not particularly limited, preferably 7～20, more preferably 7～10.As Concrete example, can enumerate benzyl etc..
In the middle of these, from the viewpoint of the absorption affinity to pigment, preferably hydroxyl, methyl or ethyl.
In addition, in above-mentioned R1In, from the viewpoint of dispersibility, preferably R1For alkyl.
In addition, R2And R3In the carbon number of alkylidene be not particularly limited, usually more than 1, be preferably more than 2, separately Outward, preferably less than 20, more preferably less than 15, more preferably less than 7.When within the above range, there is dispersibility and become Obtain tendency well.Specifically can enumerate for example：Methylene, ethylidene, propylidene, butylidene, cyclopentylene methylene, sub- hexamethylene Methylene, cyclohexylidene ethylidene and cyclohexylidene propylidene etc..From the viewpoint of dispersibility, preferably methylene, Asia Ethyl or cyclohexylidene methylene, more preferably ethylidene.
R2And R3In the carbon number of arylidene alkylene (group being linked by alkylidene and arlydene) there is no spy Different limit, usually more than 7, be preferably more than 8, additionally, it is preferred that for less than 30, more preferably less than 20, more preferably Less than 15.When within the above range, there is the tendency that dispersibility becomes good.Specifically can enumerate for example：Phenylene methylene, Asia Phenyl-ethylene and phenylene propylidene etc..From the viewpoint of dispersibility, preferably phenylene methylene.
R2And R3In the carbon number of arlydene be not particularly limited, usually more than 6, additionally, it is preferred that for less than 30, More preferably less than 20, more preferably less than 15.When within the above range, there is the tendency that dispersibility becomes good.Tool Body can enumerate such as phenylene and naphthylene etc., from the viewpoint of dispersibility, preferably phenylene.
The substituent group optionally having as these alkylidenes, arylidene alkylene and arlydene, is not particularly limited, can Enumerate for example：Hydroxyl；Carboxyl；The alkyl such as methyl, ethyl, propyl group, cyclohexyl；The aryl such as phenyl；Aralkyl such as benzyl etc..
The carbon number of abovementioned alkyl is not particularly limited, preferably 1～20, more preferably 1～10, more preferably 1～5.Alkyl can be straight-chain, can also be branched, can also be ring-type.As concrete example, can enumerate methyl, ethyl, Cyclohexyl etc..
In addition, the carbon number of above-mentioned aryl is not particularly limited, preferably 6～20, more preferably 6～10.As tool Style, can enumerate phenyl, naphthyl etc..
In addition, the carbon number of above-mentioned aralkyl is not particularly limited, preferably 7～20, more preferably 7～10.As Concrete example, can enumerate benzyl etc..
In the middle of these, from the viewpoint of sterically hindered between Inhibitory molecules, preferably hydroxyl, methyl or ethyl.
R2And R3Can be the same or different, from the viewpoint of dispersibility, preferably identical group.In the middle of these, from From the viewpoint of dispersibility, R2And R3It is preferably alkylidene independently of one another.
As the concrete example of the part-structure shown in above-mentioned formula (1), following structure can be enumerated.
[chemical formula 12]
It should be noted that in the part-structure shown in above-mentioned formula (1), formula (1) integrally becomes and to be formed by tertiary amino Adsorption group.In addition, containing the part-structure of adsorption group or base containing solvophilic by making the part-structure shown in formula (1) with other The part-structure of group links through the part-structure shown in above-mentioned formula (i), can be by the adsorption group configuration shown in formula (1) poly- In the main chain of urethane dispersant (b-1).In the case of being somebody's turn to do, the * of above-mentioned formula (1) represents and the amino first in the polyurethane skeleton of main chain The bonding position of the carbonyl of acid esters key.
In addition, as other examples, preferably there is the part-structure shown in following formula (1 ').
[chemical formula 13]
In formula (1 '), R1～R3And those in * and above-mentioned formula (1) are synonymous.RARepresent optionally have substituent group alkyl or Aryl.X-Represent 1 valency anion.
As RAAlkyl or aryl, be preferably employed as R1And those groups enumerated.
X-As long as being then not particularly limited for 1 valency anion, from the viewpoint of dispersibility, preferably X-For cl anion etc. Halide anion or methylsulfuric acid anion, more preferably halide anion, more preferably cl anion.Formula (1 ') Quaternary ammonium salt base can be obtained by carrying out the tertiary amino of formula (1) quaternized, in the case of being somebody's turn to do, X-Sometimes it is from quaternizing agent Anion.
It should be noted that in the part-structure shown in above-mentioned formula (1 '), formula (1 ') integrally becomes by quaternary ammonium salt base shape The adsorption group becoming.In addition, containing the part-structures of adsorption group or containing parent by making the part-structure shown in formula (1 ') with other The part-structure of solvent group links through the part-structure shown in above-mentioned formula (i), can be by the adsorption group shown in formula (1 ') Configuration is in the main chain of polyurethane dispersant (b-1).
In addition, as other concrete examples, part-structure shown below can be enumerated.Following part-structure is generally by containing The adsorption group that nitrogen-atoms heterocyclic radical is formed.It is believed that the adsorption group being formed by nitrogen atom heterocyclic radical is showed due to meeting Go out and be bonded and the hydrophobicity bonding based on building-up effect (packing effect) with the ionic of pigment, therefore can be with uncle Amino or quaternary ammonium salt base are similarly had an effect, thus showing good pigment adsorption.
In addition, by making this part-structure and other part-structures containing adsorption group or the knot of the part containing solvophilic group Structure links through the part-structure shown in above-mentioned formula (i), can configure the adsorption group representing with this part-structure in poly- ammonia In the main chain of ester dispersant (b-1).
[chemical formula 14]
In above-mentioned formula, * represents bonding position.
(part-structure 2 containing adsorption group)
As other preferences, the preferably at least one part-structure shown in following formula (2-1)～(2-3).By tool There is at least one part-structure shown in following formula (2-1)～(2-3), the sterically hindered of absorbed portion is relaxed, thus, There is spatial degrees of freedom raising, the tendency so as to effectively be adsorbed in pigment of adsorption section.
[chemical formula 15]
In formula (2-1), RαAnd RβRepresent the alkyl or aryl optionally with substituent group independently of one another.
Rγ、RδAnd RεRepresent independently of one another the alkylidene optionally with substituent group, the arlydene optionally with substituent group, Or the group being linked by above-mentioned alkylidene and above-mentioned arlydene, wherein, RγFor optionally have substituent group alkylidene or by In the case of the group that above-mentioned alkylidene and above-mentioned arlydene link, constitute at least one of methylene of above-mentioned alkylidene Divide and be optionally selected from ester bond, ehter bond, amino-formate bond, urea bond, amido link, imide bond, thiocarbamate key, thioether At least one bonding in key and thioester bond replaces, in addition, RγAt least can also appoint with adjacent via-NH- (C=O)-base One N atom of meaning is collectively forming urea bond, furthermore it is also possible to form amido link via carbonyl.
* represent bonding position.
[chemical formula 16]
In formula (2-2), RαAnd RβRepresent the alkyl or aryl optionally with substituent group independently of one another.
RγAnd RηRepresent independently of one another optionally have substituent group alkylidene, optionally have substituent group arlydene or The group being linked by above-mentioned alkylidene and above-mentioned arlydene, wherein, RγAnd RηIt is each independently and optionally there is substituent group Alkylidene or the group that linked by above-mentioned alkylidene and above-mentioned arlydene in the case of, constitute the Asia of above-mentioned alkylidene At least a portion of methyl is optionally selected from ester bond, ehter bond, amino-formate bond, urea bond, amido link, imide bond, thio ammonia At least one bonding in carbamate key, thioether bond and thioester bond replaces, in addition, RγAnd RηCan also via-NH- (C=O)- Base and be collectively forming urea bond with adjacent at least any one N atom, furthermore it is also possible to form amido link via carbonyl.
* represent bonding position.
[chemical formula 17]
In formula (2-3), RαAnd RβRepresent the alkyl or aryl optionally with substituent group independently of one another.
Rγ’And RδRepresent independently of one another optionally have substituent group alkylidene, optionally have substituent group arlydene or The group being linked by above-mentioned alkylidene and above-mentioned arlydene, wherein, Rγ’For optionally have substituent group alkylidene or by In the case of the group that above-mentioned alkylidene and above-mentioned arlydene link, constitute at least one of methylene of above-mentioned alkylidene Divide and be optionally selected from ester bond, ehter bond, amino-formate bond, urea bond, amido link, imide bond, thiocarbamate key, thioether At least one bonding in key and thioester bond replaces, in addition, Rγ’Can also via-NH- (C=O)-base with adjacent N atom It is collectively forming urea bond, furthermore it is also possible to form amido link via carbonyl.
Rε’Represent direct key, optionally there is the alkylidene of substituent group, optionally there is the arlydene of substituent group or by above-mentioned Asia The group that alkyl and above-mentioned arlydene link.
RζThe alkyl that represent hydrogen atom, optionally there is substituent group or the aryl optionally with substituent group.But in RζFor alkyl Or in the case of aryl, at least one in its hydrogen atom is optionally replaced by tertiary amino or nitrogen atom heterocyclic radical.
* represent bonding position.
In above-mentioned formula (2-1)～(2-3), Rα、RβAnd RζThe carbon number of alkyl be not particularly limited, but usually 1 with On, additionally, it is preferred that being less than 20, more preferably less than 10, more preferably less than 2.When within the above range, there is dispersion Property becomes good tendency.
Specifically can enumerate for example：Methyl, ethyl, propyl group, butyl, amyl group, hexyl, cyclopenta, cyclohexyl, suberyl and ring Octyl group etc..From the viewpoint of dispersibility, preferably methyl, ethyl, propyl group, cyclopenta or cyclohexyl, more preferably methyl or Ethyl, more preferably methyl.
Rα、RβAnd RζThe carbon number of aryl be not particularly limited, usually more than 6, additionally, it is preferred that for less than 30, more It is preferably less than 20, more preferably less than 15.When within the above range, there is the tendency that dispersibility becomes good.Specifically Such as phenyl and naphthyl etc. can be enumerated, from the viewpoint of dispersibility, preferably phenyl.
RαAnd RβCan be the same or different, from the viewpoint of dispersibility, preferably identical group.
The substituent group optionally having as these alkyl and aryl, is not particularly limited, and can enumerate for example：Hydroxyl；Carboxylic Base；The alkyl such as methyl, ethyl, propyl group, cyclohexyl；The aryl such as phenyl；Aralkyl such as benzyl etc..
The carbon number of abovementioned alkyl is not particularly limited, preferably 1～20, more preferably 1～10, more preferably 1～5.Alkyl can be straight-chain, can also be branched, can also be ring-type.As concrete example, can enumerate methyl, ethyl, Cyclohexyl etc..
In addition, the carbon number of above-mentioned aryl is not particularly limited, preferably 6～20, more preferably 6～10.As tool Style, can enumerate phenyl, naphthyl etc..
In addition, the carbon number of above-mentioned aralkyl is not particularly limited, preferably 7～20, more preferably 7～10.As Concrete example, can enumerate benzyl etc..
In the middle of these, from the viewpoint of never hindering pigment adsorption because of intermolecular space steric hindrance, preferably hydroxyl, first Base or ethyl.
In addition, from the viewpoint of dispersibility, RαAnd RβIt is preferably alkyl independently of one another.In addition, the viewpoint from dispersibility Set out, preferably RζFor hydrogen atom or alkyl.
In above-mentioned formula (2-1)～(2-3), Rγ、Rγ’、Rδ、Rε、Rε’And RηThe alkylidene optionally with substituent group carbon former Subnumber is not particularly limited, and usually more than 1, is preferably more than 2, additionally, it is preferred that for less than 30, more preferably less than 20, enter One step is preferably less than 15.When within the above range, there is the tendency that dispersibility becomes good.
Alkylidene can also be able to be ring-type for chain, alternatively, it is also possible to be the alkylene of alkylidene by chain and ring-type The group that base links.From the viewpoint of dispersibility, the alkylidene of preferably chain.
Specifically can enumerate for example：Methylene, dimethylene, trimethylene, tetramethylene, cyclopentylene methylene, sub- ring Hexyl methylene, cyclohexylenedimethylene and cyclohexylidene trimethylene etc..From the viewpoint of dispersibility, preferably methylene Base, dimethylene or trimethylene, more preferably dimethylene or trimethylene.
Rγ、Rγ’、Rδ、Rε、Rε’And RηIn the case that optionally there is the alkylidene of substituent group, as above-mentioned formula (2-1)～ (2-3) concrete structure, can enumerate for example following structure.
[chemical formula 18]
In above-mentioned formula (2-1)～(2-3), Rγ、Rγ’、Rδ、Rε、Rε’And RηIn by optionally have substituent group alkylidene and The carbon number optionally with the group that the arlydene of substituent group links is not particularly limited, and usually more than 6, is preferably More than 7, additionally, it is preferred that being less than 30, more preferably less than 20, more preferably less than 15.When within the above range, exist Dispersibility becomes good tendency.As long as in addition, the number of alkylidene is just not particularly limited for more than 1, from the sight of dispersibility Point sets out, and preferably less than 3.
Specifically can enumerate for example：By 1 arlydene optionally with substituent group and 1 alkylidene optionally with substituent group The group linking, the arlydene optionally by 2 with substituent group are via 1 alkylidene link optionally with substituent group Become group, optionally be there is the base that the alkylidene of substituent group links via 1 arlydene optionally with substituent group by 2 Roll into a ball and by the alkylidene optionally with substituent group and optionally there is the group that the arlydene of substituent group alternately links.
As the concrete example of the group being linked by above-mentioned alkylidene and above-mentioned arlydene, following group can be enumerated.
[chemical formula 19]
Wherein, from the viewpoint of dispersibility, the group shown in preferably above-mentioned formula (b3).
As Rγ、Rγ’、Rδ、Rε、Rε’And RηIn at least any one is to be linked by above-mentioned alkylidene and above-mentioned arlydene Group in the case of above-mentioned formula (2-1)～(2-3) concrete structure, for example following structure can be enumerated.
[chemical formula 20]
In the middle of these, from dispersibility aspect, preferably as (2-1-b), (2-2-b), (2-3-b) etc., RγOr Rγ’It is by the alkylidene optionally with substituent group and the structure optionally with the group that the arlydene of substituent group links.This feelings Under condition, from dispersibility aspect, preferably Rδ、Rε、Rε’And RηFor alkylidene.
In above-mentioned formula (2-1)～(2-3), Rγ、Rγ’、Rδ、Rε、Rε’And RηThe arlydene optionally with substituent group carbon former Subnumber is not particularly limited, and usually more than 6, additionally, it is preferred that for less than 30, more preferably less than 20, more preferably 15 Below.When within the above range, there is the tendency that dispersibility becomes good.Specifically phenylene, naphthylene etc. can be enumerated, from dispersion From the viewpoint of property, preferably phenylene.
As Rγ、Rγ’、Rδ、Rε、Rε’And RηIn the above-mentioned formula (2-1) in the case that at least arbitrarily group is arlydene～ (2-3) concrete structure, can enumerate for example following structure.
[chemical formula 21]
In the middle of these, R preferably as (2-1-c), (2-2-c) or (2-3-c) etc.γOr Rγ’Structure for arlydene.
As the R in above-mentioned formula (2-1)～(2-3)γ、Rγ’、Rδ、Rε、Rε’And RηAlkylidene, arlydene, by alkylidene The substituent group optionally having with the group that arlydene links, is not particularly limited, and can enumerate for example：Methyl, ethyl, ring The alkyl such as hexyl；The aryl such as phenyl；Aralkyl such as benzyl etc..
The carbon number of abovementioned alkyl is not particularly limited, preferably 1～20, more preferably 1～10, more preferably 1～5.Alkyl can be straight-chain, can also be branched, can also be ring-type.As concrete example, can enumerate methyl, ethyl, Cyclohexyl etc..
In addition, the carbon number of above-mentioned aryl is not particularly limited, preferably 6～20, more preferably 6～10.As tool Style, can enumerate phenyl, naphthyl etc..
In addition, the carbon number of above-mentioned aralkyl is not particularly limited, preferably 7～20, more preferably 7～10.As Concrete example, can enumerate benzyl etc..
In the middle of these, from the viewpoint of handling easiness and dispersibility, preferably methyl.
As previously described, in Rγ、Rγ’And RηIt is each independently the alkylidene optionally with substituent group or by above-mentioned alkylene In the case of the group that base and above-mentioned arlydene link, constitute at least a portion optionally quilt of the methylene of above-mentioned alkylidene Selected from ester bond, ehter bond, amino-formate bond, urea bond, amido link, imide bond, thiocarbamate key, thioether bond and thioesters At least one bonding in key replaces.In the middle of these, it is bonded as preferred, from the viewpoint of dispersibility, can enumerate in composition State those that at least a portion of the methylene of alkylidene replaced by amino-formate bond or ester bond.
As the concrete structure of above-mentioned formula (2-1)～(2-3) under such circumstances, for example following structure can be enumerated.
[chemical formula 22]
R particularly from the viewpoint of dispersibility, in preferably above-mentioned formula (2-1)γIt is by above-mentioned alkylidene and above-mentioned Asia Group that aryl links and constitute its alkylidene methylene a part by amino-formate bond replace all Structure as above-mentioned formula (2-1-d ').
In addition, the R from the viewpoint of dispersibility, in preferably above-mentioned formula (2-2)γAnd RηFor alkylidene and constitute to Such as above-mentioned formula (2-2-d) or (2-2- that at least a portion of the methylene of few alkylidene of any one is replaced by ester bond D ') as structure.
In addition, the R from the viewpoint of dispersibility, in preferably above-mentioned formula (2-3)γ’、RδAnd Rε’It is unsubstituted alkylene The structure as such as above-mentioned formula (2-3-a) of base.Additionally, it is preferred that using the R in above-mentioned formula (2-3)γ’For alkylidene or by upper The part stating alkylidene and the above-mentioned arlydene group linking and the methylene constituting its alkylidene is by carbamic acid The such as above-mentioned formula (2-3-d) that ester bond, thiocarbamate key, ester bond or thioether bond replace or (2-3-d ') are such Structure.
In addition, as previously described, RγCan also via-NH- (C=O)-base with adjacent at least any one N atom It is collectively forming urea bond, furthermore it is also possible to form amido link via carbonyl.
Particularly, from the viewpoint of dispersibility, the R of above-mentioned formula (2-1)γPreferably with and RδAnd RεThe N atom of bonding is common Form urea bond via-NH- (C=O)-base.As the concrete structure of above-mentioned formula (2-1) under such circumstances and (2-2), can Enumerate for example following structure.
[chemical formula 23]
In addition, as previously described, Rγ’Urea can also be collectively forming via-NH- (C=O)-base with adjacent N atom Key, furthermore it is also possible to form amido link via carbonyl.As the concrete structure of above-mentioned formula (2-3) under such circumstances, can Enumerate for example following structure.
[chemical formula 24]
Similarly, RηUrea bond can also be collectively forming via-NH- (C=O)-base with adjacent N atom, in addition, also may be used To form amido link via carbonyl.As the concrete structure of above-mentioned formula (2-2) under such circumstances, can enumerate for example following Structure.
[chemical formula 25]
In addition, RζIn the case of alkyl or aryl, at least one in its hydrogen atom is optionally by tertiary amino or nitrogen atom Heterocyclic radical replaces.As the concrete structure of above-mentioned formula (2-3) under such circumstances, for example following structure can be enumerated.
[chemical formula 26]
In above-described above-mentioned formula (2-1)～(2-3), from the viewpoint of dispersibility, preferably following structure.
In above-mentioned formula (2-1), RγIt is preferably the group being linked by above-mentioned alkylidene and above-mentioned arlydene, now, excellent At least a portion that choosing constitutes the methylene of above-mentioned alkylidene is replaced by amino-formate bond, additionally, it is preferred that via-NH- (C= O)-base and be collectively forming urea bond with adjacent N atom.In addition, in the case of being somebody's turn to do, preferably Rδ、RεFor alkylidene.As such tool Style, can enumerate above-mentioned formula (2-1-e) shown below.
[chemical formula 27]
In addition, in above-mentioned formula (2-1), RγIt is preferably alkylidene, in the case of being somebody's turn to do, preferably comprise the methylene of alkylidene extremely A few part is replaced by ester bond.In addition, in the case of being somebody's turn to do, preferably Rδ、RεFor alkylidene.As such concrete example, can enumerate following Shown above-mentioned formula (2-1-d).
[chemical formula 28]
In addition, in above-mentioned formula (2-2), RγIt is preferably the group being linked by above-mentioned alkylidene and above-mentioned arlydene, should In the case of, at least a portion preferably comprising the methylene of above-mentioned alkylidene is replaced by amino-formate bond, additionally, it is preferred that warp Urea bond is collectively forming with adjacent N atom by-NH- (C=O)-base.In addition, in the case of being somebody's turn to do, preferably RηFor alkylidene.As Such concrete example, can enumerate above-mentioned formula (2-2-e) shown below.
[chemical formula 29]
In addition, in above-mentioned formula (2-2), RγIt is preferably alkylidene, in the case of being somebody's turn to do, preferably comprise the methylene of above-mentioned alkylidene At least a portion of base is replaced by ester bond.In addition, in the case of being somebody's turn to do, preferably RηFor alkylidene.Such concrete example can be enumerated following Shown above-mentioned formula (2-2-d).
[chemical formula 30]
In addition, in above-mentioned formula (2-2), RγIt is preferably alkylidene.In addition, in such a situation it is preferred that RηFor alkylidene, excellent The part that choosing constitutes the methylene of above-mentioned alkylidene is at least replaced by ester bond.Such concrete example can be enumerated shown below upper State formula (2-2-d ').
[chemical formula 31]
In addition, in above-mentioned formula (2-3), preferably Rγ’And RδFor alkylidene, preferably Rε’For direct key or alkylidene, this feelings Under condition, preferably RζFor hydrogen atom.As such concrete example, above-mentioned formula (2-3-a) shown below can be enumerated.
[chemical formula 32]
In addition, in above-mentioned formula (2-3), preferably Rγ’It is the group being linked by above-mentioned alkylidene and above-mentioned arlydene, In the case of being somebody's turn to do, at least a portion of methylene preferably comprising above-mentioned alkylidene is by amino-formate bond and/or sulfo-amino first Acid esters key replaces.In addition, in the case of being somebody's turn to do, preferably RδFor alkylidene, preferably Rε’For direct key.Additionally, it is preferred that RζFor hydrogen atom.Make For such concrete example, above-mentioned formula (2-3-d) shown below can be enumerated.
[chemical formula 33]
In addition, in above-mentioned formula (2-3), preferably Rγ‘For alkylidene, in the case of being somebody's turn to do, preferably comprise the Asia of above-mentioned alkylidene At least a portion of methyl is replaced by ester bond and thioether bond.In addition, in the case of being somebody's turn to do, preferably RδFor alkylidene, preferably Rε’For direct Key.Additionally, it is preferred that RζFor hydrogen atom.As such concrete example, above-mentioned formula (2-3-d ') shown below can be enumerated.
[chemical formula 34]
It should be noted that the R in above-mentioned formula (2-1)α、Rβ, N and RγBecome the adsorption group being formed by tertiary amino.Equally Ground, the R in above-mentioned formula (2-2)α、Rβ, N and RγBecome the adsorption group being formed by tertiary amino.In addition, the R in above-mentioned formula (2-3)α、Rβ, N and Rγ’Become the adsorption group being formed by tertiary amino.In the case of these, the * in formula represents and the ammonia in polyurethane skeleton The bonding position of the carbonyl of carbamate key or urea bond.
In addition, by making the part-structure shown in above-mentioned formula (2-1)～(2-3) and other part-structures containing adsorption group Or the part-structure containing solvophilic group links through the part-structure shown in above-mentioned formula (i), formula (2-1)～(2-3) can be made In contained adsorption group become the group being bonded with the main chain of polyurethane dispersant (b-1).
In addition, as other preferences, the preferably part-structure shown in following formula (2-1 ')～(2-3 ').
[chemical formula 35]
In formula (2-1 '), Rα～RεAnd those in * and formula (2-1) are synonymous.RAAnd X-Synonymous with those in formula (1 ').
[chemical formula 36]
In formula (2-2 '), Rα～RηAnd those in * and formula (2-2) are synonymous.RAAnd X-Synonymous with those in formula (1 ').
[chemical formula 37]
In formula (2-3 '), Rα～RζAnd those in * and formula (2-3) are synonymous.RAAnd X-Synonymous with those in formula (1 ').
In addition, as other concrete examples, part-structure shown below can be enumerated.In following part-structure, nitrogenous Atom heterocycle base becomes adsorption group.
[chemical formula 38]
In above-mentioned formula, * represents bonding position.
For specific adsorption group, compared with the situation in the polyurethane skeleton being present in main chain, preferably relatively The pendant type existing as side chain in the polyurethane skeleton of main chain.In particular it is preferred that nitrogen-atoms in adsorption group with respect to On the polyurethane skeleton of main chain, immediate atom separates at least one atom and bonding.That is, preferably it is bonded to the absorption of main chain Group.
Particularly, the nitrogen-atoms in more preferably specific adsorption group are immediate with respect on the polyurethane skeleton of main chain Atom separates at least 2 atoms, the nitrogen-atoms of particularly preferably specific adsorption group with respect on the polyurethane skeleton of main chain Close atom separates at least 3 atoms.
Nitrogen-atoms preferably in adsorption group with respect to atom immediate on the polyurethane skeleton of main chain separate 20 with Lower atom, more preferably separates less than 10 atoms.Hereinafter, also by atom immediate on the polyurethane skeleton of this main chain with specific The nitrogen-atoms of adsorption group between atomic number be referred to as " intervening atoms number ".
For example, in the case of having the part-structure of above-mentioned formula (2-3-a), as described below, the nitrogen in adsorption group is former Son separates 1 carbon atom with respect to the carbon atom of the methine in polyurethane skeleton.
[chemical formula 39]
(content ratio of the part-structure containing adsorption group)
Polyurethane dispersant (b-1) can be for example the dispersant with the above-mentioned part-structure containing adsorption group, permissible There is a kind of above-mentioned part-structure containing adsorption group, alternatively, it is also possible to have the above-mentioned part containing adsorption group of more than two kinds Structure.
For example, it is possible to make the part-structure of all tertiary-amino-containings of adsorption group, it is equally possible that making adsorption group complete Portion is the part-structure containing quaternary ammonium salt base, can also make all part knots containing heterocyclic radical with nitrogen-atoms of adsorption group Structure.
From the viewpoint of dispersibility and the compatibility, the preferably all tertiary aminos of adsorption group.It is also possible to make in the case of being somebody's turn to do It has tertiary amino of more than two kinds, but from the viewpoint of dispersibility, preferably has a kind of tertiary amino, more preferably have selected from upper State the part-structure of any a kind of tertiary-amino-containing in formula (1) and (2-1)～(2-3), further preferably have shown in formula (2-1) Tertiary-amino-containing part-structure.
On the other hand, from from the viewpoint of the development dissolubility alkaline developer, the preferably all quaternary ammoniums of adsorption group Alkali.It should be noted that tertiary amino can be carried out quaternary ammonium salt base using quaternizing agent by quaternary ammonium salt base obtaining, but due to If whole tertiary aminos are carried out quaternary ammonium salt baseization, there is the tendency generating the impurity from quaternizing agent in large quantities, therefore, From the viewpoint of suppression impurity generates, formed more and make part tertiary amino remaining thus and having tertiary amino and quaternary ammonium salt base Adsorption group.
Accordingly, as adsorption group, preferably there is both tertiary amino and quaternary ammonium salt base, from the viewpoint of the validation manufacturing Set out, more preferably selected from the combination of combination, above-mentioned formula (2-1) and (2-1 '), the above-mentioned formula (2-2) of above-mentioned formula (1) and (1 ') Any a kind of combination in the combination of the combination of (2-2 ') and above-mentioned formula (2-3) and (2-3 '), more preferably above-mentioned formula (2-1) combination with (2-1 ').
In the case of having both tertiary amino and quaternary ammonium salt base, its content ratio is not particularly limited, but from dispersibility From the viewpoint of, the part-structure preferably containing quaternary ammonium salt base rubs for 1 with respect to the content ratio of the part-structure of tertiary-amino-containing Your more than %, more preferably 5 moles more than %, more preferably 10 moles of more than %, additionally, it is preferred that for 99 moles of % with Under, more preferably 95 moles below %, more preferably 80 moles below %, be still more preferably 60 moles of below %, Particularly preferably 40 moles below %, most preferably 30 moles of below %.
Similarly, the part knot containing adsorption group from the viewpoint of dispersibility, in optimization polyurethane dispersant (b-1) The content ratio of structure is more than 5 mass %, is more preferably more than 10 mass %, is more preferably more than 20 mass %, in addition, Below preferably 90 mass %, below more preferably 50 mass %, below more preferably 40 mass %, it is particularly preferably 30 Below quality %.
In addition, the content ratio of specific adsorption group is preferably 0.001 mole with respect to 100g polyurethane dispersant (b-1) Above, more preferably more than 0.01 mole, more preferably more than 0.05 mole, additionally, it is preferred that be less than 0.8 mole, more It is preferably less than 0.4 mole, more preferably less than 0.2 mole.Hereinafter, as specific adsorption group content, " to rub The unit of that/100g " represents the ratio of this specific adsorption group with respect to 100g polyurethane dispersant (b-1).
(solvophilic group)
Polyurethane dispersant (b-1) comprises solvophilic group.The solvophilic group having with regard to polyurethane dispersant (b-1) Species for, as long as showing that the intermiscibility with solvent is just not particularly limited.From the viewpoint of dispersibility, preferably close molten Agent group comprises at least one of polyether chain and polyester chain.In addition, in the case that polyurethane dispersant (b-1) has main chain, From the viewpoint of dispersibility, preferably solvophilic group be comprise at least one of polyether chain and polyester chain and with main chain key The group closing.
Polyurethane dispersant (b-1) preferably comprises the part-structure containing solvophilic group comprising above-mentioned solvophilic group, As previously described, from the viewpoint of dispersibility, preferably contain solvophilic group part-structure to each other or above-mentioned containing absorption base Linked by the part-structure shown in above-mentioned formula (i) between the part-structure of group and the part-structure containing solvophilic group.
Specific part-structure for the part-structure containing solvophilic group is not particularly limited, preferably following formula (3-1) part-structure shown in～(3-3).R in formula (3-1)～(3-3)θBe solvophilic group with O atom, in addition for With solvophilic group be bonded position.
[chemical formula 40]
In formula (3-1), RθRepresent polyether chain and/or polyester chain.
Rγ、RδAnd RεRepresent independently of one another the alkylidene optionally with substituent group, the arlydene optionally with substituent group, Or the group being linked by above-mentioned alkylidene and above-mentioned arlydene, wherein, RγFor optionally have substituent group alkylidene or by In the case of the group that above-mentioned alkylidene and above-mentioned arlydene link, constitute at least one of methylene of above-mentioned alkylidene Divide and be optionally selected from ester bond, ehter bond, amino-formate bond, urea bond, amido link, imide bond, thiocarbamate key, thioether At least one bonding in key and thioester bond replaces, in addition, RγCan also be former with 1 adjacent N via-NH- (C=O)-base Son is collectively forming urea bond, furthermore it is also possible to form amido link via carbonyl.
In addition, RγAmino-formate bond can also be collectively forming via-NH- (C=O)-base with 1 adjacent O atom, Furthermore it is also possible to form ester bond via carbonyl.
* represent bonding position.
[chemical formula 41]
In formula (3-2), RθRepresent polyether chain and/or polyester chain.
RγAnd RηRepresent independently of one another optionally have substituent group alkylidene, optionally have substituent group arlydene or The group being linked by above-mentioned alkylidene and above-mentioned arlydene, wherein, RγAnd RηIt is each independently and optionally there is substituent group Alkylidene or the group that linked by above-mentioned alkylidene and above-mentioned arlydene in the case of, constitute the Asia of above-mentioned alkylidene At least a portion of methyl is optionally selected from ester bond, ehter bond, amino-formate bond, urea bond, amido link, imide bond, thio ammonia At least one bonding in carbamate key, thioether bond and thioester bond replaces, in addition, RγAnd RηCan also via-NH- (C=O)- Base and be collectively forming urea bond with 1 adjacent N atom, furthermore it is also possible to form amido link via carbonyl.
In addition, RγAmino-formate bond can also be collectively forming via-NH- (C=O)-base with 1 adjacent O atom, Furthermore it is also possible to form ester bond via carbonyl.
* represent bonding position.
[chemical formula 42]
In formula (3-3), RθRepresent polyether chain and/or polyester chain.
Rγ’And RδRepresent independently of one another optionally have substituent group alkylidene, optionally have substituent group arlydene or The group being linked by above-mentioned alkylidene and above-mentioned arlydene, wherein, Rγ’For optionally have substituent group alkylidene or by In the case of the group that above-mentioned alkylidene and above-mentioned arlydene link, constitute at least one of methylene of above-mentioned alkylidene Divide and be optionally selected from ester bond, ehter bond, amino-formate bond, urea bond, amido link, imide bond, thiocarbamate key, thioether At least one bonding in key and thioester bond replaces.
In addition, Rγ’Carbamate can also be collectively forming via-NH- (C=O)-base with 1 adjacent O atom Key, furthermore it is also possible to form ester bond via carbonyl.
Rε’Represent direct key, optionally there is the alkylidene of substituent group, optionally there is the arlydene of substituent group or by above-mentioned Asia The group that alkyl and above-mentioned arlydene link.
Rζ’The alkyl that represent hydrogen atom, optionally there is substituent group or the aryl optionally with substituent group, wherein, Rζ’For appointing In the case of the choosing alkyl with substituent group or the aryl optionally with substituent group, at least one in its hydrogen atom is optionally by Rθ- O-Rγ’- replace.
* represent bonding position.
Rγ、Rγ’、Rδ、Rε、Rε’And RηIn the carbon number of the alkylidene optionally with substituent group be not particularly limited, but It is usually more than 1, is preferably more than 2, additionally, it is preferred that being less than 20, more preferably less than 15, more preferably less than 7.? When in above range, there is the tendency that dispersibility becomes good.Specifically can enumerate：Methylene, dimethylene, trimethylene, four Methylene, pentamethylene, hexa-methylene, heptamethylene, cyclopentylene methylene, cyclohexylidene methylene, cyclohexylidene two are sub- Methyl, cyclohexylidene trimethylene etc., from the viewpoint of dispersibility, preferably dimethylene, trimethylene, tetramethylene, Pentamethylene or hexa-methylene, more preferably trimethylene, tetramethylene or pentamethylene.
In above-mentioned formula (3-1)～(3-3), Rγ、Rγ’、Rδ、Rε、Rε’And RηLinked by above-mentioned alkylidene and above-mentioned arlydene The carbon number of group be not particularly limited, usually more than 6, be preferably more than 7, additionally, it is preferred that for less than 30, more It is preferably less than 20, more preferably less than 15.When within the above range, there is the tendency that dispersibility becomes good.In addition, As long as the number of the alkylidene being had then is not particularly limited for more than 1, but from the viewpoint of dispersibility, preferably 3 Individual following.
Specifically can enumerate for example：By 1 arlydene optionally with substituent group and 1 alkylidene optionally with substituent group The group linking, the arlydene optionally by 2 with substituent group are via 1 alkylidene link optionally with substituent group Become group and linked via 1 arlydene optionally with substituent group by 2 alkylidenes optionally with substituent group Group.As the concrete example of the group being linked by above-mentioned alkylidene and above-mentioned arlydene, can enumerate above-mentioned formula (b1)～ (b5) group shown in.
Rγ、Rγ’、Rδ、Rε、Rε’And RηIn the carbon number of the arlydene optionally with substituent group be not particularly limited, lead to It is often more than 6, additionally, it is preferred that being less than 30, more preferably less than 20, more preferably less than 15.When within the above range, There is the tendency that dispersibility becomes good.Specifically phenylene, naphthylene etc. can be enumerated, from the viewpoint of dispersibility, preferably Phenylene.
In the middle of these, from the viewpoint of dispersibility, Rγ、Rγ’It is preferably alkylidene, arlydene or by above-mentioned alkylidene The group linking with above-mentioned arlydene, Rδ、Rε、Rε’And RηIt is preferably alkylidene.
As the R in above-mentioned formula (3-1)～(3-3)γ、Rγ’、Rδ、Rε、Rε’And RηOptionally have substituent group alkylidene, Optionally there is the arlydene of substituent group, the replacement optionally being had by the group that above-mentioned alkylidene and above-mentioned arlydene link Base, is not particularly limited, and can enumerate the alkyl such as methyl, ethyl, cyclohexyl；The aryl such as phenyl；Aralkyl such as benzyl etc..
The carbon number of abovementioned alkyl is not particularly limited, preferably 1～20, more preferably 1～10, more preferably 1～5.Alkyl can be straight-chain, can also be branched, can also be ring-type.As concrete example, can enumerate methyl, ethyl, Cyclohexyl etc..
In addition, the carbon number of above-mentioned aryl is not particularly limited, preferably 6～20, more preferably 6～10.As tool Style, can enumerate phenyl, naphthyl etc..
In addition, the carbon number of above-mentioned aralkyl is not particularly limited, preferably 7～20, more preferably 7～10.As Concrete example, can enumerate benzyl etc..
In the middle of these, from the viewpoint of handling easiness and dispersibility, preferably alkyl, more preferably methyl.
As previously described, in Rγ、Rγ’And RηIt is each independently the alkylidene optionally with substituent group or by above-mentioned alkylene In the case of the group that base and above-mentioned arlydene link, constitute at least a portion optionally quilt of the methylene of above-mentioned alkylidene Selected from ester bond, ehter bond, amino-formate bond, urea bond, amido link, imide bond, thiocarbamate key, thioether bond and thioesters At least one bonding in key replaces.
In the middle of these, it is bonded as preferred, from the viewpoint of dispersibility, RγAmino-formate bond or ester can be enumerated Key, Rγ’Thiocarbamate key, amino-formate bond or ester bond can be enumerated.In addition, with regard to RηFor, preferably it is not substituted.Special It is not, from the viewpoint of dispersibility, preferably above-mentioned formula (3-1), the R of (3-2)γFor alkylidene or by above-mentioned alkylidene and above-mentioned The group that arlydene links an and part for the methylene constituting its alkylidene is taken by amino-formate bond or ester bond Generation.As its concrete example, can be listed below.
[chemical formula 43]
In addition, in above-mentioned formula (3-3), R can be enumeratedγ’It is the base being linked by above-mentioned alkylidene and above-mentioned arlydene A part for group and the methylene constituting its alkylidene is replaced by amino-formate bond and/or thiocarbamate key Structure.As its concrete example, can be listed below.
[chemical formula 44]
In addition, as previously described, RγAnd RηIndependently of one another can via-NH- (C=O)-base with adjacent N atom It is collectively forming urea bond, alternatively, it is also possible to form amido link via carbonyl.
In the middle of these, it is bonded as preferred, from the viewpoint of dispersibility, with regard to RγFor, preferably via-NH- (C= O)-base and be collectively forming urea bond with adjacent N atom, in addition, with regard to RηFor, preferably not via upper and adjacent N atom between State bonding.
In addition, RγAnd Rγ’Can be collectively forming with 1 adjacent O atom via-NH- (C=O)-base independently of one another Amino-formate bond, alternatively, it is also possible to form ester bond via carbonyl.
Particularly, the R from the viewpoint of dispersibility, in preferably above-mentioned formula (3-1), (3-2)γFor alkylidene or sub- virtue Base and be collectively forming urea bond with adjacent N atom via-NH- (C=O)-base.Additionally, it is preferred that via-NH- (C=O)- Base and be collectively forming amino-formate bond with 1 adjacent O atom, additionally, it is preferred that form ester bond via carbonyl.As its tool Style, can be listed below.
[chemical formula 45]
In addition, in above-mentioned formula (3-3), R can be enumeratedγ’It is the base being linked by above-mentioned alkylidene and above-mentioned arlydene A part for group and the methylene constituting its alkylidene is replaced and via-NH- (C=O)-base by thiocarbamate key And it is collectively forming the structure of amino-formate bond with 1 adjacent O atom.Its concrete example can be listed below.
[chemical formula 46]
Rζ’The alkyl that represent hydrogen atom, optionally there is substituent group or the aryl optionally with substituent group, and, Rζ’For alkane In the case of base or aryl, at least one in its hydrogen atom can also be by Rθ-O-Rγ’- replace.
Rζ’In the carbon number of alkyl be not particularly limited, but usually more than 1, be preferably more than 2, additionally, it is preferred that For less than 20, more preferably less than 10, more preferably less than 6.When within the above range, there is dispersibility becomes good Tendency.
Specifically can enumerate for example：Methyl, ethyl, propyl group, butyl, amyl group, hexyl, cyclopenta, cyclohexyl, suberyl and ring Octyl group etc..From the viewpoint of dispersibility, preferably methyl, ethyl, propyl group, cyclopenta or cyclohexyl, more preferably methyl, Ethyl or cyclohexyl, more preferably methyl or cyclohexyl.
Rζ’In the carbon number of aryl be not particularly limited, usually more than 6, additionally, it is preferred that for less than 30, more preferably For less than 20, more preferably less than 15.When within the above range, there is the tendency that dispersibility becomes good.Specifically can arrange Citing such as phenyl and naphthyl etc., from the viewpoint of dispersibility, preferably phenyl.
The substituent group optionally having as these alkyl, aryl, is not particularly limited, and can enumerate for example：Hydroxyl；Carboxylic Base；The alkyl such as methyl, ethyl, propyl group, cyclohexyl；The aryl such as phenyl；Aralkyl such as benzyl etc..
The carbon number of abovementioned alkyl is not particularly limited, preferably 1～20, more preferably 1～10, more preferably 1～5.Alkyl can be straight-chain, can also be branched, can also be ring-type.As concrete example, can enumerate methyl, ethyl, Cyclohexyl etc..
In addition, the carbon number of above-mentioned aryl is not particularly limited, preferably 6～20, more preferably 6～10.As tool Style, can enumerate phenyl, naphthyl etc..
In addition, the carbon number of above-mentioned aralkyl is not particularly limited, preferably 7～20, more preferably 7～10.As Concrete example, can enumerate benzyl etc..
In the middle of these, from the viewpoint of suppression hinders to the absorption of pigment, preferably hydroxyl, methyl or ethyl.
In addition, in above-mentioned Rζ’In, from the viewpoint of dispersibility, preferably Rζ’For hydrogen atom.
As RθPolyether chain, the such as polyether chain shown in following formula (3-4) can be enumerated.In addition, as polyester chain, can arrange It is exemplified below the polyester chain shown in the formula of stating (3-5) or (3-6).
[chemical formula 47]
In above-mentioned formula (3-4), RbRepresent the alkyl optionally with substituent group, RcRepresent the alkylidene optionally with substituent group. N represents 1～100 integer.* represent the bonding position with adjacent O atom.
In addition, in above-mentioned formula (3-5) and (3-6), Rb’Represent the alkyl optionally with substituent group, Rc’Represent and optionally have The alkylidene of substituted base.N represents 1～100 integer.* represent the bonding position with adjacent O atom.
RbThe carbon number of alkyl be not particularly limited, usually more than 1, additionally, it is preferred that for less than 50, more preferably Less than 10, more preferably less than 6.When within the above range, there is the tendency that dispersibility becomes good.
Specifically can enumerate for example：Methyl, ethyl, propyl group, isopropyl, butyl, amyl group, hexyl, cyclopenta, cyclohexyl, ring Heptyl and cyclooctyl etc..From the viewpoint of dispersibility, preferably methyl, ethyl, propyl group or butyl, more preferably methyl or second Base, more preferably methyl.
The substituent group optionally having as alkyl, is not particularly limited, and can enumerate for example：Hydroxyl；Carboxyl；Methyl, second The alkyl such as base, propyl group, cyclohexyl；The aryl such as phenyl；Aralkyl such as benzyl etc..
The carbon number of abovementioned alkyl is not particularly limited, preferably 1～20, more preferably 1～10, more preferably 1～5.Alkyl can be straight-chain, can also be branched, can also be ring-type.As concrete example, can enumerate methyl, ethyl, Cyclohexyl etc..
In addition, the carbon number of above-mentioned aryl is not particularly limited, preferably 6～20, more preferably 6～10.As tool Style, can enumerate phenyl, naphthyl etc..
In addition, the carbon number of above-mentioned aralkyl is not particularly limited, preferably 7～20, more preferably 7～10.As Concrete example, can enumerate benzyl etc..
In the middle of these, from the viewpoint of being conducive to alkali-developable or being conducive to substrate closely sealed, preferably hydroxyl, methyl Or ethyl.
In addition, RcIn the carbon number of alkylidene be not particularly limited, usually more than 1, be preferably more than 2, in addition, It is preferably less than 20, more preferably less than 15, more preferably less than 7.When within the above range, there is dispersibility becomes good Good tendency.
Specifically can enumerate for example：Methylene, ethylidene, propylidene, isopropylidene, butylidene, cyclopentylene methylene, Asia Cyclohexylmethylene, cyclohexylidene ethylidene and cyclohexylidene propylidene etc..From the viewpoint of dispersibility, preferably methylene Base, ethylidene, propylidene, isopropylidene or butylidene, more preferably ethylidene, propylidene or isopropylidene.
The substituent group optionally having as alkylidene, is not particularly limited, and can enumerate for example：Hydroxyl；Carboxyl；Methyl, The alkyl such as ethyl, propyl group, cyclohexyl；The aryl such as phenyl；Aralkyl such as benzyl etc..
The carbon number of abovementioned alkyl is not particularly limited, preferably 1～20, more preferably 1～10, more preferably 1～5.Alkyl can be straight-chain, can also be branched, can also be ring-type.As concrete example, can enumerate methyl, ethyl, Cyclohexyl etc..
In addition, the carbon number of above-mentioned aryl is not particularly limited, preferably 6～20, more preferably 6～10.As tool Style, can enumerate phenyl, naphthyl etc..
In addition, the carbon number of above-mentioned aralkyl is not particularly limited, preferably 7～20, more preferably 7～10.As Concrete example, can enumerate benzyl etc..
In the middle of these, from the viewpoint of being conducive to alkali-developable or being conducive to substrate closely sealed, preferably hydroxyl, methyl Or ethyl.
N is 1～100 integer, but from the viewpoint of dispersibility, preferably more than 4, more preferably more than 6, in addition, It is preferably less than 60, more preferably less than 40.
Rb’The carbon number of alkyl be not particularly limited, usually more than 1, be preferably more than 2, additionally, it is preferred that being 50 Below, more preferably less than 40.
Change R alternatively, it is also possible to the polarity according to contained solvent (e) in photosensitive polymer combinationb’Alkyl Carbon number.In the case that solvent (e) is polar solvent, preferably Rb’Alkyl carbon number be more than 1 and less than 12.Another Aspect, in the case that solvent (e) is non-polar solven, preferably Rb’Alkyl carbon number be more than 9 and less than 30.Above-mentioned In the range of when, there is the tendency that dispersibility becomes good.
Specifically, solvent (e) be polar solvent in the case of, preferably methyl, ethyl, propyl group, isopropyl, butyl, Amyl group, hexyl, heptyl, octyl group, nonane -1- base, decane -1- base, hendecane -1- base or dodecane -1- base.
Solvent (e) be non-polar solven in the case of, preferably octyl group, nonane -1- base, decane -1- base, hendecane -1- base, Dodecane -1- base, tridecane -1- base, the tetradecane -1- base, pentadecane -1- base, eicosane -1- base or melissane -1- base.
In addition, for such medium polar solvent for methyl proxitol acetate, preferably decane -1- base, 11 Alkane -1- base, dodecane -1- base or tridecane -1- base.
The substituent group optionally having as alkyl, is not particularly limited, and can enumerate for example：Hydroxyl；Carboxyl；Methyl, second The alkyl such as base, propyl group, cyclohexyl；The aryl such as phenyl；Aralkyl such as benzyl etc..From being conducive to alkali-developable or be conducive to substrate From the viewpoint of closely sealed, preferably hydroxyl, methyl or ethyl.
In addition, Rc’In the carbon number of alkylidene be not particularly limited, usually more than 1, be preferably more than 2, in addition, It is preferably less than 50, more preferably less than 35, more preferably less than 26.
Change R alternatively, it is also possible to the polarity according to contained solvent (e) in photosensitive polymer combinationc’Alkylidene Carbon number.In the case that solvent (e) is polar solvent, preferably Rc’Alkylidene carbon number be more than 1 and less than 8. On the other hand, in the case that solvent (e) is non-polar solven, preferably Rc’Alkylidene carbon number be more than 9 and less than 26. When within the above range, there is the tendency that dispersibility becomes good.
Specifically, solvent (e) be polar solvent in the case of, preferably methylene, ethylidene, propylidene, isopropylidene, Butylidene, pentylidene, hexylidene, heptamethylene or octylene (or eight methylene).
In the case that solvent (e) is non-polar solven, preferably eight methylene, nine methylene, decamethylene, 11 methylenes Base, ten dimethylenes, ten trimethylenes, ten tetramethylenes, ten pentamethylenes, two decamethylenes or three decamethylenes.Preferably root According to the polarity of solvent, they are combined.
In addition, for such medium polar solvent for methyl proxitol acetate, preferably propylidene, butylidene, Pentylidene or hexylidene.
So, as RθPolyester chain, the polyester chain shown in above-mentioned formula (3-5) or (3-6) can be enumerated, from synthesis easy From the viewpoint of property, the polyester chain shown in preferably above-mentioned formula (3-5).
It should be noted that in the case that polyurethane dispersant (b-1) has main chain, formula (3-1)～(3-3) is and master The solvophilic group of chain bonding, the * in formula represents the carbonyl with the amino-formate bond in the polyurethane skeleton of main chain or urea bond Bonding position.
(content ratio of solvophilic group)
Polyurethane dispersant (b-1) can be for example the dispersant with the above-mentioned part-structure containing solvophilic group, can To have a kind of above-mentioned part-structure containing solvophilic group, alternatively, it is also possible to have above-mentioned group containing solvophilic of more than two kinds Part-structure.Particularly, contain simultaneously there is the part-structure containing solvophilic group of polyether chain and there is containing of polyester chain During the part-structure of solvophilic group, dispersion effect can be further enhanced, be therefore more highly preferred to.
The part-structure containing solvophilic group with polyester chain is with respect to the portion containing solvophilic group with polyether chain The quality ratio of separation structure is preferably more than 1/99, more preferably more than 3/97, more preferably more than 5/95, in addition, excellent Elect less than 99/1, more preferably less than 97/3, more preferably less than 95/5 as.
From the viewpoint of dispersibility, polyurethane dispersant (b-1) more preferably has selected from above-mentioned formula (3-1)～(3-3) In any a kind of part-structure, further preferably there is the part-structure shown in formula (3-1).
Similarly, the part-structure containing solvophilic group from the viewpoint of dispersibility, in polyurethane dispersant (b-1) Content ratio be preferably more than 5 mass %, more than more preferably 10 mass %, more than more preferably 20 mass %, more More than more preferably 30 mass %, more than particularly preferably 40 mass %, more than most preferably 50 mass %, in addition, excellent Elect below 90 mass % as, below more preferably 80 mass %, below more preferably 70 mass %.
Polyurethane dispersant (b-1) can also be in addition to beyond solvophilic group and adsorption group, also there is other The dispersant of functional group.As other functional groups, such as active energy ray-curable unsaturated group etc. can be enumerated.Specifically may be used Enumerate for example：The unsaturated groups such as vinyl, acryloyl group and methylacryloyl.
It is believed that passing through active like this energy ray-curable unsaturated group, making photonasty group There is the tendency of sensitivity raising in the case of compound, but then, be recognized as there is these functional groups in dispersion React and the tendency of gelation occurs, therefore from the scattered aspect of the pigment in view of ageing stability, preferably not Active energy ray-curable unsaturated group.
(the reasons why show effect)
<Dispersibility improves effect>
Used in the present invention, polyurethane dispersant (b-1) is characterised by comprising the part-structure shown in above-mentioned formula (i). It is believed that by comprising the part-structure shown in above-mentioned formula (i), can be by solvophilic group or adsorption group, especially contain The part-structure of solvophilic group or the part-structure containing adsorption group configure on straight line such that it is able to improve the phase to solvent Dissolubility and the adsorptivity to pigment entirety.Furthermore it is possible to think that the nitrogen-atoms in amino-formate bond position are also beneficial to face The absorption of material, based on the synergy with adsorption group, can make pigment adsorption become good further.
Particularly, make solvophilic group be comprise polyether chain and/or the group of polyester chain in the case of, exist and following incline To：Its by this position with photosensitive polymer combination in solvent (e) affine thus stretching in a solvent, thus in pigment In the case of being intended to during dispersion condense, space bit resistance part can be become and given play to the function of preventing pigment from cohesion occurring.
In addition, if so that after in the polarity of polyether chain and polyester chain and solvent polarity or photosensitive polymer combination The mode that the polarity of the alkali soluble resin (d) of narration or photopolymerization monomer is consistent is constituted, then there are following tendencies：Chain part It is susceptible in a solvent stretch and so that sterically hindered effect is increased, so that dispersibility becomes good.
In particular it is preferred that comprising the solvophilic group with polyether chain and both solvophilic groups with polyester chain. It is believed that by having both, there are following tendencies：It is easily tailored as making the polarity with solvent for the polarity of solvophilic group It is consistent, solvophilic group stretches in a solvent further, sterically hindered effect increases further, better dispersed can be obtained State, even if also can stably keep dispersity after passing through for a long time.
Further, preferably adsorption group and main chain polyurethane skeleton away from.By making specific adsorption group and master Chain polyurethane skeleton away from, exist during pigment adsorption sterically hindered diminish, tendency that pigment adsorption improves further.
<Process patience and raising thermostability and form high fine fine rule by improving alkali development>
By using the photosensitive polymer combination containing polyurethane dispersant (b-1), flat board can be applied to by manufacture Even if the fine light filter of computer or fine display etc. and make particularly through the work of alkali development or high-temperature process Also fine high fine rule can be stably formed in sequence.
In order to be stably formed fine fine rule, need to make this narrow line shape be stably formed in alkali development, and make Even if in its curing process based on more than 200 DEG C of high-temperature heating treatment behind, thermal deformation is also less, stably keeping should Shape.
It is believed that due to pigment and dispersion for the photosensitive polymer combination containing polyurethane dispersant (b-1) The absorption affinity of agent is strong, thus high with respect to the patience of alkaline developer, therefore, is temporarily forming during alkali development after uv irradiation Even if fine fine rule in the case of being impregnated in alkaline developer further, also can suppress developer solution in this fine rule Being impregnated with of the part closely sealed with substrate, can prevent embedded generation, the generation peeled off, the deformation of cone-shaped being caused by etch. Furthermore it is possible to think, even if in the case of carrying out high-temperature process in more than 200 DEG C after development and so that it is solidified, pigment with point The absorption of powder also will not weaken, and thermal deformation is few, therefore can stably keep fine narrow line shape.
Polyurethane dispersant (b-1) due to having the part-structure shown in above-mentioned formula (i), therefore as already mentioned it is possible to Think, it is easily adsorbed at pigment entirety, and, can be occurred with pigment by the part of amino-formate bond or adsorption group Strongly adsorb, thus pigment is wrapped into.
Particularly, in the case of making solvophilic group be to comprise polyether chain and/or the group of polyester chain, exist and following incline To：This solvophilic group has the function of extending to outside pigment, meeting and alkali soluble resin in the operation manufacturing light filter Or the photopolymerization monomer being crosslinked by ultraviolet etc. is fully compatible, thus being mutually wound around.
In this way it can be considered that, the pigment adsorption based on polyurethane dispersant (b-1) and solvent affinity, can improve phase Patience for alkaline developer and the patience with respect to high-temperature process.Particularly, it is difficult to arrive at deep in ultraviolet and lead to Solidifying in the high photosensitive polymer combinations of pigment content ratio such as weak white carbon black of deep is effective.
Particularly, have concurrently optical absorption and the free radical as Photoepolymerizationinitiater initiater (c) described below is being produced Effect, can reach on a small quantity what highly sensitive oxime ester Photoepolymerizationinitiater initiater (c-1) and polyurethane dispersant (b-1) were applied in combination In the case of, the crosslinking irradiated based on ultraviolet of photopolymerization monomer or alkali soluble resin can be promoted, they and poly- ammonia can be made Mutual winding between the solvophilic group of ester dispersant becomes more strong, thus resistance to alkali-developable and thermostability can be improved, Fine narrow line shape can be stably formed.
Particularly, be used the resin comprising more aromatic ring as alkali soluble resin in the case of, there are following tendencies： High-fire resistance and high alkali resistance can be obtained based on this aromatic ring, in addition, sterically hindered also can improve based on larger in three-dimensional Thermostability and alkali resistance are such that it is able to form fine narrow line shape more stablely.
In addition, in the case of using opacifiers such as white carbon blacks, when its average primary particle diameter is less, this polyurethane dispersant (b-1) it is easier capture pigment, thus resistance to alkali-developable and thermostability improve further, can be formed fine more stablely Narrow line shape.
Polyurethane dispersant (b-1) comprise to have polyether chain solvophilic group and have polyester chain solvophilic group this In the case of both, there are following tendencies：They are easily handed over high molecular alkali soluble resin or by ultraviolet The photopolymerization monomer of connection is compatible it is easier to mutual be wound around, therefore with respect to the patience of alkaline developer and with respect to high temperature at The patience of reason improves.
In addition, further, in the case that polyether chain has the alkylidene oxide of long-chain, gather with alkali soluble resin or light Conjunction property monomer is compatible further, becomes easily mutually to be wound around, and alkali resistance and thermostability improve, and are therefore more highly preferred to.
Additionally, it is preferred that the polyurethane skeleton of adsorption group and main chain away from.By making the poly- ammonia of adsorption group and main chain Away from there are following tendencies in ester skeleton：This adsorption group be adsorbed in during pigment sterically hindered diminish, polyurethane dispersant (b-1) become easily to capture pigment, its patience with respect to alkaline developer and the patience with respect to high-temperature process increase further Plus.
[manufacture method of polyurethane dispersant (b-1)]
Polyurethane dispersant (b-1) for example can be manufactured using diisocyanate cpd.In addition, adsorption group can use Have 2 hydroxyls as the functional group reacted with NCO, imino group or mercapto and have more than 1 not with This NCO reaction the compound (hereinafter also referred to " adsorption group importing compound ") of adsorption group and obtain.
By making, above-mentioned adsorption group imports compound and diisocyanate cpd reacts and bonding, can form straight chain The polyurethane skeleton of structure.In addition, it is to be adsorbed in photoresist that this adsorption group imports contained adsorption group in compound The adsorption group of the pigment as color material (a) in compositionss.
The structure importing the specific adsorption group in compound according to above-mentioned adsorption group is different, including：This absorption base Group is included in the situation in polyurethane skeleton；And become the side chain of polyurethane skeleton, thus becoming the poly- ammonia being bonded to main chain The situation of the pendant type adsorption group of ester skeleton.
Amino-formate bond in the polyurethane skeleton of polyurethane dispersant (b-1) etc. also can be adsorbed in pigment, but passes through There is adsorption group further that be adsorbed in surface of pigments, and make this adsorption group import polyurethane skeleton or be polyurethane bone The side chain of frame and become the adsorption group of pendant type, can be shown that more good pigment adsorption.Adsorption group is pendant type Adsorption group when, there is the sterically hindered tendency diminishing during pigment adsorption, therefore preferably.The details of these situations such as institute below State.
For contained solvophilic group in polyurethane dispersant (b-1), by using only having 2 in its side end The compound of individual hydroxyl, imino group or mercapto, can be reacted with NCO by this 2 groups and be bonded to polyurethane Skeleton.
For the polyether chain of the solvophilic group preferably comprising in polyurethane dispersant (b-1), by using only at it Side end has the compound of 2 hydroxyls, imino group or mercapto, can be reacted with NCO by this 2 groups And it is bonded to polyurethane skeleton.In the case that opposite side end has the group reacting with NCO, preferably by alkyl Deng this group of replacement so as not to reacting with NCO.
So, by so that be only bonded with diisocyanate cpd with one-side ends and using as side chain from main chain Polyurethane skeleton extend mode (hereinafter referred to as " horizontal ") be bonded, the polyether lateral chain of solvophilic group can be formed.They Details as hereinafter described.
Similarly, for the polyester chain preferably comprising in solvophilic group it is also possible to by using only in its side end There is the compound of 2 hydroxyls, imino group or mercapto, and be bonded to the reaction of NCO by this 2 groups Polyurethane skeleton.In the case that opposite side end has the group reacting with NCO, preferably make it not by replacing Can react with NCO.
So, by so that being only bonded with diisocyanate cpd with one-side ends and making it poly- with respect to main chain Urethane skeleton is transversely bonded, and can form the polyester side chains of solvophilic group.Their details are also as hereinafter described.
[constituting compound (b-a), (b-b), (b-c) of polyurethane dispersant (b-1)]
The polyurethane skeleton preferably becoming the main chain of polyurethane dispersant (b-1) is essentially straight chain.As for being formed The polyisocyanate compound of the polyurethane skeleton of this straight chain, as previously described, preferably uses and has the two of 2 NCOs Isocyanate compound (b-a).
By making above-mentioned diisocyanate cpd (b-a) and being there is 2 functional groups reacted with NCO and tool The adsorption group having more than 1 adsorption group imports compound (b-b) and only has 2 and isocyanates in side end Base reaction functional group and comprise solvophilic group compound (b-c) combine, the linear chain structure having as main chain can be obtained Carbamate skeleton, the solvophilic group being bonded to this main chain and adsorption group polyurethane dispersant (b-1).
Polyurethane dispersant (b-1) is with polyurethane skeleton as backbone polymer, with solvophilic group as branched polymer Graft polymers, preferably in the main chain of the straight chain polyurethane skeleton of backbone polymer, there is specific adsorption group or tool There are the graft polymers of the specific adsorption group being bonded with main chain.
[chemical formula compound (b-a)；Constitute the diisocyanate cpd of polyurethane skeleton]
As above-mentioned diisocyanate cpd (b-a), preferably toluene di-isocyanate(TDI) (TDI), isophorone two is different Cyanate (IPDI), hexane diisocyanate (HDI), α, α-tetramethyl xylylene diisocyanate (TMXDI), diphenylmethyl Alkane -4,4 '-diisocyanate (4,4 '-MDI), diphenyl methane -2,4 '-diisocyanate (2,4 '-MDI) or dicyclohexyl first Alkane -4,4 ' diisocyanate cpd such as-diisocyanate (HMDI) or these diisocyanate cpds mixture.
In the middle of these, any diisocyanate cpd preferably in TDI, IPDI and MDI, more preferably TDI and/or MDI. As diisocyanate cpd (b-a), can also be using the diisocyanate cpd beyond above-mentioned concrete example.
Several compounds of diisocyanate cpd (b-a) are illustrated in lower-left, thus, it is possible in polyurethane dispersant (b-1) import the part-structure of bottom right in.
[chemical formula 48]
In above-mentioned formula, * represents the bonding position with the oxygen atom in amino-formate bond or the nitrogen-atoms in urea bond.
Than that described above, as long as having the diisocyanate cpd of 2 NCOs, then can be suitable for use as will be straight Chain polyurethane structural imports the diisocyanate cpd (b-a) of polyurethane dispersant (b-1).
[chemical formula compound (b-b)；There are 2 functional groups reacted with NCO and at least there is more than 1 adsorb The compound of group]
For contained adsorption group in polyurethane dispersant (b-1), in order to above-mentioned diisocyanate cpd (b- A) form polyurethane skeleton, compound (b- can be imported by the adsorption group with 2 functional groups reacted with NCO B) obtain.
As the functional group reacted with NCO, preferably hydroxyl or imino group.As the feelings with 2 this functional groups Concrete example under condition, more preferably 1 is hydroxyl and another 1 situation for imino group or 2 situations being hydroxyl, further Preferably 2 are hydroxyl.
Also there are in addition to be there is the functional group reacted with NCO the feelings of basic group in this compound (b-b) Under condition, this basic group is preferably made to be the group that will not react with NCO.As having this basic group Compound, can enumerate for example：Aliphatic tertiary amine, hindered aromatic race amine and alicyclic or aromatic nitrogen heterocyclic.As Hindered aromatic race amine, can enumerate for example in its 2 and/or 6 aniline with space steric hindrance group.
Based on the amino-formate bond being formed by this compound (b-b) and diisocyanate cpd (b-a) and/or urea Part-structure shown in above-mentioned formula (1), (2-1), (2-2) or (2-3) can be imported polyurethane dispersant (b-1) by key.
Can by shown in formula (1) part-structure import polyurethane dispersant (b-1) compound (b-b) can enumerate with different 2 functional groups of cyanic acid ester group reaction are the compound of hydroxyl.2 of this 2 hydroxyls and diisocyanate cpd (b-a) NCO forms amino-formate bond.Concrete example is described below.
Can by shown in formula (2-1) part-structure import polyurethane dispersant (b-1) compound (b-b) can enumerate with 2 functional groups of NCO reaction are the compound of hydroxyl, this 2 hydroxyls and the 2 of diisocyanate cpd (b-a) Individual NCO forms amino-formate bond.Concrete example is described below.
The compound (b-b) that part-structure shown in formula (2-2) can be imported polyurethane dispersant (b-1) can enumerate tool There are the bonding position of N atom in the part-structure shown in formula (2-2) and the imino group of bonded hydrogen atoms and former by O The bonding position of son and the compound of the hydroxyl of bonded hydrogen atoms.This imino group and hydroxyl and diisocyanate cpd (b-a) 2 NCOs form urea bond and amino-formate bond respectively.Concrete example is described below.
The compound (b-b) that the part-structure shown in formula (2-3) is contained in polyurethane dispersant (b-1) can be made can to enumerate 2 functional groups reacted with NCO are the compound of hydroxyl, this 2 hydroxyls and diisocyanate cpd (b-a) 2 NCOs form amino-formate bonds.Concrete example is described below.
[for the compound (b-b) of the part-structure shown in lead-in (1)]
Compound (b-b) is the situation of the compound that the part-structure shown in formula (1) imports polyurethane dispersant (b-1) Under, the bonding of 2 hydroxyls based on compound (b-b) and 2 NCOs of diisocyanate cpd (b-a), formula (1) The overall tertiary amine structure of shown part-structure is imported into polyurethane skeleton.
As the concrete example in the case of this, can enumerate：N methyldiethanol amine (NMDA) and N- phenyldiethanol-amine (NPDA) etc..
For example, the knot of bottom right example can based on the compound being illustrated in lower-left, be imported in polyurethane dispersant (b-1) Structure.This structure is equivalent to the part-structure shown in above-mentioned formula (1).In addition, as long as the part-structure shown in contained (1) And the compound having hydroxyl in its end then goes for the synthesis of polyurethane dispersant (b-1).In addition, by using generation The compound for hydroxyl with mercapto or amino etc. can also obtain similar urethanes.
[chemical formula 49]
In above-mentioned formula, * represents the bonding position with the carbonyl of the amino-formate bond in the polyurethane skeleton of main chain.
[for the compound (b-b) of the part-structure shown in lead-in (2-1)～(2-3)]
It is to import the part-structure shown in above-mentioned formula (2-1), (2-2) or (2-3) that adsorption group imports compound (b-b) React with NCO 2 senses in the case of the compound of polyurethane dispersant (b-1), based on compound (b-b) Roll into a ball the bonding with the NCO of diisocyanate cpd (b-a), the formula (2-1) as adsorption group, (2-2) or (2- 3) R inα、Rβ, N and Rγ(Rγ’) mutually remotely exist with respect to polyurethane skeleton.
Adsorption group imports in compound (b-b), for above-mentioned<Dispersibility improves effect>And<Alkaline-resisting aobvious by improving Shadow liquid and improve thermostability and form high fine fine rule>Described in the reasons why, be preferably able to formula (2-1), (2-2) or (2-3) Shown part-structure imports the compound of polyurethane dispersant (b-1).
The adsorption group that part-structure shown in formula (2-1), (2-2) or (2-3) is imported polyurethane dispersant (b-1) is led Enter compound (b-b) and preferably there is hydroxyl and/or imino group, thus 2 isocyanates with diisocyanate cpd (b-a) Base is bonded with amino-formate bond and/or urea bond, forms polyurethane skeleton.
In the case of being somebody's turn to do, the N atom in the part-structure shown in formula (2-1), (2-2) or (2-3), RδAnd Rε(Rε’)、O、Rη、 And C atom can be imported into polyurethane skeleton, but by making the R of tertiary amineα、Rβ, N and Rγ(Rγ’) i.e. adsorption group be bonded to polyurethane Skeleton, can with polyurethane skeleton away from.As a result, can make tertiary amine nitrogen-atoms immediate with respect on polyurethane skeleton Atom at least separates 1 atom.
The tertiary amine that the polyurethane skeleton of such linear chain structure with main chain is mutually remotely transversely bonded, exist with respect to Surface of pigments has the tendency of more preferable adsorption function.Partly or entirely carrying out quaternized and forming quaternary ammonium of tertiary amine can also be made Salt.
As quaternary ammonium salt, can enumerate in the such as part-structure shown in formula (2-1 '), (2-2 ') or (2-3 ') as Rα、 Rβ、RA、N+And Rγ(Rγ’) adsorption group.
Should in the case of, above-mentioned adsorption group by be bonded to polyurethane skeleton and with polyurethane skeleton away from, as a result, The nitrogen-atoms that quaternary ammonium salt base can be made separate at least one atom with respect to atom immediate on polyurethane skeleton.
These adsorption groups import in compound (b-b), the part-structure shown in formula (2-1) can be imported polyurethane and divide The concrete example of the compound in powder (b-1) can be listed below described example, in addition, as long as shown in contained (2-1) Part-structure and in its end, be there are 2 functional groups reacted with NCO, then can be applied to polyurethane dispersant (b-1).
Part-structure shown in formula (2-1) by the tertiary amino at least with more than 1 and can have the compound of 1 hydroxyl Etc. (b-b1) obtain.Its specific reaction is for example lower described.
First, hydroxyl and the changes containing 2 NCOs such as toluene di-isocyanate(TDI) of above-claimed cpd (b-b1) are made One NCO reaction of compound.Then, make another NCO and diethanolamine etc. containing 1 secondary amino group and extremely Secondary amino group reaction in the compound of few 2 activity hydroxies.Thus, it is possible to import 2 hydroxyls in compound (b-b1).
For example, the knot of bottom right example can based on the compound being illustrated in lower-left, be imported in polyurethane dispersant (b-1) Structure.This structure is equivalent to the part-structure shown in above-mentioned formula (2-1).
[chemical formula 50]
In above-mentioned formula, * represents the bonding position with the carbonyl of the amino-formate bond in the polyurethane skeleton of main chain.
In addition, the compound of the part-structure shown in lead-in (2-1) can also obtain by the following method.Concrete and Speech, makes the tertiary amino at least with more than 1 and has compound and diethanolamine of ethylenically unsaturated group etc. containing 1 The secondary amino group of secondary amino group and at least compound of 2 activity hydroxies carries out Michael's addition.
For example, the knot of bottom right example can based on the compound being illustrated in lower-left, be imported in polyurethane dispersant (b-1) Structure.This structure is equivalent to the part-structure shown in above-mentioned formula (2-1).
[chemical formula 51]
In above-mentioned formula, * represents the bonding position with the carbonyl of the amino-formate bond in the polyurethane skeleton of main chain.
In addition, the compound of the part-structure shown in lead-in (2-1) can also obtain by the following method.For example, also There are following methods etc.：By making to have the compound of tertiary amino and 1 hydroxyl and there is NCO and acryloxy Compound reacts, so that hydroxyl forms amino-formate bond with NCO, thus can be to the chemical combination with tertiary amino Import unsaturated group in thing, and then make this this compound and the secondary amino group of diethanolamine that Michael's addition to occur.Using the party Method can also import 2 hydroxyls.
In addition, as the compound of the part-structure shown in lead-in (2-1), including compound as described below.It is based on It is illustrated in the compound of lower-left, the structure of bottom right example can be imported in polyurethane dispersant (b-1).This structure also corresponds to Part-structure shown in above-mentioned formula (2-1).In addition, as long as the part-structure shown in contained (2-1) and in its end There are 2 hydroxyls, then go for the synthesis of polyurethane dispersant (b-1).
[chemical formula 52]
In above-mentioned formula, * represents the bonding position with the carbonyl of the amino-formate bond in the polyurethane skeleton of main chain.
In addition, the compound of the part-structure shown in lead-in (2-2) can obtain by the following method.Specifically, Can have the compound of 1 tertiary amino and 1 primary amino radical and Hydroxyethyl Acrylate etc. by making dimethylaminopropyl amine etc. There is 1 hydroxyl and the compound of ethylenically unsaturated group carries out Michael's addition and obtains.Thus, can obtain having by olefinic Unsaturated group and primary amino radical through imino group obtained from Michael's addition and have the compound of hydroxyl.
In addition, similarly, there is compound and the acrylic acid 2- (diformazan of 1 hydroxyl and primary amino radical based on monoethanolamine etc. Base amino) ethyl ester etc. have 1 tertiary amino and ethylenically unsaturated group compound Michael's addition it is also possible to be had The compound of the adsorption group of tertiary amino, hydroxyl and imino group.
For example, the knot of bottom right example can based on the compound being illustrated in lower-left, be imported in polyurethane dispersant (b-1) Structure.This structure is equivalent to the part-structure shown in above-mentioned formula (2-2).In addition, as long as comprising the portion shown in above-mentioned formula (2-2) Separation structure and have 1 hydroxyl and imino group in its end, then be applicable to polyurethane dispersant (b-1).
[chemical formula 53]
In above-mentioned formula, the * adjacent with oxygen atom represents the carbonyl with the amino-formate bond in the polyurethane skeleton of main chain Bonding position, the * adjacent with nitrogen-atoms represent the bonding position with the carbonyl of the urea bond in same skeleton.
In addition, as the compound with the part-structure shown in formula (2-3), including compound as described below.For example, Based on the compound being illustrated in lower-left, the structure of bottom right example can be imported in polyurethane dispersant (b-1).This structure is suitable In the part-structure shown in above-mentioned formula (2-3).
[chemical formula 54]
In above-mentioned formula, * represents the bonding position with the carbonyl of the amino-formate bond in the polyurethane skeleton of main chain.
In addition, as long as comprising the part-structure shown in above-mentioned formula (2-3) and in its end, there are 2 hydroxyls, then may be used It is applied to the synthesis of polyurethane dispersant (b-1).
For example, 2 hydroxyls of above-claimed cpd are replaced to replace the compound having 2 primary amino radicals and/or secondary amino group and also may be used To be applied to the synthesis of polyurethane dispersant (b-1).Additionally, comprise more than 1 specific adsorption group and replace have 2 primary The compound of amino and/or secondary amino group is readily adaptable for use in the synthesis of polyurethane dispersant (b-1).In addition, by only having 1 hydroxyl Part-structure shown in formula (2-3) can be imported polyurethane dispersant by the compound (b-b1) of base and the reaction of thioglycerol (b-1-1).
Its concrete reaction is for example lower described.First, hydroxyl and toluene di-isocyanate(TDI) of above-claimed cpd (b-b1) etc. are made One of compound containing 2 NCOs NCO reacts.
Then, another NCO and thioglycerol etc. are made containing 1 active mercapto and at least 2 activity hydroxies Compound the reaction of active mercapto.Thus, it is possible to import 2 hydroxyls in compound (b-b1).
For example, the knot of bottom right example can based on the compound being illustrated in lower-left, be imported in polyurethane dispersant (b-1) Structure.This structure is equivalent to the part-structure shown in above-mentioned formula (2-3).
[chemical formula 55]
In above-mentioned formula, * represents the bonding position with the carbonyl of the amino-formate bond in the polyurethane skeleton of main chain.
[for importing the compound (b-b) of nitrogen atom heterocyclic radical]
By using the heterocyclic compound containing nitrogen-atoms as compound (b-b), it can be polyurethane dispersant (b-1) Give good pigment adsorption function.Import being used in the case of polyurethane skeleton as heterocycles that these are contained nitrogen-atoms Import the concrete example of this compound of heterocyclic radical containing nitrogen-atoms and the structure being imported into, can be listed below.
For example, the knot of bottom right example can based on the compound being illustrated in lower-left, be imported in polyurethane dispersant (b-1) Structure.In addition, it is possible to use diverse location on heterocycle for the 2 functional group's Direct Bonding reacted with NCO, Or it is bonded in the compound of the diverse location on heterocycle via 1～10 atom.
[chemical formula 56]
In above-mentioned formula, * represents the bonding position with the carbonyl of the amino-formate bond in the polyurethane skeleton of main chain.
In addition, nitrogen atom heterocyclic radical with respect to main chain polyurethane skeleton across the above atom of at least one away from In the case of, compound shown below can be used.For example, based on the compound being illustrated in lower-left, can be in polyurethane dispersant (b-1) import the structure of bottom right example in.
In addition, it is possible to use the ring with the heterocyclic compound containing nitrogen-atoms via 1～20 atom key The compound of 2 functional groups reacted with NCO is contained in the end of 1 side chain closing.
[chemical formula 57]
The * adjacent with oxygen atom represents the bonding position with the carbonyl of the amino-formate bond in polyurethane skeleton, with nitrogen The adjacent * of atom represents the bonding position with the carbonyl of the urea bond in same polyurethane skeleton.
These compounds can also be obtained using the method same with the part-structure shown in above-mentioned formula (2-1) or (2-2) Arrive.In addition, the part for the tertiary amino being equivalent to the part-structure shown in above-mentioned formula (2-3) is the jeterocyclic chemistry containing nitrogen-atoms The situation of the structure of compound, is similarly effective, is applicable to polyurethane dispersant (b-1).
In the case of these, the heterocyclic compound containing nitrogen-atoms of compound (b-b) becomes with respect to polyurethane skeleton extremely Leave the pendant type adsorption group of more than 1 atom less.Due to above-mentioned<Dispersibility improves effect>And<Alkaline-resisting by improving Developer solution and improve thermostability and form high fine fine rule>Part the reasons why illustrate, more preferably urethanes (b-1-1) Containing this pendant type adsorption group.
Adsorption group importing compound (b-b) for the synthesis of polyurethane dispersant (b-1) can also be using other public The conventional method known and obtain.
[method importing quaternary ammonium salt base]
Method as importing quaternary ammonium salt base in polyurethane dispersant (b-1), can enumerate for example following methods：First, Lead in polyurethane dispersant (b-1) by using the compound for the part-structure shown in lead-in (2-1)～(2-3) Enter tertiary amino, then, this tertiary amino is carried out quaternized by using known any quaternizing agent.
Preferably quaternizing agent is alkyl halide, aralkyl halide, dialkyl carbonate, dialkyl sulfate or ring Oxide.Particularly preferred quaternizing agent is dimethyl sulfate, chlorotoluene or styrene oxide.For tertiary amino, can be to it A part carries out quaternization it is also possible to carry out quaternization to whole tertiary aminos.
In addition, these tertiary aminos can also be with known any organic acid compound forming salt.Preferably organic acid chemical combination Thing is the acidifying of the organophosphors such as organic sulfonic acid compound, di(2-ethylhexyl)phosphate methacryloyloxyethyl or phenyl-phosphonic acid such as vinyl sulfonic acid Compound etc..
[chemical formula compound (b-c)；In side end, be there are 2 functional groups reacted with NCO and comprise close molten The compound of agent group]
The main chain of polyurethane skeleton in polyurethane dispersant (b-1) and the horizontal solvophilic group being bonded to its side Side chain can be by making the change comprising solvophilic group only in side end with 2 functional groups reacted with NCO Compound (b-c) and above-mentioned diisocyanate cpd (b-a) react and obtain.
As react with NCO 2 functional groups, preferably hydroxyl and/or imino group of compound (b-c), more excellent Select 1 be hydroxyl and another 1 be that imino group or 2 are hydroxyl, further preferred 2 are hydroxyl.
Hereinafter, the solvophilic group for polyurethane dispersant (b-1) comprises the situation of polyether chain and/or polyester chain, spy It is not to have a case that the part-structure shown in above-mentioned formula (3-1)～(3-3) is described in detail.
Based on the amino-formate bond being formed by compound (b-c) and diisocyanate cpd (b-a) or urea bond, permissible Part-structure shown in above-mentioned formula (3-1), (3-2) or (3-3) is imported polyurethane dispersant (b-1).
Can by shown in formula (3-1) part-structure import polyurethane dispersant (b-1) compound (b-c) in isocyanide 2 functional groups of perester radical reaction are hydroxyl, 2 NCOs of this 2 hydroxyls and diisocyanate cpd (b-a) Form amino-formate bond.Concrete example is as hereinafter described.
Can by shown in formula (3-2) part-structure import polyurethane dispersant (b-1) compound (b-c) in isocyanide 2 functional groups of perester radical reaction are imino group and hydroxyl, and imino group forms urea bond and hydroxyl and Carbimide. with NCO Ester group forms amino-formate bond.Concrete example is as hereinafter described.
Can by shown in formula (3-3) part-structure import polyurethane dispersant (b-1) compound (b-c) in isocyanide 2 functional groups of perester radical reaction are hydroxyl, 2 NCOs of this 2 hydroxyls and diisocyanate cpd (b-a) Form amino-formate bond.Concrete example is as described later.
Hereinafter, illustrate for the compound (b-c) for importing solvophilic group to polyurethane dispersant (b-1).
This compound (b-c) if comprise the functional group reacted with NCO, in synthesis of polyurethane in two ends During dispersant (b-1), may hinder with respect to the poly- ammonia of straight chain because of other residual isocyanate bases and this functional group's bonding Ester skeleton and be bonded to the formation of the horizontal side chain of side.It is therefore preferable that compound (b-c) do not comprise beyond side end with The functional group of NCO reaction.
Therefore, and the end of 2 functional group's opposite side reacted with NCO there is hydroxyl etc. and Carbimide. In the case of the functional group of ester group reaction, this hydroxyl of preferred pair etc. is replaced and so that it will not be occurred instead with NCO Should.The hydrogen atom of more preferably this hydroxyl is replaced by alkyl and forms alkoxyl.
Particularly, the alkyl replacing the hydrogen atom of above-mentioned hydroxyl is more preferably the alkyl of carbon number 1～50.Alkyl May optionally be the alkyl or cycloalkyl of side chain it is also possible to replacing alkyl and importing aryl or aralkyl.
As cycloalkyl, the preferably cycloalkyl of the carbon number such as cyclopropyl, cyclohexyl 3～6.As aryl, preferably Optionally former by carbon such as the naphthyl of the alkoxyl replacement of halogen atom, the alkyl of carbon number 1～20 or carbon number 1～20, phenyl The aryl of subnumber 6～10.
As aralkyl, preferably hydrogen atom is optionally by halogen, the alkyl of carbon number 1～20 or carbon number 1～20 Alkoxyl replace 2- phenylethyl or benzyl.
Chain length containing polyether chain and/or the end alkyl of the compound of polyester chain can be according to institute in photosensitive polymer combination The property of the solvent (e) containing and suitably select.For example in the case that (e) solvent is polar organic solvent, above-mentioned end alkyl It can also be able to be preferably the alkyl of the carbon number 1～12 of side chain for straight chain.As the concrete example of alkyl, first can be enumerated Base, ethyl, propyl group and isopropyl.
In the case that polyurethane dispersant (b-1) comprises polyether lateral chain, from the viewpoint of commercially easily obtaining, excellent Select the alkyl that end alkyl is carbon number 1～4, more preferably methyl.On the other hand, (e) solvent be nonpolar organic molten In the case of agent, the carbon number of preferably above-mentioned end alkyl is more than 8.
In solvophilic group, the part (wherein, not comprising end alkyl) of the polyoxy alkylidene chain of contained polyether chain is preferred Polyoxy alkylidene for carbon number 2～4.From the viewpoint of substrate adaptation, in the polyoxy alkylidene of carbon number 2～4 The content of the polyoxyethylene comprising is preferably below 60 mass %, is more preferably below 40 mass %, particularly preferably 20 matter Amount below %, does not further preferably comprise polyoxyethylene.
The polyoxy alkylidene chain part of carbon number 2～4 can also be by ethylene oxide, propylene oxide or butylene oxide etc. The (co) polymerization of oxyalkylene and obtain, or obtained by oxolane.In the case of copolymerization, can be random copolymer, It can be block copolymer.In addition, polyoxyalkylene moieties can also be able to be side chain for straight chain.
From the viewpoint of so that dispersion ageing stability is improved, polyoxyalkylene moieties are preferably polyoxypropylene.From making From the viewpoint of dispersibility improves, the polyether chain comprising in the solvophilic group of polyurethane dispersant (b-1) preferably has carbon The alkyl of atomic number 1～10 as end alkyl and have carbon number 2～4 polyoxy alkylidene polyether chain, this situation Under, end alkyl is more preferably methyl or butyl.
Polyester chain as solvophilic group is preferably obtained by the hydroxy carboxylic acid comprising 1～26 carbon atom or its lactone Arrive.The species of hydroxy carboxylic acid suitably can select according to the property of contained solvent (e) in photosensitive polymer combination.
E () solvent is polar organic solvent in the case that, hydroxy carboxylic acid preferably up to comprises 8 carbon atoms, organic media In the case of non-polar organic liquid, hydroxy carboxylic acid preferably comprises more than 8 carbon atoms.
For polyester chain, in order that it contributes to the dissolubility of organic media, preferably by the different hydroxyl carboxylics of more than 2 Acid or its lactone obtain.Hydroxy carboxylic acid can be saturation can also be undersaturated, furthermore it is possible to be straight chain can also be Side chain.
The example of suitable hydroxy carboxylic acid is：Hydroxyacetic acid, lactic acid, 5- hydroxypentanoic acid, 6 hydroxycaproic acid, ricinoleic acid, 12- hydroxy stearic acid, sabinic acid, 5- hydroxy-dodecanoic acid, 5- hydroxydecanoic acid and 4- hydroxydecanoic acid.
The example of suitable lactone is：Beta-propiolactone and the δ-valerolactone optionally being replaced by the alkyl of carbon number 1～6 And 6-caprolactone.For example：Beta-methyl-δ-valerolactone, δ-valerolactone, 6-caprolactone, 2- methyl-epsilon-caprolactone, 3- methyl-ε-oneself Lactone, 4- methyl-epsilon-caprolactone, the 5- tert-butyl group -6-caprolactone, 7- methyl -4,4,6- trimethyl -6-caprolactone and 4,6,6- tri- Methyl-epsilon-caprolactone and their mixture.
Polyester chain particularly preferably derived from δ-valerolactone and 6-caprolactone.
The horizontal side chain of the polyether chain as solvophilic group and/or polyester chain can be formed by single monomer, in addition, Can also be formed by various of monomer composition.In addition, polyether chain can comprise polyester portion, on the contrary, polyester chain can also comprise Polyether moiety.
The polyether chain of solvophilic group in polyurethane dispersant (b-1) and/or the number-average molecular weight of polyester chain are preferably Less than 10,000, more preferably less than 4,000, more preferably less than 2,500.The number of polyether chain and/or polyester chain is divided equally Son amount is preferably more than 300, more preferably more than 600, more preferably more than 800.Below for above-mentioned higher limit, deposit In the tendency that can improve substrate adaptation, in addition, by more than for above-mentioned lower limit, existing and can improve inclining of dispersibility To.
Hereinafter, anti-with NCO for importing to the polyether chain of compound (b-c) and/or the side end of polyester chain The method of 2 functional groups answered illustrates.
In order to polyether chain and/or polyester chain side end import and compound (b-a) NCO react 2 Individual functional group, including several method.Thus, above-mentioned polyether chain and/or polyester chain can be using 2 functional groups of side end It is bonded with diisocyanate cpd (b-a) and forms the main chain as polyurethane skeleton, form polyether chain and/or polyester simultaneously The side chain of the solvophilic group of chain.
In the case that laterally the side chain of solvophilic group comprises polyether chain, comprise the compound of the polyether chain of solvophilic group (b-c) preferably in side end, be there are 2 hydroxyls being reacted with NCO or there is 1 hydroxyl and 1 imino group.Hydroxyl Base and imino group preferably up to separate 6 carbon atoms.Compound (b-c) comprises the feelings of 2 hydroxyls reacted with NCO Under condition, they preferably up to separate 17 atoms.
For 2 functional groups of the side end reacting with NCO of the compound (b-c) comprising polyether chain, make The method all importing hydroxyl for 2, can be using the method identical method with 2 hydroxyls of importing in above-claimed cpd (b-b).
For the compound (b-b) in part-structure importing polyurethane dispersant (b-1) shown in formula (3-1) is concrete Example can be listed below.In addition, as long as the part-structure shown in contained (3-1) and there are 2 hydroxyls, then in its end It is applicable to the synthesis of polyurethane dispersant (b-1).
First, side end is made to have passed through the opposite side end of the alkyl etherified polyoxy alkylidene chain of carbon number 2～4 etc. The hydroxyl at end is reacted with a NCO of the compounds containing 2 NCOs such as toluene di-isocyanate(TDI).Then, Make the secondary amino group containing 1 secondary amino group and at least compound of 2 activity hydroxies such as another NCO and diethanolamine Reaction.Thus, it is possible to import 2 hydroxyls to the side end of polyoxy alkylidene chain.
For example, the knot of bottom right example can based on the compound being illustrated in lower-left, be imported in polyurethane dispersant (b-1) Structure.This structure is equivalent to the chemical constitution shown in formula (3-1).
[chemical formula 58]
In above-mentioned formula, * represents the bonding position with the carbonyl of the amino-formate bond in the polyurethane skeleton of main chain.
In addition, the compound with the part-structure shown in above-mentioned formula (3-1) can also obtain by the following method.As The method importing 2 hydroxyls to the side end of the compound (b-c) comprising polyether chain, also includes making diethanolamine and poly- (oxygen Alkylidene) acrylate occur Michael's addition method.Its concrete example is as follows.
Based on the compound being illustrated in lower-left, the structure of bottom right example can be imported in polyurethane dispersant (b-1).Should Structure is equivalent to the part-structure shown in above-mentioned formula (3-1).
[chemical formula 59]
In above-mentioned formula, * represents the bonding position with the carbonyl of the amino-formate bond in the polyurethane skeleton of main chain.
In addition, in the case of having the part-structure shown in formula (3-2), available following methods obtain.
It is 1 in 2 functional groups of the side end reacting with NCO of the compound (b-c) comprising polyether chain In the case of hydroxyl and 1 imino group, may also be employed and import 1 hydroxyl and 1 imino group in the above-claimed cpd (b-b) The same method of method.Specifically, can have 1 hydroxyl and ethylenically unsaturated group by making Hydroxyethyl Acrylate etc. The compound that compound and the end in polyoxy alkylidene chain have 1 primary amino radical occurs Michael's addition to obtain.Thus, may be used Obtain by ethylenically unsaturated group and amino through 1 hydroxyl in imino group and hydroxy acrylate obtained from Michael's addition Base.
In addition, it is equally possible that by monoethanolamine etc. have 1 hydroxyl and primary amino radical compound and with oxidation Alkylidene chain becomes the Michael that acrylate of ester bond etc. has the compound of alkylidene oxide chain and ethylenically unsaturated group to add Become, thus obtaining hydroxyl and the imino group that the solvophilic portion of alkylidene oxide is reacted with NCO.Such compound Including following compounds.
For example, the knot of bottom right example can based on the compound being illustrated in lower-left, be imported in polyurethane dispersant (b-1) Structure.This structure is equivalent to the part-structure shown in formula (3-2).In addition, as long as the part-structure shown in contained (3-2) And there is 1 hydroxyl and 1 imino group, then it is applicable to the synthesis of polyurethane dispersant (b-1).
[chemical formula 60]
The * adjacent with oxygen atom represent with the carbonyl of the amino-formate bond in the polyurethane skeleton of main chain be bonded position Put, the * adjacent with nitrogen-atoms represents the bonding position with the carbonyl of the urea bond in same skeleton.
In addition, in the case of being equivalent to the structure of the part-structure shown in above-mentioned formula (3-3), similarly having has The effect of effect, is applicable to the synthesis of polyurethane dispersant (b-1-1).
The compound importing the part-structure shown in above-mentioned formula (3-3) is the compound in side end with 2 hydroxyls. Part-structure shown in above-mentioned formula (3-3) for example can have polyethers, diisocyanate cpd and the sulfur of 1 hydroxyl using end Obtain for glycerol.Its specific reaction is for example lower described.
First, end is made to have hydroxyl and toluene di-isocyanate(TDI) of the polyethers of 1 hydroxyl etc. containing 2 isocyanates One NCO reaction of compound.Then, another NCO and thioglycerol etc. are made containing 1 active mercaptan The active mercapto reaction of base and at least compound of 2 activity hydroxies.Thus, can get the side end in polyethers to be imported with The compound of 2 hydroxyls.
For example, the knot of bottom right example can based on the compound being illustrated in lower-left, be imported in polyurethane dispersant (b-1) Structure.This structure is equivalent to the part-structure shown in formula (3-3).
[chemical formula 61]
In above-mentioned formula, * represents the bonding position with the carbonyl of the amino-formate bond in the polyurethane skeleton of main chain.
The compound that structure shown in above-mentioned formula (3-3) imports polyurethane dispersant (b-1) is that have 2 in side end The compound of individual hydroxyl, but 2 oxygen atoms in the part-structure shown in above-mentioned formula (3-3) are by 2 primary amino radicals and/or secondary amino group The compound replacing can also be suitable for use as compound (b-c) used in the synthesis of polyurethane dispersant (b-1).
Used in the synthesis of the polyurethane dispersant (b-1) comprising polyester chain in solvophilic group, compound (b-c) is excellent 2 hydroxyls reacting with NCO are contained in the one end being selected in the compound comprising polyester chain.Its hydroxyl preferably up to separates 17 atoms.Particularly preferred 2 hydroxyls separate more than 5 atoms.
The end of polyester chain be hydroxyl situation and for carboxyl situation any in the case of, all can side end End imports 2 hydroxyls reacting with NCO.
In the case that the end of polyester chain is hydroxyl, can be by the hydroxyl as chain termination compound described below One or more hydroxy carboxylic acid or its lactone polymerisation is made to manufacture in the presence of compound.
It is used and be preferably following formula as polyester obtained from the hydroxy-containing compounds of chain termination compound described below (4) polyester shown in.
R9O(OC-A-O)wH (4)
In formula (4), w is 5～150, R9For the alkyl of carbon number 1～50, A be carbon number 1～26 alkylidene or The alkenylene of carbon number 2～26.
For side end 2 hydroxyls reacting with NCO of importing to the compound of formula (4), can adopt with front The side end to polyethers of face narration imports the method identical method of 2 hydroxyls.
In addition, the side end to the compound of formula (4) imports 1 hydroxyl reacting with NCO and 1 imido The method that the method for base may also be employed importing 1 hydroxyl and 1 imino group with the side end above describing to polyethers.
For example, the knot of bottom right example can based on the compound being illustrated in lower-left, be imported in polyurethane dispersant (b-1) Structure.This structure is equivalent to the part-structure shown in above-mentioned formula (3-1) or the part-structure shown in formula (3-2).In addition, as long as Be comprise the part-structure shown in above-mentioned formula (3-1) or the part-structure shown in formula (3-2) and its end only have 2 with The functional group such as the hydroxyl of NCO reaction or imino group, then go for polyurethane dispersant (b-1).
[chemical formula 62]
The * adjacent with oxygen atom represent with the carbonyl of the amino-formate bond in the polyurethane skeleton of main chain be bonded position Put, the * adjacent with nitrogen-atoms represents the bonding position with the carbonyl of the urea bond in same polyurethane skeleton.
In addition, in the case of being equivalent to the structure of the part-structure shown in above-mentioned formula (3-3), it may have effectively Effect, is applicable to polyurethane dispersant (b-1).
For the structure being equivalent to the part-structure shown in the above-mentioned formula (3-3) comprising polyester chain, may also be employed with phase Identical structure when explanation in the structure comprising the part-structure shown in the above-mentioned formula (3-3) of polyether chain.
For example, the knot of bottom right example can based on the compound being illustrated in lower-left, be imported in polyurethane dispersant (b-1) Structure.This structure is equivalent to the part-structure shown in above-mentioned formula (3-3).
[chemical formula 63]
In above-mentioned formula, * represents the bonding position with the carbonyl of the amino-formate bond in the polyurethane skeleton of main chain.
The end of polyester chain be carboxyl in the case of, can by as chain termination compound described below containing carboxyl One or more hydroxy carboxylic acid or its lactone polymerisation is made to manufacture in the presence of compound.
It is used and be preferably following formula as polyester obtained from the carboxylated compound of chain termination compound described below (5) polyester shown in.
R9CO(O-A-CO)wOH (5)
In formula (5), R9, A and w identical with the definition of above-mentioned formula (4).
The polyester of formula (4) and/or formula (5) generally can by making one or more hydroxy carboxylic acid in inert atmosphere, esterification In the presence of catalyst, jointly react and manufacture in 50～250 DEG C with hydroxy-containing compounds or carboxylated compound.Typical work Sequence condition is recorded in International Publication No. 2001/80987.
For 2 hydroxyls reacting with NCO to the side end importing of the compound of above-mentioned formula (5), can make The compound of formula (5) and the diol reaction such as ethylene glycol or propylene glycol and be converted into monohydroxy compound, and be directed to gained list hydroxyl Radical derivative, is carried out using the compound identical method with formula (4).
For example, the knot of bottom right example can based on the compound being illustrated in lower-left, be imported in polyurethane dispersant (b-1) Structure.This structure is equivalent to the part-structure shown in above-mentioned formula (3-1) or the part-structure shown in formula (3-2).
In addition, as long as comprise the part-structure shown in above-mentioned formula (3-1) or the part-structure shown in formula (3-2), And in its end, only be there is the functional groups such as 2 hydroxyls being reacted with NCO or imino group, then it is applicable to polyurethane and divide The synthesis of powder (b-1).
[chemical formula 64]
In above-mentioned formula, the * adjacent with oxygen atom represents the carbonyl with the amino-formate bond in the polyurethane skeleton of main chain Bonding position, the * adjacent with nitrogen-atoms represent the bonding position with the carbonyl of the urea bond in same polyurethane skeleton.
In addition, in the case of being equivalent to the structure of the part-structure shown in above-mentioned formula (3-3), it may have effectively Effect, is applicable to the synthesis of polyurethane dispersant (b-1).
For the structure being equivalent to the part-structure shown in the above-mentioned formula (3-3) comprising polyester chain, may also be employed with phase Identical structure when explanation in the structure comprising the part-structure shown in the above-mentioned formula (3-3) of polyether chain.
In addition, the method for the functional group reacted with NCO to the end importing of polyether chain and/or polyester chain also may be used With using other well known method.For example, following methods etc. are also included：Can be by making with NCO and acryloyl-oxy The compound of base forms amino-formate bond with having the polyethers of 1 hydroxyl or polyester chain reaction in side end, thus The side end with the compound of polyether chain or polyester chain imports unsaturated group, and makes itself and diethanolamine carry out Michael Addition.With it, 2 hydroxyls can also be imported to the side end of polyether chain or polyester chain.
The main chain with polyurethane skeleton, the side of the solvophilic group being bonded with polyether chain and/or polyester chain as side Chain and the urethanes (b-1-1) of specific adsorption group, in the range of its characteristic will not being impacted, Can be polyacrylate and/or the polyene hydrocarbon reaction making to have 2 functional groups reacted with NCO in side end Obtained from compound.
In order to import 2 functional groups reacted with NCO to polyacrylate and/or polyolefinic side end, Can using above-mentioned end to polyether chain or polyester chain import 2 hydroxyls method or with import 1 hydroxyl and 1 imino group In the case of identical method.
In addition, when synthesizing polyacrylate and/or polyolefinic polymer, can be by using having the poly- of 2 hydroxyls Close the dihydroxy functionality chain-transferring agent such as initiator or thioglycerol and obtain.
By above-mentioned become side end have 2 functional groups reacted with NCO polyacrylate and/ Or the reaction of the NCO of polyolefinic compound and diisocyanate cpd (b-a), can be formed and be bonded to poly- ammonia The horizontal polyacrylate of ester skeleton side and/or polyolefin chain.
[the arbitrary other structures optionally comprising in polyurethane dispersant (b-1)]
Additionally, polyurethane dispersant (b-1) can also contain can be by following compound (b-d), (b-e), (b-f) Urethane reaction, urea reaction and the structure that imports.
Compound (b-d)：There is the one kind or two or more of the compound of 2 functional groups reacting with NCO.
Compound (b-e)：Comprise 1 functional group reacting with NCO and play a role as chain terminating agent Compound one kind or two or more.
Compound (b-f)：Comprise 1 NCO and a kind or 2 of compound played a role as chain terminating agent More than kind.
From these compounds (b-d), (b-e), (b-f) structure can by make these compounds (b-d), (b-e), (b-f) jointly react with compound (b-a), (b-b), (b-c) and be directed into the polyurethane bone of polyurethane dispersant (b-1) Frame.
More specifically, can be directed in polyurethane skeleton from the structure of compound (b-d), from compound (b-e), (b-f) structure can import two ends of polyurethane skeleton.
Above-claimed cpd (b-d) preferably only has 2 functional groups reacted with NCO.
The preferred functional group of compound (b-d) is amino or hydroxyl, more preferably diamidogen or glycol, more preferably two Alcohol.Compound (b-d) is mainly used as changing the deliquescent chain extender of polyether polyols.The number of compound (b-d) Average molecular weight is not particularly limited, but preferably 32～3,000.
The example of preferably diamidogen is：Ethylenediamine, 1,4- butanediamine and 1,6- hexamethylene diamine.The example of preferably glycol is： 1,6-HD, 1,4 cyclohexane dimethanol (CHDM), 1,2- dodecanediol, 2- phenyl -1,2- propylene glycol, 1,4- benzene diformazan Alcohol, 1,4- butanediol and neopentyl glycol.
Glycol can also be the polyethers such as poly- (C2～4- aklylene glycol), polyester or polyacrylic acid glycol.Polyalkylene two Alcohol can be the homopolymer comprising repeated oxidation ethylidene, oxypropylene or oxybutylene comprising its mixture or Random or block copolymer.
Lower-left example goes out the several of compound (b-d), thus, it is possible to import bottom right in urethanes (b-1-1) Part-structure.
[chemical formula 65]
H-OCH2CH2CH2CH2CH2CH2O-H *-OCH2CH2CH2CH2CH2CH2O-*
H2N-CH2CH2-NH2*-HN-CH2CH2-NH-*
H2N-CH2CH2CH2CH2CH2CH2-NH2*-HN-CH2CH2CH2CH2CH2CH2-NH-*
In above-mentioned formula, the * adjacent with oxygen atom represents the carbonyl with the amino-formate bond in the polyurethane skeleton of main chain Bonding position, the * adjacent with nitrogen-atoms represent the bonding position with the carbonyl of the urea bond in same polyurethane skeleton.
In addition, as long as only having 2 functional groups reacted with NCO, then can be suitable for use as can will be above-mentioned Part-structure imports the compound (b-d) of polyurethane dispersant (b-1).
Polyurethane skeleton in polyurethane dispersant (b-1) preferably substantially has the characteristic of straight chain.But, in any one-tenth In the case of there is polyhydric alcohol or the polyisocyanates that the degree of functionality as impurity is more than 2 in point, import a small amount of dividing sometimes Prop up structure.
As in following disclosures, the chain termination compound as compound (b-e) is that have and NCO The compound of the simple function of 1 functional group of reaction.The simple function group of compound (b-e) is preferably amino or hydroxyl.Compound (b-e) it is bonded to the end of the polyurethane skeleton of main chain of polyurethane dispersant (b-1) and become end group.
Preferably chain termination compound can be enumerated：Use with the compound (b-c) constituting polyurethane dispersant (b-1) Identical polyalkylene oxide monoalkylether, polyalkylene oxide monoalkylether amine or the compound shown in above-mentioned formula (4) end group Petchem for hydroxyl.
Lower-left example goes out compound (b-e), thus, it is possible to import the part knot of bottom right in polyurethane dispersant (b-1) Structure.
[chemical formula 66]
C4H9(OCH2CH3CH)nO-H C4H9(OCH2CH3CH)nO-*
C3H7(OCH2CH2)n-O-H C3H7(OCH2CH2)n-O-*
C12H25(OOCC5H10)n-O-H C12H25(OOCC5H10)n-O-*
C12H25-O-(C5H10OCO)n-C2H4O-H C12H25-O-(C5H10OCO)n-C2H4O-*
In above-mentioned formula, * represents the bonding position with the carbonyl of the amino-formate bond in the polyurethane skeleton of main chain.
In addition, as long as only be there is 1 functional group reacted with NCO in side end, then can be suitable for use as Above-mentioned part-structure can be imported the compound (b-e) of polyurethane dispersant (b-1).
From the viewpoint of dispersibility and dispersion ageing stability, compound (b-e) preferably comprises polyether chain and/or polyester The solvophilic group of chain, but in addition, as long as only having 1 hydroxyl, 1 primary amino radical, 1 secondary amino group or 1 mercapto Compound, then there is chain termination, compound (b-e) can be suitable for use as.
As above-claimed cpd (b-e) it is also possible in the model that the effect of polyurethane dispersant (b-1) will not be impacted In enclosing, replace having the compound of solvophilic group of polyether chain and/or polyester chain and using having same structure Polyacrylate or polyolefin.
The monoisocyanate compound of compound (b-f) also can play a role as chain termination compound, is bonded to work Two ends for the straight chain polyurethane skeleton of the main chain of polyurethane dispersant (b-1).Monoisocyanates as compound (b-f) The concrete example of compound, including carbanil, once but this compound residual, may need to carry out post processing, therefore preferably Carry out chain termination using (b-e) compound.
[synthesis of polyurethane dispersant (b-1)]
With respect to the gross mass of the whole raw material of polyurethane dispersant (b-1), typical case during synthesis of polyurethane dispersant (b-1) Raw material usage amount be：The compound (b-a) of 10～50 mass %, the compound (b-b) of 1～24 mass %, 10～80 matter The compound (b-c) of amount %, the compound (b-d) of 0～25 mass %, the compound (b-e) of 0～50 mass % and 0～20 matter The compound (b-f) of amount %.
Constitute the compound (b-c) of horizontal side chain in polyurethane dispersant (b-1) and two ends constituting polyurethane skeleton The mass ratio of the compound (b-e) at end is preferably more than the 35% of the gross mass of the whole raw material of polyurethane dispersant (b-1).
Can also separately inclusion compound (b-c) and compound (b-e) the compound and the bag that comprise polyether chain Compound containing polyester chain, but preferably comprise both simultaneously.The compound just comprising polyether chain and the compound comprising polyester chain Quality ratio for, with respect to the gross mass of compound (b-c) and compound (b-e), preferably 1:99～99:1st, more preferably For 3:97～97:3rd, more preferably 5:95～95:5.
When polyurethane dispersant (b-1) comprises polyether chain and polyester chain as solvophilic group, forming thin slice (tablet) or during high fine rule light filter BM, in formation process with respect to alkaline developer patience or high-temperature process when patience meeting Become more good, therefore preferably.In addition, the adsorption group of polyurethane dispersant (b-1) is the specific suction being bonded with main chain During attached group, specific adsorption group can fully be adsorbed in pigment, thus easily will have patience or height with respect to developer solution The pigment of patience when temperature is processed is pulled into therefore particularly preferably.
Polyurethane dispersant (b-1) can be prepared using the arbitrary known method being known in the art.In general, it is poly- Urethane dispersant (b-1) can by under the conditions of substantially anhydrous, generally in the inert atmosphere of 0～130 DEG C of temperature, appoint In the presence of being selected in atent solvent and optionally in the presence of a catalyst, make one kind or two or more diisocyanate cpd (b-a) at least react and obtain with one kind or two or more compound (b-b) and one kind or two or more compound (b-c).
Alternatively, it is also possible to one or more compounds (b-d) optionally and as chain extender generation effect and compound (b-e) and compound (b-f) i.e. as chain termination compound generation effect one or more compound common implementings any anti- Should.
For inert atmosphere, it is possible to use arbitrarily non-active gas carrying out, preferably nitrogen.
The preparation of polyurethane dispersant (b-1) can be implemented in the presence of a catalyst.Particularly a preferred catalyst is two The tin complex of fatty acid or the tertiary amines such as butyl tin dilaurate (DBTDL).
During synthesis of polyurethane dispersant (b-1), Carbimide. in the compound entirety being reacted in synthesis by adjustment Ester group and the ratio of the molal quantity of functional group reacting with NCO, can form various products.
In oneainstance, the total mole number that can make the NCO in compound (b-a) is less than compound (b- B), (b-c) and the compound (b-d) using as needed, the total moles of the functional group reacted with NCO of (b-e) Number.Should in the case of, exist all terminal isocyanate groups all react, will not the inclining of remaining unreacted terminal isocyanate group To.
Or it is also possible to make always rubbing of the NCO being provided by compound (b-a) and arbitrary compound (b-f) Your number be more than compound (b-b), (b-c) and the compound (b-d) using as desired, (b-e) anti-with NCO The total mole number of the functional group answered.Should in the case of, there are gained urethanes (b-1-1) and become and comprise residual isocyanate The tendency of the prepolymer of base.
Therefore, for this prepolymer, can optionally before being dissolved in solvent so as to from and different prepolymer chain Other chain extender such as compound (b-d) of bonding and/or compound (b-e) i.e. chain termination compound reaction.
In addition, in the case of there is the prepolymer comprising residual isocyanate base, chain extending reaction can be come using water itself Implement.Or, it is possible to use polyhydric alcohol, amino alcohol, first or second aliphatic, ester ring type, aromatic series or heterocyclic polyamines, spy Be not diamidogen, hydrazine or replace hydrazine and implement.
As chain extender, generally can enumerate and for example as described below be there are more than 2 senses reacted with NCO The chain extender of group, but in order to keep the carbamate skeleton of straight chain, preferably only be there are 2 senses reacted with NCO The chain extender of group.
As the chain extender being typically used, can enumerate for example：Ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, Cyclohexylidene diamidogen, piperazine, 2- methyl piperazine, phenylenediamine, toluenediamine, benzene dimethylamine, 4,4 '-di-2-ethylhexylphosphine oxide (2- chlorobenzene Amine), 3,3 '-two chloro- 4,4 '-benzidines, 2,6- diamino-pyridine, 4,4 '-diaminodiphenyl-methane, methane diamidogen, Azines such as benzene dimethylamine, isophorone diamine, hydrazine, dimethylhydrazine etc..
As chain extender used in there is the synthesis of polyurethane dispersant (b-1) of straight chain polyurethane skeleton, preferably Only be there is the chain extender of 2 functional groups reacted with NCO, particularly preferred hexamethylene diamine.
Chain extending reaction can be carried out under the arbitrary temp in high temperature, low temperature and room temperature.Preferably temperature is about 5～95 ℃.
In the case of adopting prepolymer method in the preparation of polyurethane dispersant (b-1), in order to control gained polyurethane to divide The molecular weight of powder (b-1), can be adjusted to the amount of chain extender and chain termination compound.
The molal quantity of the functional group reacted with NCO in chain extender and the free isocyanate groups in prepolymer Molal quantity of substantially equal in the case of, easily reach high molecular.And in order to obtain the polyurethane dispersant (b- of low-molecular-weight 1), in the reaction with polyurethane prepolymer, increase chain terminating agent etc. in the combining of chain extender and chain terminating agent and be adjusted ?.
In order to control viscosity, can generate polyurethane dispersant (b-1) or its prepolymer before, add therebetween or thereafter Atent solvent.As preferred solvent, can enumerate for example：Acetone, butanone, dimethylformamide, dimethyl acetylamide, two sweet Diethylene glycol dimethyl ether, N-Methyl pyrrolidone, butyl acetate, acetic acid methoxyl group propyl ester, ethyl acetate, ethylene glycol and propylene glycol oxalic acid The sterically hindered alcohol such as the alkyl ether of ester, ethylene glycol and propylene glycol acetate, toluene, dimethylbenzene and the tert-butyl alcohol and DAA.More Preferably solvent is ethyl acetate, butyl acetate, acetic acid methoxyl group propyl ester and N-Methyl pyrrolidone.
[physical property of polyurethane dispersant (b-1)]
From the viewpoint of dispersibility, the amine number in the solid constituent 1g of polyurethane dispersant (b-1) is preferably More than 10mgKOH/g, more preferably more than 20mgKOH/g.In addition, from the viewpoint of dispersibility, preferably 180mgKOH/g Below, it is more preferably below 110mgKOH/g, more preferably below 70mgKOH/g.
From the aspect of dispersion effect, the number-average molecular weight of polyurethane dispersant (b-1) is preferably 2, more than 000, more It is preferably 3, more than 000, particularly preferably 4, more than 000, from the viewpoint of dispersibility and lowering viscousity, preferably 50,000 Below, more preferably less than 40,000, more preferably less than 30,000, particularly preferably less than 20,000.
In addition, with respect to 100g polyurethane dispersant (b-1), solvophilic group is preferably more than 0.001 Morgan, more excellent Elect more than 0.005 Morgan as, more than more preferably 0.01 Morgan, more than particularly preferably 0.02 Morgan, in addition, Below preferably 0.5 Morgan, below more preferably 0.2 Morgan, below further preferred 0.1 Morgan, particularly preferably Below 0.08 Morgan.Hereinafter, represent this solvophilic group as solvophilic group content, with the unit of " Morgan/100g " Ratio.
It should be noted that described " Morgan " of solvophilic group refers to, for the solvophilic in feeding intake during synthesis The raw material of group, is worth divided by obtained from its number-average molecular weight with its inventory.In addition, using this solvophilic group " mole Root ", value corresponding for its 100g in overall with the inventory solid constituent amount beyond catalyst is defined as solvophilic base " Morgan/100g " of group.
<Other embodiment>
The other embodiment of the polyurethane dispersant (b-1) as the present invention, can enumerate non-linear, that is, have and comprise point Prop up the embodiment of the main chain of structure, it is, main chain has the embodiment that at least Zhi Huawei 3 pitches above branch.
In the present embodiment, as described later, it is in addition to have more than 1 at least Zhi Huawei 3 in main chain and pitch above point Beyond structure, the polyurethane skeleton with main chain is the close structure of embodiment of linear chain structure, thus it is considered that its Favorable dispersibility in photosensitive polymer combination.Can be additionally considered to, the alkali development in patterning or more than 200 DEG C of height During temperature is processed, synergistically improve alkali patience by combining with oxime ester Photoepolymerizationinitiater initiater (c-1) or alkali soluble resin (d) etc. And thermostability, thus can form high fine fine rule.
The polyurethane dispersant (b-1) of present embodiment if main chain except with the bonding part of solvophilic group and There is beyond the bonding part of adsorption group and adsorption group branched structure, be then not particularly limited, as this branched structure, can arrange It is exemplified below and state the part-structure shown in formula (ii).
[chemical formula 67]
In above-mentioned formula (II), ReRepresent 3 yuan of alcoholic compound residue, * represents bonding position.It should be noted that it is described Alcoholic compound residue refers to remove its residue obtained from hydrogen atom from whole hydroxyls of alcoholic compound.
The carbon number of 3 yuan of alcoholic compound residue in above-mentioned formula (ii) is not particularly limited, and preferably more than 1, more It is preferably more than 2, more preferably more than 3, additionally, it is preferred that being less than 100, being more preferably less than 50, more preferably Less than 10.More than for above-mentioned lower limit, there is the tendency that can form the branched structure with good stretching, extension, in addition, logical Cross as, below above-mentioned higher limit, existing and making dispersibility become good tendency.
As the concrete example of 3 yuan of alcoholic compound residue, can enumerate：Trimethylolethane, trimethylolpropane, 1,2,3- Glycerol, 1,3,5- penta triol, 1,5,10- last of the ten Heavenly stems triol, 1,2,3- trihydroxy benzene, 1,2,4- trihydroxy benzene, 1,3,5- trihydroxy Benzene and end have the alcoholic compound residue of the polyoxyalkylene compounds of 3 branches of 3 hydroxyls etc..From having good stretching, extension From the viewpoint of branchedness, preferably trimethylolethane, trimethylolpropane, Glycerin, 1,3,5- penta triols The alcoholic compound residue of alcoholic compound residue, more preferably trimethylolethane, trimethylolpropane or Glycerin.
As the concrete example of preferred 3 yuan of alcoholic compound residue, can be listed below.
[chemical formula 68]
In the middle of these, from the viewpoint of the branchedness with good stretching, extension, further preferred ReFor trimethylolethane Or the alcoholic compound residue of trimethylolpropane.
In addition, the main chain of the polyurethane dispersant (b-1) of present embodiment can also the bonding part with solvophilic group, Adsorption group and with the bonding part of adsorption group beyond comprise linear chain structure.As linear chain structure, preferably adopt above-mentioned formula (i) Shown part-structure.
In the case of being somebody's turn to do, the linear chain structure being comprised for main chain is not particularly limited with the ratio of branched structure, with respect to Linear chain structure and the total amount of branched structure, more than branched structure preferably 1 mass %, are more preferably more than 5 mass %, in addition, It is preferably below 100 mass %, be more preferably below 80 mass %, below further preferred 60 mass %.
More than for above-mentioned lower limit, exist and can improve polyester construction position or that polyether structure position is brought is molten The tendency of agent affinity, in addition, by below for above-mentioned higher limit, exist can reduce sterically hindered, can active adsorption in face The tendency of material.
In addition, the containing of the specific adsorption group of polyurethane dispersant (b-1) with regard to present embodiment, adsorption group Ratio, specific solvophilic group, the content ratio of solvophilic group, with transitivity, preferably adopt aforesaid those.
In addition, the manufacture method of the polyurethane dispersant (b-1) of present embodiment is except forming reaction in carbamate Beyond middle this one side using monomer more than a small amount of trifunctional, identical with the manufacture method above describing.By using three Monomer more than sense, can form several branch points on main chain.
As monomer more than trifunctional as used herein, polyhydric alcohol, polyamines or polyisocyanates can be enumerated, preferably polynary Alcohol or polyamines, particularly preferred polyhydric alcohol.
There is the tendency being susceptible to gelation in the polyurethane dispersant (b-1) of present embodiment, therefore preferably with will not The mode that gelation occurs synthesizes.From such a viewpoint, the number-average molecular weight of polyurethane dispersant (b-1) is preferably 40, Less than 000, more preferably less than 30,000.On the other hand, from the aspect of dispersion effect, polyurethane dispersant (b-1) Number-average molecular weight more preferably at least more than 3,000, more preferably at least more than 5,000.
The polyurethane dispersant (b-1) of present embodiment can pass through in the method above describing using compound (b- A ') and (b-d ') replace compound (b-a) and (b-d) and synthesize.
[chemical formula compound (b-a ')：Polyisocyanate compound]
As long as polyisocyanate compound (b-a ') contains the compound with more than 3 NCOs, then can make Polyurethane skeleton becomes branched structure, but preferably makes to branch into low branch.
The compound with more than 3 NCOs can also not only be comprised in polyisocyanate compound (b-a '), Also comprise above-mentioned diisocyanate cpd (b-a).In addition, using reacting with NCO containing having more than 3 In the case that the compound of the compound of functional group is as compound (b-d ') described below, polyisocyanate compound (b- A ') can also be only made up of diisocyanate cpd.
The average functional group number of polyisocyanate compound (b-a ') is preferably more than 2.0, additionally, it is preferred that for less than 2.5, More preferably less than 2.2.In addition, using containing the compound with more than 3 functional groups reacted with NCO In the case that compound is as compound (b-d '), the average functional group number of polyisocyanate compound (b-a ') is particularly preferably 2.0.
Here, in the case of there is the mixture of compound of different functional groups number, described average functional group number Refer to the meansigma methodss of its functional group number, available following formula calculates.
Average functional group number=
[summation of { (functional group number) × (there is the molal quantity of the compound of this functional group number) }]/(always the rubbing of compound That number)
Average functional group number be 2.0 compound (b-a ') identical with above-claimed cpd (b-a).
[chemical formula compound (b-d ')：There are more than 3 functional groups reacted with NCO thus being polyurethane skeleton Give the compound of branched structure]
Above-claimed cpd (b-d) has 2 functional groups reacted with NCO, thus forms the polyurethane bone of straight chain Frame, and compound (b-d ') is due at least containing the compound with more than 3 functional groups reacted with NCO, thus Branched structure can be imported by the polyurethane skeleton of this chain linked to owner.
Compound (b-d ') can also be had the compound of 2 functional groups reacted with NCO and have 3 The mixture of the compound of the functional group reacted with NCO above.Should in the case of, compound (b-d ') and Carbimide. The average of the functional group of ester group reaction is preferably more than 2.01, more preferably more than 2.1, additionally, it is preferred that for less than 4, more excellent Elect less than 3 as.
Be there is the compound of more than 3 functional groups reacted with NCO and by this in compound (b-d ') The concrete example of the part-structure of polyurethane dispersant (b-1) that compound brings is as described below.
As the low molecular weight polyols with more than 3 hydroxyls, can enumerate for example：Trimethylolpropane, tetramethylolmethane And dipentaerythritol etc..As the polyamines with more than 3 amino, can enumerate for example：Diethyl triamine, three (2- amino-ethyls) Amine, trien etc..
In addition, to carry out the synthesis of poly alkylene glycol or lactone by using having the compound of 3 or 4 hydroxyls Polymerization, can get preferred number average molecular weight is 200～2,000 triol or the oligomer compounds of tetrol, can be used as Compound (b-d ').As compound (b-d '), the preferably low molecular compound with 3 hydroxyls.
The particular instantiation of the compound with more than 3 functional groups reacted with NCO in compound (b-d ') Example is in lower-left, thus, it is possible to import the part-structure of bottom right in polyurethane dispersant (b-1).
[chemical formula 69]
In above-mentioned formula, the * adjacent with oxygen atom represents the carbonyl with the amino-formate bond in the polyurethane skeleton of main chain Bonding position, the * adjacent with nitrogen-atoms represents the bonding position with the carbonyl of the urea bond in the polyurethane skeleton of main chain, with sulfur The adjacent * of atom represents the bonding position with the thiourea key in the polyurethane skeleton of main chain.
In addition, as long as having the compound of more than 3 hydroxyls and/or primary amino radical, secondary amino group, then can suitably use Make compound (b-d ').
In addition, the number-average molecular weight of compound (b-d ') is preferably 32～3,000, these compounds can use a kind, Can use multiple.
Hereinafter, the amount for the NCO in compound (b-a '), (b-b), (b-c), (b-d '), (b-e) and with The amount of the functional group of NCO reaction illustrates.
Isocyanates in the polyurethane dispersant (b-1) of present embodiment substantially on be to be brought by compound (b-a ') 's.On the other hand, the functional group reacted with NCO can be brought by compound (b-b), (b-c), (b-d '), (b-e).Excellent Choosing as described below by the amount making these functional groups reach equal in the way of use these compounds.
{ the isocyanates radix in (b-a ') } × { molal quantity of (b-a ') }={ anti-with NCO in (b-b) The functional group number answered } × { molal quantity of (b-b) }+{ functional group number reacted with NCO in (b-c) } × { (b-c) Molal quantity+{ functional group number reacted with NCO in (b-d ') } × { molal quantity of (b-d ') }+{ in (b-e) The functional group number reacted with NCO } × { molal quantity of (b-e) }
It should be noted that in the case that the compound of (b-a ')～(b-e) is mixture, using the official of this mixture Can the average functional group number of group and the total mole number of mixture.
In addition, the preferred structure of the polyurethane dispersant (b-1) of present embodiment can be by using following compound And obtain.
Isocyanates radix in (b-a ')：2
(b-b) functional group number reacted with NCO in：2
(b-c) functional group number reacted with NCO in：2
The functional group number reacted with NCO in (b-d ')：Comprise the mixture of 2 and more than 3, averagely Functional group number at least more than 2.
(b-e) functional group number reacted with NCO in：1
The branched structure of the polyurethane dispersant (b-1) of present embodiment is preferably low order.Described low order can utilize following Definition representing.First, it is considered to remove the change playing a role as chain terminating agent in the functional group reacted with NCO Compound (b-b) beyond compound (b-e), (b-c), the average functional group number of (b-d ').Be defined as " except chain terminating agent with The average of the outer functional group reacted with NCO ".
" average of the functional group reacted with NCO in addition to chain terminating agent "=A/B
Wherein, A and B is as described below.
A={ functional group number reacted with NCO in (b-b) } × { molal quantity of (b-b) }+{ in (b-c) The functional group number reacted with NCO } × { molal quantity of (b-c) }+{ official reacting with NCO in (b-d ') Number can be rolled into a ball } × { molal quantity of (b-d ') }
B={ molal quantity of (b-b) }+{ molal quantity of (b-c) }+{ molal quantity of (b-d ') }
The polyurethane dispersant (b-1) that present embodiment can be made is " anti-with NCO in addition to chain terminating agent The urethanes that the average of the functional group answered " is more than 2.In order that it is " anti-with NCO in addition to chain terminating agent The average of the functional group answered " is more than 2, preferably uses the average of the compound reacting with the NCO of compound (b-d ') The compound that functional group number is more than 2.For this reason, so that compound (b-d ') is at least contained and there are more than 3 reacting with NCO Functional group compound.
The functional group reacted with NCO of compound (b-d ') is preferably hydroxyl, amino, particularly preferably hydroxyl. Compound (b-d ') can also be the mixture of several compounds.
In addition, " average of the functional group reacted with NCO in addition to chain terminating agent " preferably greater than 2.0 and For less than 3.0." average of the functional group reacted with NCO in addition to chain terminating agent " be preferably less than 2.6, more It is preferably less than 2.4, more preferably less than 2.3.
" average of the functional group reacted with NCO in addition to chain terminating agent " is preferably low order.By making " average of the functional group reacted with NCO in addition to chain terminating agent " is low order, exists and can suppress to be divided by polyurethane That powder (b-1) winding of itself causes and the alkali soluble resin in solvent or photosensitive polymer combination or optical polymerism The tendency of the compatibility poor of monomer.Additionally, there are can prevent from being caused by the winding of dispersant space bit resistive big thus The tendency that suppression is deteriorated to the adsorption of pigment.Thus it is intended to alkaline-resisting aobvious when dispersibility in a solvent, fine rule are formed Thermostability when shadow liquid patience and high-temperature process become well, the effect of the present invention can be given full play of.
It should be noted that the number-average molecular weight of the polyurethane dispersant (b-1) of present embodiment be preferably 3,000 with Above, more preferably 5, more than 000, and preferably 40, less than 000, more preferably 30, less than 000.
<Other dispersants>
Dispersant (b) in the photosensitive polymer combination of the present invention includes at least above-mentioned polyurethane dispersant (b-1), Will not because in the range of the effect of the present invention being impacted using polyurethane dispersant (b-1) it is also possible to be applied in combination poly- Other dispersants (b-2) beyond urethane dispersant (b-1).
As other dispersants (b-2), preferably macromolecule dispersing agent, further, from dispersion stabilization aspect, preferably There is carboxyl；Phosphate；Sulfonic group；Or their alkali；Primary amino radical, secondary amino group or tertiary amino；Quaternary ammonium salt base；Pyridine, pyrimidine or The macromolecule dispersing agent of the functional groups such as the nitrogen atom heterocyclic radical of pyrazine etc..Wherein, particularly preferably have primary amino radical, secondary amino group or Tertiary amino；Quaternary ammonium salt base；The macromolecule dispersing agent of the basic functionalities such as the nitrogen atom heterocyclic radical of pyridine, pyrimidine or pyrazine etc..
In addition, the macromolecule dispersing agent being applied in combination as other, can enumerate for example：Polyurethane dispersant (b-1) Carbamatess dispersant in addition, acrylic dispersants, polyethyleneimine amine dispersant, the dispersion of polyallyl amine Agent, the dispersant being formed by the monomer and macromonomer with amino, polyoxyethylene alkyl ether class dispersant, polyoxyethylene two Esters dispersant, polyethers phosphoric acid class dispersant, polyester phosphoric acid class dispersant, sorbitan esters of fatty race esters dispersant and fat Race's modified poly ester class dispersant etc..
The concrete example of the dispersant being applied in combination as such other, can enumerate：The EFKA being represented with trade name [registered trade mark, similarly hereinafter.EFKA company system], Disperbyk (registered trade mark, similarly hereinafter, BYK-Chemie company system), BYK- Disparlon (registered trade mark, similarly hereinafter, nanmu this chemical conversion Co. Ltd. system), SOLSPERSE (registered trade mark, similarly hereinafter, Lubrizol Company system), KP (Shin-Etsu Chemial Co., Ltd's system), Polyflow or Floren (Kyoeisha Chemical Co., Ltd.'s system), Ajisper (registered trade mark, similarly hereinafter, Ajinomoto Fine-Techno Co. Ltd. system) etc..
More specifically, can enumerate for example：EFKA-4046, -4047 (BASF AG's systems), Disperbyk-111, -161, - 162nd, -163, -166, -167, -182, -2000, -2001 (BYK-Chemie company systems), BYK-DisparlonDA-7301, ED-701 (nanmu this chemical conversion Co. Ltd. system), SOLSPERSE-22000, -24000,28000 (Lubrizol company system), Floren KDG-2400 (common prosperity KCC system) and Ajisper PB-821, -881 (Ajinomoto Fine- Techno Co. Ltd. system) etc..
In these macromolecule dispersing agents only a kind can be applied in combination it is also possible to combine with polyurethane dispersant (b-1) Using two or more.
Amino in above-mentioned other dispersants, preferably in addition to the polyurethane dispersant (b-1) with basic functionality Formate ester macromolecule dispersing agent and/or acrylic polymer dispersant, particularly preferred carbamatess macromolecule dispersion Agent.It is also preferable to there is basic functionality and there is polyester and/or the macromolecule dispersing agent of polyethers key.
If want specific example as carbamatess macromolecule dispersing agent preferred chemical constitution, example can be enumerated As：By making, toluene diisocyanate trimer is such to be had the polyisocyanate compound of more than 3 NCOs, divides There is in son the having the compound of solvophilic group or have chain extension of number-average molecular weight 300～10,000 of 1 or 2 hydroxyl The compound of base and same intramolecular have the weight average molecular weight obtained from compound reaction of 1 active hydrogen and tertiary amino 1,000～200,000 dispersion resin etc..
In such resin, the import volume that same intramolecular has the compound of active hydrogen and tertiary amino is preferably instead Amine number after answering is controlled in the amount of the scope of 1～100mgKOH/g.More preferably in the scope of 5～95mgKOH/g.
As such commercially available dispersant, including Disperbyk-161, -162, -163, -166, -167, -182 (BYK-Chemie company system) or EFKA-4046, -4047 (BASF AG's systems) etc..
In the present invention, amine number is using acid basic amine group to be neutralized with titration, and represented with the mg number of KOH and acid number Corresponding value, specifically, can be utilized following method to be measured.When amine number is less than above range, there is dispersibility The tendency declining, in addition, if exceeding above range, is then easily caused developability and reduces.
<The assay method of amine number>
Amine number becomes the quality table of the KOH of equivalent with the alkali number with the every 1g of solid constituent in addition to solvent in dispersant sample Show, can be measured by following methods.
Accurate weighing 0.5～1.5g dispersant sample in the beaker of 100mL, and the acetic acid using 50mL.Use Possesses the automatic titration device of pH electrode, using the HClO of 0.1mol/L4(perchloric acid) acetic acid solution is neutralized to this solution Titration.To titrate pH point of inflexion on a curve as titration end-point, obtain amine number using following formula.
Amine number [mgKOH/g]=(561 × V)/(W × S)
[wherein, W：Represent the dispersant sample amount of weighing [g], V：Represent in the titer [mL] of titration end-point, S：Represent and divide The solid component concentration [quality %] of powder sample.]
[Photoepolymerizationinitiater initiater (c)]
The Photoepolymerizationinitiater initiater (c) containing in the photosensitive polymer combination of the present invention is characterised by including at least oxime ester Photoepolymerizationinitiater initiater (c-1).
<Oxime ester Photoepolymerizationinitiater initiater (c-1)>
In the present invention, as Photoepolymerizationinitiater initiater (c), as the oxime of 9 oxime derivate class (oximes and oxime compound) Ester is effective, and its reason is as described below.
That is, in the present invention, it is used oxime ester Photoepolymerizationinitiater initiater (c-1) to draw as photopolymerization in photosensitive polymer combination When sending out agent (c), the specific polyurethane dispersant (b-1) as dispersant (b) is when light filter makes etc., with respect to alkali development The patience of liquid improves, and can suppress the thermal deformation in hot setting process behind, therefore, it is possible to be readily formed existing market The fine fine rule of upper required height.
As described above, polyurethane dispersant (b-1) can be utilized adsorption group or carbamate bone used in the present invention The position of frame captures pigment, good using the resin in the position and photosensitive polymer combination of polyester chain or polyether chain or monomer Ground compatible thus being mutually wound around, or, can by behind using ultraviolet, make photonasty by Photoepolymerizationinitiater initiater (c) The resin of resin combination or monomer crosslink, and thus make further as the resistance to alkali-developable of effect of the present invention and thermostability Improve.This effect can be by being applied in combination and obtaining into one polyurethane dispersant (b-1) and oxime ester Photoepolymerizationinitiater initiater (c-1) Step improves.
Particularly, ultraviolet be difficult to the substrate and thread pattern arriving at bonding portion or in ultraviolet exposure due to The presence of mask and lead to ultraviolet to be blocked thus the side surface part of thread pattern that weakens, by making oxime ester Photoepolymerizationinitiater initiater (c-1) coexist with polyurethane dispersant (b-1), alkaline developer patience and the effect of thermostability can be made synergistically to improve, thus It is readily formed high fine fine rule.
Further, since having structure, the transmission luminous energy absorbing ultraviolet in the structure of oxime ester Photoepolymerizationinitiater initiater (c-1) concurrently Structure and the structure producing free radical, therefore high and stable with respect to thermal response using sensitivity on a small quantity i.e., with a small amount of It is capable of the design of highly sensitive photosensitive polymer combination.Particularly, from the i ray with respect to exposure light source (365nm), from the viewpoint of light absorption, there is optionally substituted carbazyl and (there is the base of optionally substituted carbazole ring Group) oxime ester Photoepolymerizationinitiater initiater (c-1) in the case of can show its architectural characteristic well, thus more preferably.
At present, market require obscurity high, and on the other hand it is desirable to the BM (black matrix") of thin film, pigment concentration Become more and more higher.In this context, oxime ester Photoepolymerizationinitiater initiater (c-1) can give play to function effectively.
As the oxime compound of oxime ester Photoepolymerizationinitiater initiater (c-1), can enumerate and comprise the knot shown in following formulas (22) The compound of structure part, preferably enumerates the oxime ester compound shown in following formulas (23).
[chemical formula 70]
In above-mentioned formula (22), R22Represent respectively the alkanoyl of optionally substituted carbon number 2～12, carbon number 1～ 20 heteroarylalkanoyl, the enoyl- of carbon number 3～25, the cycloalkanoyl of carbon number 3～8, carbon number 3～20 Alkoxycarbonylalkanoyl, the phenyloxycarbonyl alkanoyl of carbon number 8～20, the Heteroaryloxycarbonyl of carbon number 3～20 Alkanoyl, the aminoalkylcarbonyl of carbon number 2～10, the aroyl of carbon number 7～20, the heteroaryl of carbon number 1～20 The aryloxycarbonyl of acyl group, the alkoxy carbonyl of carbon number 2～10 or carbon number 7～20.
[chemical formula 71]
In above-mentioned formula (23), R21aRepresent hydrogen atom or the alkyl of optionally substituted carbon number 1～20, carbon are former respectively The thiazolinyl of subnumber 2～25, the aryl of carbon number 6～20, the heteroaryl alkyl of carbon number 1～20, carbon number 3～20 Alkoxy carbonyl alkyl, the phenyloxycarbonyl alkyl of carbon number 8～20, the Heteroaryloxycarbonyl alkyl of carbon number 1～20 Or heteroaryl sulfanyl, the aminoalkyl of carbon number 1～20, the alkanoyl of carbon number 2～12, carbon number 3～25 Enoyl-, the cycloalkanoyl of carbon number 3～8, the aroyl of carbon number 7～20, the 4-hetaroylpyrazol of carbon number 1～20, The cycloalkyl alkane of the alkoxy carbonyl of carbon number 2～10, the aryloxycarbonyl of carbon number 7～20 or carbon number 6～20 Base.
R21bRepresent the arbitrary substituent group comprising aromatic ring or hetero-aromatic ring.
It should be noted that R21aCan also be with R21bIt is collectively forming ring, its link group can be enumerated optionally to have respectively and take The alkylidene of carbon number 1～10 of Dai Ji, poly- ethylidene [- (CH=CH)r-] or poly- ethynylene [- (C ≡ C)r-] or by The group that they combine.It should be noted that r is 0～3 integer.
R22aRepresent and the R in above-mentioned formula (22)22Same group.
Wherein, from the viewpoint of sensitivity, as the R in above-mentioned formula (22)22And the R in above-mentioned formula (23)22a, Preferably enumerate the alkanoyl of carbon number 2～12, the heteroarylalkanoyl of carbon number 1～20, the ring of carbon number 3～8 Alkanoyl, more preferably enumerates the alkanoyl of carbon number 2～10, further preferably enumerates the alkanoyl of carbon number 2～5.
As the R in above-mentioned formula (23)21a, from the viewpoint of dissolubility in a solvent, sensitivity, preferably arrange Lift the alkyl of optionally substituted carbon number 1～20, the cycloalkyl-alkyl of optionally substituted carbon number 1～10 or appoint The aryl of the substituted carbon number 6～20 of choosing.More preferably enumerate methyl, ethyl, propyl group, cyclopentyl ethyl, optionally by 4- (2- Methoxyl group -1- methyl) ethyoxyl -2- aminomethyl phenyl or N- acetyl group-N- acetoxyl group amino propyl group.
In addition, as the R in above-mentioned formula (23)21b, preferably enumerate optionally substituted carbazyl, optionally substituted Thioxanthene ketone group or optionally substituted thiophenyl.As R21bAnd in the case of containing the carbazyl optionally with substituent group, go out The reasons why above describing more preferably.In addition, the oxime ester initiator with the carbazyl with nitro is also effective.
As oxime ester Photoepolymerizationinitiater initiater (c-1), containing optionally substituted carbazyl as R21bWhen, for aforesaid Reason and more preferably.Further, preferably there is the carbazyl of at least one group in being selected from the group：Optionally substituted carbon is former The aryl of subnumber 6～25, the aryl carbonyl of optionally substituted carbon number 7～25, optionally substituted carbon number 5～25 Heteroaryl, the Heteroarylcarbonyl of optionally substituted carbon number 6～25 and nitro.Particularly, go out from the viewpoint of sensitivity Send out, preferably there is at least one group in benzoyl, toluyl, naphthoyl, thienyl carbonyl and nitro Carbazyl.When the substituent group that carbazyl optionally has is these groups, there are following tendencies：Will not be to Photoepolymerizationinitiater initiater Sensitivity causes appreciable impact, even if slightly impact can also be by adjusting the interpolation of light exposure or adjustment Photoepolymerizationinitiater initiater Measure and form desired fine rule.
In addition, from the viewpoint of effective transmission of the luminous energy absorbing, these groups are preferably bonded to 3 of carbazyl. Similarly, the C atom in above-mentioned formula (23) is preferably bonded to 6 of carbazyl.
In addition, the H atom being bonded to the N atom of carbazyl can also be replaced by arbitrary substituent group, as arbitrarily taking Dai Ji, from the viewpoint of dissolubility in a solvent, the preferably alkyl of carbon number 1～20, more preferably carbon number 1 ～10 alkyl, the alkyl of further preferred carbon number 1～5.
As the commercially available product of such oxime ester Photoepolymerizationinitiater initiater (c-1), including BASF AG OXE-02, Changzhou strength Electronics corporation's TR-PBG-304, TR-PBG-314 or ADEKA company system NCI-831 etc..
As in the present invention as oxime ester Photoepolymerizationinitiater initiater (c-1) preferred oxime ester compound, specifically can enumerate The compound of the example below, but it is not only restricted to these compounds completely.
[chemical formula 72]
[chemical formula 73]
[chemical formula 74]
[chemical formula 75]
On the other hand, as the ketoxime ester compound of oxime ester Photoepolymerizationinitiater initiater (c-1), can enumerate and comprise following formulas (24) compound of the structure division shown in, preferably enumerates the oxime ester compound shown in following formulas (25).
[chemical formula 76]
In above-mentioned formula (24), R24With the R in above-mentioned formula (22)22Synonymous.
[chemical formula 77]
In above-mentioned formula (25), R23aRepresent optionally substituted phenyl, the alkyl of carbon number 1～20, carbon atom respectively The thiazolinyl of number 2～25, the heteroaryl alkyl of carbon number 1～20, the alkoxy carbonyl alkyl of carbon number 3～20, carbon atom The phenyloxycarbonyl alkyl of number 8～20, the alkyl alkylthio base of carbon number 2～20, the Heteroaryloxycarbonyl of carbon number 1～20 Alkyl or heteroaryl sulfanyl, the aminoalkyl of carbon number 1～20, the alkanoyl of carbon number 2～12, carbon number 3～ 25 enoyl-, the cycloalkanoyl of carbon number 3～8, the aroyl of carbon number 7～20, the heteroaryl acyl of carbon number 1～20 Base, the cycloalkanes of the alkoxy carbonyl of carbon number 2～10, the aryloxycarbonyl of carbon number 7～20 or carbon number 6～20 Base alkyl.
R23bRepresent the arbitrary substituent group comprising aromatic ring or hetero-aromatic ring.
It should be noted that R23aCan also be with R23bIt is collectively forming ring, its link group can be enumerated optionally to have respectively and take The alkylidene of carbon number 1～10 of Dai Ji, poly- ethylidene (- (CH=CH)r-), poly- ethynylene (- (C ≡ C)r-) or by The group that they combine.It should be noted that r is 0～3 integer.
R24aRepresent the alkanoyl of optionally substituted carbon number 2～12, the enoyl- of carbon number 3～25, carbon respectively The cycloalkanoyl of atomic number 4～8, the benzoyl of carbon number 7～20, the 4-hetaroylpyrazol of carbon number 3～20, carbon number 2～10 alkoxy carbonyl, the aryloxycarbonyl of carbon number 7～20, the heteroaryl of carbon number 2～20 or carbon number 2 ～20 alkyl amino-carbonyl.
As the R in above-mentioned formula (24)24And the R in above-mentioned formula (25)24a, preferably enumerate carbon number 2～12 Alkanoyl, the virtue of the heteroarylalkanoyl of carbon number 1～20, the cycloalkanoyl of carbon number 3～8 or carbon number 7～20 Acyl group.
As the R in above-mentioned formula (25)23a, preferably enumerate unsubstituted ethyl, propyl group or butyl or by methoxyl group Ethyl or propyl group that carbonyl instead of.In addition, as the R in above-mentioned formula (25)23b, preferably enumerate optionally substituted click Oxazolyl, optionally substituted thiophenyl, and for that reason, more preferably as R23bAnd contain carbazyl.
As in the present invention as oxime ester Photoepolymerizationinitiater initiater (c-1) preferred ketoxime ester compound, specifically can arrange Lift the compound of the example below, but be not only restricted to these compounds completely.
[chemical formula 78]
[chemical formula 79]
As the commercially available product of such oxime ester Photoepolymerizationinitiater initiater (c-1), the OXE-01 manufacturing including BASF AG or normal TR-PBG-305 that state electronic strong company manufactures etc..
These oximes and ketoxime ester compound are known compound in itself, for example, Japanese Unexamined Patent Publication 2000-80068 public affairs A series of one of compounds described in report or Japanese Unexamined Patent Publication 2006-36750 publication.
Above-mentioned oxime ester Photoepolymerizationinitiater initiater (c-1) can be used alone a kind it is also possible to be applied in combination two or more.
<Other Photoepolymerizationinitiater initiaters>
Photoepolymerizationinitiater initiater (c) in the present invention includes at least above-mentioned oxime ester Photoepolymerizationinitiater initiater (c-1), but will not Because in the range of the effect of the present invention being impacted using oxime ester Photoepolymerizationinitiater initiater (c-1) it is also possible to be applied in combination oxime Other Photoepolymerizationinitiater initiaters (c-2) beyond ester Photoepolymerizationinitiater initiater (c-1).Furthermore it is also possible to adding as desired and making With additives such as accelerator, sensitizing dyestufves.
As other Photoepolymerizationinitiater initiaters (c-2), can enumerate for example：Japanese Unexamined Patent Application 59-152396 publication, Japan are special Open the metallocene compound comprising luxuriant titanium derivative class described in clear 61-151197 publication；Japanese Unexamined Patent Publication 2000-56118 United imidazole derivative number described in publication；Halomethylation described in Japanese Unexamined Patent Publication 10-39503 publicationDiazole derives N- aryl-alpha-amido the acids such as thing, halomethyl Striazine derivative, N-phenylglycine, N- aryl-a-amino acid salt, N- The free radical activators such as aryl-a-amino acid esters or alpha-aminoalkyl phenyl ketone derivatives；Etc..
Specifically, as luxuriant titanium derivative class, can enumerate for example：Titanocene dichloride, dicyclopentadienyl Double (2,3,4,5,6- phenyl-pentafluoride -1- base) titanium of diphenyl titanium, dicyclopentadienyl, double (the 2,3,5,6- tetrafluoro of dicyclopentadienyl Benzene -1- base) titanium, dicyclopentadienyl double (2,4,6- trifluoro-benzene -1- base) titanium, dicyclopentadienyl two (2,6- difluorobenzene -1- Base) titanium, dicyclopentadienyl two (2,4 difluorobenzene -1- base) titanium, double (2,3,4,5,6- five fluorine of two (methyl cyclopentadienyls) Benzene -1- base) titanium, two (methyl cyclopentadienyl) two (2,6- difluorobenzene -1- base) titanium and dicyclopentadienyl [the fluoro- 3- of 2,6- bis- (pyrroles's -1- base)-benzene -1- base] titanium etc..
In addition, as united imidazole derivative class, can enumerate for example：2- (2 '-chlorphenyl) -4,5- diphenyl-imidazole dimerization Body, 2- (2 '-chlorphenyl) -4,5- double (3 '-methoxyphenyl) imidazoles dimer, 2- (2 '-fluorophenyl) -4,5- diphenyl-imidazole Dimer, 2- (2 '-methoxyphenyl) -4,5- diphenyl-imidazole dimer and (4 '-methoxyphenyl) -4,5- diphenyl-imidazole Dimer etc..
In addition, as halomethylationOxadiazole derivative class, can enumerate for example：2- trichloromethyl -5- (2 '-benzofuran Base) -1,3,4-Diazole, 2- trichloromethyl -5- [β-(2 '-benzofuranyl) vinyl] -1,3,4-Diazole, 2- trichlorine Methyl -5- [β-(2 '-(6 "-benzofuranyl) vinyl)] -1,3,4-Diazole and 2- trichloromethyl -5- furyl -1,3, 4-Diazole etc..
In addition, as halomethyl Striazine derivative class, can enumerate for example：Double (the trichlorine of 2- (4- methoxyphenyl) -4,6- Methyl) s-triazine, double (trichloromethyl) s-triazine of 2- (4- methoxyl group naphthyl) -4,6-, 2- (4- ethoxynaphthyl) -4,6- be double (trichloromethyl) s-triazine and double (trichloromethyl) s-triazine of 2- (4- ethoxy carbonyl naphthyl) -4,6- etc..
In addition, as alpha-aminoalkyl phenyl ketone derivatives class, can enumerate for example：2- methyl isophthalic acid-[4- (methyl mercapto) benzene Base] -2- morpholinopropane -1- ketone, 2- benzyl -2- dimethylamino -1- (4- morpholino phenyl)-butanone -1,2- benzyl -2- two Methylamino -1- (4- morpholino phenyl) butane -1- ketone, 4- dimethyl aminoethyl benzoate, 4- dimethylamino isoamyl Yl benzoic acid ester, 4- diethyl amino benzoylformaldoxime, 4- dimethylamino propiophenone, 2- ethylhexyl -1,4- dimethylamino benzene Formic acid esters, 2,5- double (4- diethylamino benzal) Ketohexamethylene, 7- diethylamino -3- (4- diethylamino benzoyl) Coumarin and 4- (diethylamino) chalcone derivative etc..
Further, it is also possible to enumerate for example：Benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin are different The benzoin alkyl ethers such as propyl ether；The anthrones such as 2- methyl anthrone, 2- ethyl anthrone, 2- tert-butyl group anthrone, 1- chrloroanthracene ketone derive Species；Benzophenone, Michler's keton, 2 methyl benzophenone, 3- methyl benzophenone, 4- methyl benzophenone, 2- chlorodiphenyl first The benzophenone derivates classes such as ketone, 4- bromine benzophenone, 2- carboxyl benzophenone；2,2- dimethoxy -2- phenyl acetophenone, 2, 2- diethoxy acetophenone, 1- hydroxycyclohexylphenylketone, alpha-hydroxy-2-methylpropiophenone, 1- hydroxyl-1- Methylethyl- (p-isopropyl phenyl) ketone, 1- hydroxyl -1- (to dodecylphenyl) ketone, 2- methyl-(4 '-methyl mercapto phenyl) -2- morpholino - The acetophenone derivs classes such as 1- acetone, 1,1,1- trichloromethyl-(to butyl phenyl) ketone；Thiaxanthone, 2- ethyl thiaxanthone, 2- are different Propyl group thiaxanthone, CTX, 2,4- dimethyl thioxanthone, 2,4- diethyl thioxanthone, 2,4- diisopropylthioxanthone etc. Thioxanthone species；Spread out to (dimethylamino) ethyl benzoate, to benzoate such as (diethylamino) ethyl benzoate Biological species；The acridine derivatives classes such as 9- phenylacridine, 9- (p-methoxyphenyl) acridine；The fens such as 9,10- dimethylbiphenyl azophenlyene Oxazine derivatives class；Anthracyclinone derivatives class such as benzanthrone etc..
For these other Photoepolymerizationinitiater initiaters, it is also both can be only using a kind, it is possible to use two or more.
<Accelerator>
As accelerator, can enumerate for example：2-mercaptobenzothiazole, 2- sulfydryl benzoAzoles, 2-mercaptobenzimidazole etc. There is sulfhydryl compound or the multifunctional sulfhydryl compound of aliphatic of heterocycle etc..Accelerator can be used alone a kind it is also possible to group Conjunction uses two or more.
<Sensitizing dyestuff>
In order to improve induction sensitivity it is also possible to be applied in combination in Photoepolymerizationinitiater initiater (c) as desired and image The corresponding sensitizing dyestuff of the wavelength of exposure light source.As these sensitizing dyestufves, Japanese Unexamined Patent Publication 4-221958 public affairs can be enumerated Ton pigment described in report, Japanese Unexamined Patent Publication 4-219756 publication, Japanese Unexamined Patent Publication 3-239703 publication, same to 5- Described in No. 289335 publications, there is the coumarin pigment of heterocycle, Japanese Unexamined Patent Publication 3-239703 publication, same to 5-289335 Number the 3- oxo coumarin compound described in publication, the methylene lanaurin described in Japanese Unexamined Patent Publication 6-19240 publication, Additionally, Japanese Unexamined Patent Application 47-2528 publication, Japanese Unexamined Patent Application 54-155292 publication, Japanese Patent Publication 45- also can be enumerated No. 37377 publications, Japanese Unexamined Patent Application 48-84183 publication, Japanese Unexamined Patent Application 52-112681 publication, Japanese Unexamined Patent Application 58- No. 15503 publications, Japanese Unexamined Patent Application 60-88005 publication, Japanese Unexamined Patent Application 59-56403 publication, Japanese Unexamined Patent Publication 2-69 Number publication, Japanese Unexamined Patent Application 57-168088 publication, Japanese Unexamined Patent Publication 5-107761 publication, Japanese Unexamined Patent Publication 5-210240 Pigment with dialkyl amido benzene skeleton number described in publication, Japanese Unexamined Patent Publication 4-288818 publication etc..
In these sensitizing dyestufves, preferably sensitizing dyestuff containing amino is it is further preferred that have in same intramolecular Amino and the compound of phenyl.Particularly preferably for example：4,4 '-dimethylamino benzophenone, 4,4 '-diethylamino two Benzophenone, 2- aminobenzophenone, 4- aminobenzophenone, 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, The benzophenone compounds such as 3,4- diaminobenzophenone；2- (to dimethylaminophenyl) benzoAzoles, 2- are (to diethyl Aminophenyl) benzoAzoles, 2- (to dimethylaminophenyl) benzo [4,5] benzoAzoles, 2- (to dimethylaminophenyl) Benzo [6,7] benzoDouble (to the diethylamino phenyl) 1,3,4- of azoles, 2,5-Azoles, 2- (to dimethylaminophenyl) benzene And thiazole, 2- (to diethylamino phenyl) benzothiazole, 2- (to dimethylaminophenyl) benzimidazole, 2- are (to diethyl Aminophenyl) benzimidazole, 2,5- double (to diethylamino phenyl) 1,3,4- thiadiazoles, (to dimethylaminophenyl) pyrrole Pyridine, (to diethylamino phenyl) pyridine, (to dimethylaminophenyl) quinoline, (to diethylamino phenyl) quinoline, (to two Methylamino phenyl) pyrimidine, (to diethylamino phenyl) pyrimidine etc. contain to compound of dialkylaminophenyl etc..
Wherein, most preferably 4,4 '-dialkyl amido benzophenone.
Sensitizing dyestuff is also both to have can be used alone a kind it is also possible to be applied in combination two or more.
[alkali soluble resin (d)]
As the resin of the photosensitive polymer combination being applicable to the present invention, alkali soluble resin (d) can be adopted.This As long as alkali soluble resin (d) is to the photosensitive polymer combination being coated with the present invention containing this resin simultaneously used in bright After film is exposed obtained from drying, exposure portion and non-exposed portion can be made to occur with respect to the dissolubility of alkaline developer The resin of change is just not particularly limited, it is however preferred to have the alkali-soluble of at least one of carboxyl and ethylenically unsaturated group Resin (d-1), more preferably has the alkali soluble resin of carboxyl and ethylenically unsaturated group.
Specifically can enumerate for example：There is epoxy (methyl) acrylate and the acrylic copolymeric resin of carboxyl.As Preferably example, more specifically, can enumerate as epoxy (methyl) acrylate (D1-1) described below, epoxy (first Base) acrylate (D1-2), acrylic copolymeric resin (D2-1), acrylic copolymeric resin (D2-2), acrylic acid copolymer tree Fat (D2-3) and acrylic copolymeric resin (D2-4) and the resin recorded.These resins can use a kind, it is possible to use 2 kinds More than.
In above-mentioned, particularly preferably there is epoxy (methyl) acrylate of carboxyl.Its reason is as described below.
Alkali soluble resin (d) use in the present invention containing above describe there is carbamate skeleton and parent is molten It is compatible well in the polyurethane dispersant (b-1) of agent group and adsorption group and the photosensitive polymer combination of solvent (e), The polyether chain of polyurethane dispersant (b-1) and/or polyester chain and high molecular alkali soluble resin (d) become prevents color material (a) The space bit resistance part of cohesion, thus keep good dispersity.
In addition, make light filter when, there occurs well the compatible polyether chain of polyurethane dispersant (b-1) and/or Polyester chain and high molecular alkali soluble resin (d) can mutually be wound around, or, the adsorption group of polyurethane dispersant (b-1) or Polyurethane skeleton can be adsorbed in color material (a) and capture high color material (a) of patience, thus, at high temperature in alkali development or thereafter During reason, diminished by the etch based on alkaline developer or thermally-induced deformation.
In addition, when making light filter, in order that non-exposed portion is dissolved in alkaline developer, as adhesive resin, can adopt With having the alkali soluble resin of the acidic functionalities such as hydroxyl, carboxyl, phosphate, sulfonic group.Particularly, in alkali soluble resin In the case that there is carboxyl, compared with there is hydroxyl, there is the tendency being easier to be dissolved in alkaline developer.
In addition, phosphate or sulfonic acidity are higher than carboxyl, but it is sometimes prone to and the tool in photosensitive polymer combination Alkaline Photoepolymerizationinitiater initiater, photopolymerization monomer, dispersant, other additive is had to react and lead to storage stability to become Difference.
In addition, in the case that the acidic-group of alkali soluble resin is carboxyl, dispersion will not be impacted, with dispersant (b) affine weaker, there is the etch that can suppress to be caused by alkaline developer further in alkali development or high temperature behind By the tendency of thermally-induced deformation during reason.
Further, in the case that alkali soluble resin has ethylenically unsaturated group, there are following tendencies：By ultraviolet Irradiate and crosslink, so that the polyether chain of above-mentioned polyurethane dispersant (b-1) and/or polyester chain and alkali soluble resin D the mutual winding between () becomes more strong, the alkaline developer patience of ultraviolet irradiation portion and thermostability become very large.
In addition, in the case that alkali soluble resin (d) has ethylenically unsaturated group, being applied in combination polyurethane dispersant (b-1) improve further with the effect brought of oxime ester Photoepolymerizationinitiater initiater (c-1).
Particularly, ultraviolet be difficult to the substrate and thread pattern arriving at bonding portion or in ultraviolet exposure due to The presence of mask and lead to ultraviolet to be blocked thus the side surface part of thread pattern that weakens, by having olefinic unsaturated group The alkali soluble resin of group is applied in combination with polyurethane dispersant (b-1) and oxime ester Photoepolymerizationinitiater initiater (c-1), exists and can assist Improve together alkaline developer patience and thermostability, thus easily forming the tendency of high fine fine rule.
In addition, being used epoxy (methyl) acrylate solvable as the alkali with carboxyl and ethylenically unsaturated group In the case of property resin, more addition unsaturated group or carboxyl can be made in resin.In addition, aromatic ring can more be imported Structure or the sterically hindered big ester ring type structure of importing are such that it is able to make resistance to alkaline developer and thermostability improve further.
<Epoxy (methyl) acrylate>
As epoxy (methyl) acrylate with carboxyl, can enumerate for example：Following epoxy (methyl) propylene Acid ester resin (D1-1) and/or epoxy (methyl) acrylate (D1-2).
<Epoxy (methyl) acrylate (D1-1)>
By making α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester and epoxy resin addition, again Make itself and epoxy (methyl) acrylate obtained from the reaction of at least one of polyprotic acid and its anhydride.
<Epoxy (methyl) acrylate (D1-2)>
Make α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester and epoxy resin addition, make it again With polyhydric alcohol and epoxy (methyl) acrylate obtained from the reaction of at least one of polyprotic acid and its anhydride.
As becoming the former of epoxy (methyl) acrylate (D-1) and epoxy (methyl) acrylate (D-2) The epoxy resin of material, can enumerate for example：Bisphenol A type epoxy resin (for example, Mitsubishi chemical Co., Ltd's system " Epikote (registration Trade mark, similarly hereinafter) 828 ", " Epikote 1001 ", " Epikote 1002 ", " Epikote 1004 " etc.), bisphenol type epoxy tree Epoxide (for example, Nippon Kayaku K. K's system " NER-1302 " obtained from the alcohol hydroxyl group of fat is reacted with epichlorohydrin (76 DEG C of epoxide equivalent 323, softening point)), bisphenol F type resin (for example, Mitsubishi chemical Co., Ltd's system " Epikote 807 ", " EP-4001 ", " EP-4002 ", " EP-4004 etc. "), the alcohol hydroxyl group of bisphenol f type epoxy resin and epichlorohydrin reacted and obtain The epoxy resin (for example, Nippon Kayaku K. K's system " NER-7406 " (66 DEG C of epoxide equivalent 350, softening point)) that arrives, bisphenol S Type epoxy resin, biphenyl glycidyl ether (for example, Mitsubishi chemical Co., Ltd's system " YX-4000 "), phenol novolak type ring Oxygen tree fat (for example, Nippon Kayaku K. K's system " EPPN-201 ", Mitsubishi chemical Co., Ltd's system " EP-152 ", " EP-154 ", Dow chemical company system " DEN-438 "), (adjacent// to) cresol novolak type epoxy resin (for example, Japanese chemical medicine strain System " EOCN (the registered trade mark of formula commercial firm.Similarly hereinafter) -102S ", " EOCN-1020 ", " EOCN-104S "), isocyanuric acid three shrink sweet Grease (for example, Misao Kusano's system " TEPIC (registered trade mark) "), triphenol methylmethane type epoxy resin (for example, Japan " EPPN (the registered trade mark of chemical medicine Co. Ltd. system.Similarly hereinafter) -501 ", " EPN-502 ", " EPPN-503 "), alicyclic epoxy resin (Daisel chemical industry Co., Ltd's system " Celloxide (registered trade mark, similarly hereinafter) 2021P ", " Celloxide EHPE "), will Dicyclopentadiene and phenol reacted obtained from phenolic resin carry out glycidated epoxy resin (for example, DIC be public Department system " EXA-7200 ", Nippon Kayaku K. K's system " NC-7300 ") and following formula (d1)～(d4) shown in epoxy resin Deng.
Specifically can enumerate for example：Nippon Kayaku K. K system " XD- as the epoxy resin shown in following formulas (d1) 1000 ", the Nippon Kayaku K. K's system " NC-3000 " as the epoxy resin shown in following formulas (d2) and as following Nippon Steel Chemical Co., Ltd's system " ESF-300 " of epoxy resin shown in formula (d4) etc..
[chemical formula 80]
In above-mentioned formula (d1), b11 represents meansigma methodss, represents 0～10 number.R11Represent hydrogen atom, halogen atom, carbon atom The alkyl of number 1～8, the cycloalkyl of carbon number 3～10, phenyl, naphthyl or biphenyl.It should be noted that existing in 1 molecule Multiple R11Can identical can also be different.
[chemical formula 81]
In above-mentioned formula (d2), b12 represents meansigma methodss, represents 0～10 number.R21Represent hydrogen atom, halogen atom, carbon atom The alkyl of number 1～8, the cycloalkyl of carbon number 3～10, phenyl, naphthyl or xenyl.It should be noted that existing in 1 molecule Multiple R21Can identical can also be different.
[chemical formula 82]
In above-mentioned formula (d3), X represents the link group shown in following formulas (d3-1) or (d3-2).Wherein, molecule knot The adamantane structure of more than 1 is comprised, b13 represents 2 or 3 integer in structure.
[chemical formula 83]
In above-mentioned formula (d3-1) and (d3-2), R31～R34And R35～R37Represent that optionally there is substituent group independently of one another Adamantyl, hydrogen atom, the alkyl of carbon number 1～12 optionally with substituent group or the phenyl optionally with substituent group. In addition, the bonding position in symbol * expression (d3) in various.
[chemical formula 84]
In above-mentioned formula (d4), p and q represents 0～4 integer, R independently of one another41And R42Represent alkyl independently of one another Or halogen atom, R43And R44Represent alkylidene independently of one another, x and y represents more than 0 integer independently of one another.
In the middle of these, preferably use the epoxy resin representing with the arbitrary formula in formula (d1)～(d4).
As α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester, can enumerate for example：(methyl) Acrylic acid .beta.-methylacrylic acid, adjacent vinyl benzoic acid, a vinyl benzoic acid, to vinyl benzoic acid, (methyl) acrylic acid α position The monocarboxylic acids such as haloalkyl, alkoxyl, halogen atom, nitro, cyano group substituent, succinic acid 2- (methyl) acryloyloxyethyl ester, Adipic acid 2- (methyl) acryloyloxyethyl ester, phthalic acid 2- (methyl) acryloyloxyethyl ester, 2- (methyl) acryloyl-oxy Base ethyl ester, maleic acid 2- (methyl) acryloyloxyethyl ester, succinic acid 2- (methyl) acryloxy propyl ester, adipic acid 2- (first Base) acryloxy propyl ester, four hydrogen phthalate 2- (methyl) acryloxy propyl ester, phthalic acid 2- (methyl) acryloyl-oxy Base propyl ester, maleic acid 2- (methyl) acryloxy propyl ester, succinic acid 2- (methyl) acryloxy butyl ester, adipic acid 2- (first Base) acryloxy butyl ester, hydrogen phthalate 2- (methyl) acryloxy butyl ester, phthalic acid 2- (methyl) acryloxy Butyl ester, maleic acid 2- (methyl) acryloxy butyl ester, addition 6-caprolactone, beta-propiolactone, γ-fourth on (methyl) acrylic acid The monomer of the lactone such as lactone, δ-valerolactone or in (methyl) hydroxyalkyl acrylates, tetramethylolmethane three (methyl) The monomer of acid (anhydride) and (methyl) such as addition succinic acid (acid anhydride), phthalic acid (acid anhydride), maleic acid (acid anhydride) on acrylate Acrylic acid dimer etc..
In the middle of these, from the aspect of sensitivity, particularly preferably (methyl) acrylic acid.
As making α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester and epoxy resin addition Method, can adopt known method.For example, it is possible in the presence of esterification catalyst, make α in 50～150 DEG C of temperature, β-no Saturation monocarboxylic acid or the α with carboxyl, β-unsaturated monocarboxylic ester is reacted with epoxy resin.
As esterification catalyst as used herein, can be using for example：Triethylamine, trimethylamine, benzyldimethylamine, 2,4 and benzyl Quaternary ammonium salt such as the tertiary amines such as diethylamide and tetramethyl ammonium chloride, tetraethylammonium chloride, Dodecyl trimethyl ammonium chloride etc..
It should be noted that epoxy resin, α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester, And esterification catalyst all both can be used alone a kind it is also possible to be applied in combination two or more.
α, β-unsaturated monocarboxylic or the α with carboxyl, the usage amount of β-unsaturated monocarboxylic ester is with respect to epoxy resin Epoxy radicals 1 equivalent, preferably in the scope of 0.5～1.2 equivalent, further preferably in the scope of 0.7～1.1 equivalent.
α, β-unsaturated monocarboxylic or the α with carboxyl, when the usage amount of β-unsaturated monocarboxylic ester is few, unsaturated group Import volume not enough, and then lead to the reaction with polyprotic acid and/or its anhydride also to become insufficient.
In addition, remaining substantial amounts of epoxy radicals are not favourable.On the other hand, if this usage amount is many, α can be led to, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester remaining as unreacted reactant.In the case of arbitrarily Confirm the tendency of curing characteristicss variation.
As polyprotic acid and/or its anhydride, can enumerate be selected from maleic acid, succinic acid, itaconic acid, phthalic acid, four Hydrogen phthalate, hexahydro phthalic acid, Pyromellitic Acid, trimellitic acid, benzophenone tetrabasic carboxylic acid, methyl hexahydro phthalic acid, Endo-methylene group four hydrogen phthalate, chlorendic acid, methyl four hydrogen phthalate and biphenyltetracarboxyacid acid and these sour anhydride etc. In one kind or two or more.
Preferably maleic acid, succinic acid, itaconic acid, phthalic acid, four hydrogen phthalates, hexahydro phthalic acid, equal benzene tetramethyl Acid, trimellitic acid or biphenyltetracarboxyacid acid or these sour anhydride.Particularly preferred four hydrogen phthalates, biphenyltetracarboxyacid acid, tetrahydrochysene are adjacent Phthalate anhydride or biphenyl tetracarboxylic dianhydride.
Additive reaction with regard to polyprotic acid and/or its anhydride, it is possible to use known method, can with α, β-insatiable hunger With monocarboxylic acid or the α with carboxyl, under the conditions of β-unsaturated monocarboxylic ester is with respect to the additive reaction identical of epoxy resin, continue Continue reaction and obtain object.
The addition amount of polyprotic acid and/or its anhydride composition is preferably such that carboxylic epoxy (methyl) acrylic acid of generation The acid number of ester resin reaches the degree of 10～150mgKOH/g scope, more preferably make described acid number reach 20～ The degree of 140mgKOH/g scope.
When the acid number of carboxylic epoxy (methyl) acrylate is less than above range, there is alkali-developable deficiency Tendency, in addition, when exceeding above range, confirm the tendency of curing performance variation.
It should be noted that trihydroxy methyl third can also be added in the additive reaction synthesis of polyprotic acid and/or its anhydride The polyhydric alcohol such as alkane, tetramethylolmethane, dipentaerythritol and import multiple branching construction.
Epoxy (methyl) acrylate (D1-1), (D1-2) generally can be by epoxy resin and α, β-unsaturation Monocarboxylic acid or the α with carboxyl, in the reactant of β-unsaturated monocarboxylic ester mixing polyprotic acid and/or its anhydride after or To epoxy resin and α, β-unsaturated monocarboxylic or the α with carboxyl, in the reactant of β-unsaturated monocarboxylic ester, mixing is many After unit's acid and/or its anhydride and polyhydric alcohol, heated and obtained.
In the case of being somebody's turn to do, polyprotic acid and/or its anhydride are not particularly limited with the order by merging of polyhydric alcohol.By heating, many Unit's acid and/or its anhydride meeting and be present in epoxy resin and α, β-unsaturated monocarboxylic or the α with carboxyl, the single carboxylic of β-unsaturation There is additive reaction in any hydroxyl in the mixture of the reactant of acid esters and polyhydric alcohol.
If the usage amount of polyhydric alcohol is very few, effect is weak, if excessively, exist there is thickening or gelation can Can property, accordingly, with respect to epoxy resin ingredient with α, β-unsaturated monocarboxylic or ester moiety have the α, β-unsaturation of carboxyl The reactant of monocarboxylate's composition, usually about 0.01～0.5 mass times, is preferably about 0.02～0.2 mass times.
Epoxy (methyl) acrylate (D1-1) that so obtains, the acid number of (D1-2) be usually 10mgKOH/g with Upper, preferably more than 50mgKOH/g.When acid number is less than 10mgKOH/g, developability may be led to not enough.
In addition, if acid number is too high, then the alkali patience existing problems of photosensitive polymer combination (that is, can be due to alkali sometimes Property the presence of developer solution and cause rough surface or the film decrement of patterned surfaces), it is therefore preferable that acid number be 200mgKOH/g with Under, more preferably below 150mgKOH/g.
Epoxy (methyl) acrylate (D1-1), (D1-2) based on gel permeation chromatography (GPC) measure and obtain The weight average molecular weight (Mw) being converted into polystyrene be preferably more than 1,000, more preferably more than 1,500.Additionally, it is preferred that being Less than 10,000, more preferably less than 8,000, further preferred less than 6,000.Weight average molecular weight (Mw), can if too small The problem of sensitivity, coating strength or alkali patience aspect can be caused, if excessive, cause developability or re-dissolved sometimes The problem of aspect.
<Acrylic copolymeric resin>
As acrylic copolymeric resin, can be using for example in Japanese Unexamined Patent Publication 7-207211 publication, Japanese Unexamined Patent Publication 8- No. 259876 publications, Japanese Unexamined Patent Publication 10-300922 publication, Japanese Unexamined Patent Publication 11-140144 publication, Japanese Unexamined Patent Publication 11-174224 publication, Japanese Unexamined Patent Publication 2000-56118 publication, Japanese Unexamined Patent Publication 2003-233179 publication, Japanese Unexamined Patent Publication Various macromolecular compounds described in each publication such as 2007-270147 publication etc., but preferably following (D2-1)～(D2- 4) resin etc..Wherein, in the resin of (D2-1)～(D2-4), the resin of preferably (D2-1) and (D2-3).
(D2-1)：With respect to the copolymer of (methyl) acrylate containing epoxy radicals and other free radical polymerization monomers, Make the resin obtained from least a portion addition of epoxy radicals that unsaturated monoacid had with this copolymer or make polynary Anhydride and resin (the hereinafter also referred to " (D2- obtained from least a portion addition of the hydroxyl being generated by this additive reaction 1) resin ")
(D2-2)：Main chain contains the straight-chain alkali soluble resin (hereinafter also referred to " (D2-2) resin ") of carboxyl
(D2-3)：Make unsaturated compound containing epoxy radicals with obtained from the carboxy moiety addition of above-mentioned (D2-2) resin Resin (hereinafter also referred to " (D2-3) resin ")
(D2-4)：(methyl) acrylic resin (hereinafter also referred to " (D2-4) resin ")
It should be noted that above-mentioned (D2-1) resin is also included within the concept of epoxy (methyl) acrylate.
Hereinafter, illustrate for above-mentioned each resin.
<(D2-1) resin>
As (D2-1) with respect to (methyl) acrylate containing epoxy radicals and other free radical polymerization monomers copolymerization Thing, makes the resin obtained from least a portion addition of epoxy radicals that unsaturated monoacid had with this copolymer or makes Multi-anhydride and the resin obtained from least a portion addition of the hydroxyl being generated by this additive reaction, more specifically, can Enumerate：" rub with other free radical polymerization monomers 10～95 with respect to 5～90 moles of % of (methyl) acrylate containing epoxy radicals The copolymer of your %, makes 10～100 moles of % additions of epoxy radicals that unsaturated monoacid had with this copolymer obtain Resin or make multi-anhydride with obtained from 10～100 moles of % additions of hydroxyl being generated by this additive reaction Resin ".
As " (methyl) acrylate containing epoxy radicals " of constituting (D2-1) resin, can enumerate for example：(methyl) propylene Acid glycidyl ester, (methyl) acrylic acid 3,4- epoxy radicals butyl ester, (methyl) acrylic acid (3,4- epoxycyclohexyl) methyl ester, (first Base) acrylic acid 4- hydroxybutyl glycidyl ether etc..Wherein, preferably (methyl) glycidyl acrylate.These contain epoxy radicals (methyl) acrylate can be used alone a kind it is also possible to be applied in combination two or more.
As the other free radical polymerization monomers with above-mentioned (methyl) acrylic ester copolymer containing epoxy radicals, preferably have List (methyl) acrylate of structure shown in following formulas (11).
[chemical formula 85]
In above-mentioned formula (11), R81～R88Represent the alkyl of hydrogen atom or carbon number 1～3, R independently of one another87And R88 Can also be interconnected and form ring.In above-mentioned formula (11), by R87And R88The ring linking and being formed is preferably aliphatic ring, Can be any ring in saturated rings or unsaturation ring, preferably its carbon number is 5～6.
Wherein, as the structure shown in above-mentioned formula (11), preferably shown in following formula (11a), (11b) or (11c) Structure.
[chemical formula 86]
By importing these structures in alkali soluble resin, the photosensitive polymer combination of the present invention is being used for colour filter In the case of piece or image display device, its thermostability and intensity can be improved.
As list (methyl) acrylate with the structure shown in above-mentioned formula (11), as long as it is then permissible to have this structure Using various lists (methyl) acrylate, but list (methyl) acrylate shown in particularly preferably following formula (12).
[chemical formula 87]
In above-mentioned formula (12), R89Represent hydrogen atom or methyl, R90Represent the structure shown in above-mentioned formula (11).
In above-mentioned (methyl) acrylate containing epoxy radicals with the copolymer of other free radical polymerization monomers, it is being derived from In the repetitives of " other free radical polymerization monomer ", preferably comprise 5～90 moles of % from having above-mentioned formula (11) The repetitives of list (methyl) acrylate of shown structure, particularly preferably contain 15～50 moles of %.
It should be noted that as in addition to list (methyl) acrylate with the structure shown in above-mentioned formula (11) " other free radical polymerization monomer ", is not particularly limited.
(D2-1) above-mentioned (methyl) acrylate containing epoxy radicals in resin and above-mentioned other free radical polymerization monomer Copolymer, preferably by 5～90 moles of % of repetitives from (methyl) acrylate containing epoxy radicals with from other The copolymer that 10～95 moles of % of the repetitives of free radical polymerization monomer are formed, is particularly preferably 30～70 to be rubbed by the former The copolymer that your % and 70～30 moles of % of the latter is formed.
In (D2-1) resin, make unsaturated monoacid (polymerizable component) and multi-anhydride with above-mentioned containing epoxy radicals The epoxy radicals partial reaction of the copolymer of (methyl) acrylate and other free radical polymerization monomer.
Here, as " the unsaturated monoacid " with epoxy radicals addition, various monoacid can be used, for example, tool can be enumerated There is the unsaturated carboxylic acid of ethylenical unsaturated double bonds.As concrete example, can enumerate：(methyl) acrylic acid .beta.-methylacrylic acid, adjacent vinyl benzene Formic acid, a vinyl benzoic acid, to vinyl benzoic acid, alpha-position by haloalkyl, alkoxyl, halogen atom, nitro or cyano group etc. Monocarboxylic acids such as (methyl) acrylic acid replacing etc..Wherein, preferably (methyl) acrylic acid.These unsaturated monoacid are permissible It is used alone a kind it is also possible to be applied in combination two or more.By the such composition of addition, can give poly- for (D2-1) resin Conjunction property.
Generally make 10～100 moles of % additions of the epoxy radicals that these unsaturated monoacid and above-mentioned copolymer have, But 50～100 moles of % additions preferably with described epoxy radicals.
Further, as " many with the hydroxyl addition making to generate during the unsaturation monoacid of addition in the epoxy radicals of copolymer First anhydride ", can use various multi-anhydrides.Can enumerate for example：Maleic anhydride, succinic anhydrides, itaconic anhydride, phthalic acid The dibasic acid anhydrides such as acid anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride and chlorendic anhydride；Trimellitic anhydride, equal benzene tetramethyl The anhydride of the acid more than ternarys such as anhydride, benzophenone tetracarboxylic anhydride and biphenyltetracarboxyacid acid acid anhydride.Wherein, preferred tetrahydrochysene O-phthalic Anhydride and succinic anhydrides.These multi-anhydrides can be used alone a kind it is also possible to be applied in combination two or more.
By the such composition of addition, alkali-soluble can be given for (D2-1) resin.
Generally make these multi-anhydrides and pass through addition unsaturation monoacid in the epoxy radicals that above-mentioned copolymer has And 10～100 moles of % additions of the hydroxyl generating, preferably with 30～80 moles of % additions.
<(D2-2) resin>
Contain the straight-chain alkali soluble resin of carboxyl as (D2-2) main chain, as long as there is carboxyl just there is no special limit Fixed, typically by obtained from the polymerization of the polymerizable monomer containing carboxyl.
As carboxylic polymerizable monomer, can enumerate for example：(methyl) acrylic acid, maleic acid .beta.-methylacrylic acid, itaconic acid, Fumaric acid, succinic acid 2- (methyl) acryloyloxyethyl ester, adipic acid 2- (methyl) acryloyloxyethyl ester, maleic acid 2- (first Base) acryloyloxyethyl ester, hexahydro phthalic acid 2- (methyl) acryloyloxyethyl ester, phthalic acid 2- (methyl) acryloyl-oxy Base ethyl ester, succinic acid 2- (methyl) acryloxy propyl ester, adipic acid 2- (methyl) acryloxy propyl ester, maleic acid 2- (first Base) acryloxy propyl ester, hydrogen phthalate 2- (methyl) acryloxy propyl ester, phthalic acid 2- (methyl) acryloxy Propyl ester, succinic acid 2- (methyl) acryloxy butyl ester, adipic acid 2- (methyl) acryloxy butyl ester, maleic acid 2- (methyl) Acryloxy butyl ester, hydrogen phthalate 2- (methyl) acryloxy butyl ester and phthalic acid 2- (methyl) acryloxy fourth The vinyl monomers such as ester；Make acrylic acid and the lactone additions such as 6-caprolactone, beta-propiolactone, gamma-butyrolacton and δ-valerolactone Monomer；Make (methyl) hydroxyalkyl acrylates and succinic acid, maleic acid and phthalic acid and their anhydride etc. Monomer of acid or anhydride addition etc..These monomers can be used alone a kind it is also possible to be applied in combination two or more.
These, it is preferred to (methyl) acrylic acid or succinic acid 2- (methyl) acryloyloxyethyl ester, further preferred It is (methyl) acrylic acid.
In addition, (D2-2) resin can also be to make above-mentioned carboxylic polymerizable monomer to gather with the other without carboxyl The resin of conjunction property monomer copolymerization.In the case of being somebody's turn to do, as other polymerizable monomers, it is not particularly limited, Japan can be set forth in Monomer described in JP 2009-52010 publication etc..In addition, in these polymerizable monomers, from the side that pigment-dispersing is excellent Setting out in face, particularly preferably comprises the copolymer resin of (methyl) benzyl acrylate.
<(D2-3) resin>
The unsaturated compound containing epoxy radicals is made to obtain with the carboxy moiety addition of above-mentioned (D2-2) resin at (D2-3) Resin in, as the unsaturated compound containing epoxy radicals with the carboxy moiety addition of (D2-2) resin, as long as intramolecular There is ethylenically unsaturated group and the compound of epoxy radicals is just not particularly limited.
The unsaturated compound containing epoxy radicals as this, can enumerate for example：(methyl) glycidyl acrylate, pi-allyl Glycidyl ether, α-ethylacrylate ethylene oxidic ester, crotyl glycidyl ether, (different) .beta.-methylacrylic acid glycidyl Ether, N- (3,5- dimethyl -4- glycidyl) benzylacrylamide and (methyl) acrylic acid 4- hydroxybutyl glycidyl Ether etc. contains the unsaturated compound of non-ring type epoxy radicals.From the viewpoint of the dispersibility of thermostability and pigment, preferably following note The ester ring type carrying contains the unsaturated compound of epoxy radicals.
Here, as the ester ring type epoxy radicals of the unsaturated compound containing ester ring type epoxy radicals, can enumerate for example：2,3- ring Oxygen cyclopenta, 3,4- epoxycyclohexyl and 7,8- epoxy [three rings [5.2.1.0] decyl- 22- yl] base etc..In addition, as olefinic not Saturated group, is preferably derived from the ethylenically unsaturated group of (methyl) acryloyl group.
<(D2-4) resin>
As (D2-4) (methyl) acrylic resin, can enumerate and make the compound shown in following formulas (6) be necessary (methyl) acrylic resin obtained from the polymerizing monomer components of composition.
[chemical formula 88]
In above-mentioned formula (6), R71And R72Represent hydrogen atom or the carbon number 1 optionally with substituent group independently of one another ～25 alkyl.
Hereinafter, the compound for formula (6) is described in detail.
In ether dimer shown in formula (6), as with R71And R72The carbon number optionally with substituent group representing 1～25 alkyl, is not particularly limited, and can enumerate for example：Methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, uncle The straight-chain such as butyl, tertiary pentyl, stearyl, lauryl and 2- ethylhexyl or the alkyl of branch-like；The aryl such as phenyl；Hexamethylene Base, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl and 2- methyl -2- adamantyl etc. Ester ring type base；The alkyl that 1- methoxy ethyl and 1- ethoxyethyl group etc. are optionally replaced by alkoxyl；Benzyl etc. is optionally by aryl Alkyl replacing etc..In the middle of these, from the viewpoint of thermostability, particularly preferred methyl, ethyl, cyclohexyl and benzyl etc. are so Be difficult the substituent group with primary carbon atom or secondary carbon left away in the presence of acid or heat.It should be noted that R71And R72Can be identical substituent group or different substituents.
As the ether dimer shown in formula (6), particularly preferably 2,2 '-[oxo is double (methylene)] double -2- acrylic acid Methyl ester, 2,2 '-[oxo is double (methylene)] double -2- ethyl acrylate, 2,2 '-[oxo is double (methylene)] double -2- acrylic acid rings Own ester or 2,2 '-[oxo is double (methylene)] double -2- acrylic acid dibenzyl esters.These ether dimers can only be used alone a kind, Two or more can be applied in combination.
The dimeric ratio of above-mentioned ether obtaining in monomer component during (D2-4) resin is not particularly limited, but all single In body composition, usually 2～60 mass %, preferably 5～50 mass %.
(D2-4) resin preferably has acidic group.By having acidic group, can be using the present invention obtained from this resin Photosensitive polymer combination becomes the cross-linking reaction that can form ester bond by acidic group with epoxy reaction (hereinafter also referred to as " acid-curable epoxide ") and occur solidify photosensitive polymer combination or can in alkaline developer by uncured portion development Photosensitive polymer combination.
As above-mentioned acidic group, it is not particularly limited, such as carboxyl, phenolic hydroxyl group and acid anhydride etc. can be enumerated.In resin Every 1 molecule in these contained acidic groups can be only a kind or two or more.
In order to import acidic group in (D2-4) resin, using the monomer for example with acidic group and/or " can be after polymerisation The monomer of imparting acidic group " (hereinafter also referred to " in order to import the monomer of acidic group ") is as monomer component.It should be noted that Be used " monomer that acidic group can be given after polymerisation " as monomer component in the case of, need to carry out after polymerisation assigning Give the process of acidic group.
As the above-mentioned monomer with acidic group, can enumerate for example：(methyl) acrylic acid or itaconic acid etc. have the list of carboxyl Body；N- hydroxyphenyl-maleimides etc. have the monomer of phenolic hydroxyl group；Maleic anhydride or itaconic anhydride etc. have acid anhydride Monomer etc..In these monomers, particularly preferably (methyl) acrylic acid.
As the above-mentioned monomer that can give acidic group after polymerisation, can enumerate for example：(methyl) acrylic acid 2- hydroxy methacrylate Etc. the monomer with hydroxyl；(methyl) glycidyl acrylate etc. has the monomer of epoxy radicals；(methyl) acrylic acid 2- isocyanide Acetoacetic ester etc. has monomer of NCO etc..
These can be used alone a kind it is also possible to be applied in combination two or more in order to the monomer importing acidic group.
Obtain in the case that monomer component during (D2-4) resin also comprises the above-mentioned monomer in order to import acidic group, it contains Ratio is usually 5～70 mass % in whole monomer components, is preferably 10～60 mass %.
Obtain in monomer component during (D2-4) resin in addition to above-mentioned necessary monomer component it is also possible to as needed And comprise other copolymerizable monomers.
In the photosensitive polymer combination of the present invention, preferably comprise above-mentioned epoxy (methyl) acrylate (D1- 1), epoxy (methyl) acrylate (D1-2), (D2-1) resin, (D2-2) resin, (D2-3) resin and (D2-4) resin In any one as alkali soluble resin (d), further preferably comprise epoxy (methyl) acrylate (D1-1), ring Any one in oxygen (methyl) acrylate (D1-2), (D2-1) resin and (D2-3) resin, particularly preferably at least wraps Containing epoxy (methyl) acrylate (D1-1) and/or epoxy (methyl) acrylate (D1-2).
<Other alkali soluble resins>
Except above-mentioned epoxy (methyl) acrylate (D1-1), epoxy in the photosensitive polymer combination of the present invention Beyond (methyl) acrylate (D1-2), (D2-1)～(D2-4) resin, can also contain as alkali soluble resin (b) Other alkali soluble resins one kind or two or more.
Other alkali soluble resins are simultaneously unrestricted, and selection in commonly used resin from photosensitive polymer combination is Can.For example, Japanese Unexamined Patent Publication 2007-271727 publication, Japanese Unexamined Patent Publication 2007-316620 publication, Japanese Unexamined Patent Publication can be enumerated Alkali soluble resin described in 2007-334290 publication etc. etc..
[color material (a)]
The photosensitive polymer combination of the present invention contains coloured material (a).Color material (a) refers to the photoresist group of the present invention The material of compound coloring.As color material (a), dyestuff, pigment can be used, from the aspect such as thermostability and light resistance, preferably face Material.
As pigment, can enumerate for example：Blue pigment, viridine green, red pigment, yellow uitramarine, violet pigment, orange The pigment of the shades of colours such as pigment, brown or black pigment.In addition, as its structure, except such as azo, phthalocyanine Class, quinoline azone class, benzimidazole ketone, isoindoline ketone, twoOrganic face such as piperazine class, indanthrone kinds, perylene kinds Beyond material, various inorganic pigments etc. can also be enumerated.
Hereinafter, the concrete example of pigment that can use in the present invention is shown with pigment sequence number.It should be noted that it is following Terms such as " the C.I. paratoneres 2 " enumerated refers to pigment call number (C.I.).
As red pigment, can enumerate for example：C.I. paratonere 1,2,3,4,5,6,7,8,9,12,14,15,16,17, 21、22、23、31、32、37、38、41、47、48、48:1、48:2、48:3、48:4、49、49:1、49:2、50:1、52:1、52: 2、53、53:1、53:2、53:3、57、57:1、57:2、58:4、60、63、63:1、63:2、64、64:1、68、69、81、81:1、 81:2、81:3、81:4、83、88、90:1、101、101:1、104、108、108:1、109、112、113、114、122、123、 144、146、147、149、151、166、168、169、170、172、173、174、175、176、177、178、179、181、184、 185、187、188、190、193、194、200、202、206、207、208、209、210、214、216、220、221、224、230、 231、232、233、235、236、237、238、239、242、243、245、247、249、250、251、253、254、255、256、 257th, 258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275 and 276. Wherein, preferably enumerate C.I. pigment red 48:1st, 122,168,177,202,206,207,209,224,242 or 254, one can be entered Step preferably enumerates C.I. paratonere 177,209,224,254.
As blue pigment, can enumerate for example：C.I. pigment blue 1,1:2、9、14、15、15:1、15:2、15:3、15:4、 15:6、16、17、19、25、27、28、29、33、35、36、56、56:1、60、61、61:1、62、63、66、67、68、71、72、 73rd, 74,75,76,78 and 79.Wherein, preferably enumerate C.I. pigment blue 15,15:1、15:2、15:3、15:4 or 15:6, can enter One step preferably enumerates C.I. pigment blue 15:6.
As viridine green, can enumerate for example：C.I. naphthol green 1,2,4,7,8,10,13,14,15,17,18,19,26, 36th, 45,48,50,51,54 and 55.Wherein, C.I. pigment Green 7,36 or 58 are preferably enumerated.
As yellow uitramarine, can enumerate for example：C.I. pigment yellow 1,1:1、2、3、4、5、6、9、10、12、13、14、16、 17、24、31、32、34、35、35:1、36、36:1、37、37:1、40、41、42、43、48、53、55、61、62、62:1、63、65、 73、74、75、81、83、87、93、94、95、97、100、101、104、105、108、109、110、111、116、117、119、 120、126、127、127:1、128、129、133、134、136、138、139、142、147、148、150、151、153、154、 155、157、158、159、160、161、162、163、164、165、166、167、168、169、170、172、173、174、175、 176、180、181、182、183、184、185、188、189、190、191、191:1、192、193、194、195、196、197、 198th, 199,200,202,203,204,205,206,207 and 208.Wherein, preferably enumerate C.I. pigment yellow 83,117,129, 138th, 139,150,154,155,180 or 185, can further preferably enumerate C.I. pigment yellow 83,138,139,150 or 180.
As orange pigment, can enumerate for example：C.I. pigment orange 1,2,5,13,16,17,19,20,21,22,23,24, 34th, 36,38,39,43,46,48,49,61,62,64,65,67,68,69,70,71,72,73,74,75,77,78 and 79.Its In, preferably enumerate C.I. pigment orange 38 or 71.
As violet pigment, can enumerate for example：C.I. pigment violet 1,1:1、2、2:2、3、3:1、3:3、5、5:1、14、15、 16th, 19,23,25,27,29,31,32,37,39,42,44,47,49 and 50.Wherein, preferably enumerate C.I. pigment violet 19 or 23, can further preferably enumerate C.I. pigment Violet 23.
In addition, the photosensitive polymer combination of the present invention is the resin black matrix photosensitive polymer combination of light filter In the case of, as color material (a), the color material of black can be used.Black color material can be single black color material, or, also may be used To be the black pigment being mixed by red, green and blue etc..In addition, these color materials can be from inorganic or organic pigment, dyestuff In suitably select.
, can enumerate for example for preparing the color material of black color material as being used in mixed way：Victoria pure blue (42595), auramine O (41000), カ チ ロ Application Block リ リ ア Application ト Off ラ PVC Application (basic 13), rhodamine 6G CP (45160), rhodamine B (45170), Safranine O K70:100 (50240), the red X of small-mouthed jar (42080), No.120/ thunder Austria Nore are yellow (Lionol Yellow) (21090), thunder Austria's Nore Huang GRO (21090), Si Mule fast yellow 8GF (21105), benzidine yellow 4T-564D (21095), Si Mule fast red 4015 (12355), the thunder Austria's red 7B4401 of Nore (15850), Fastogen Blue TGR-L (74160), thunder Austria's Nore indigo plant SM (26150), thunder Austria Nore indigo plant ES (pigment blue 15:6), Lionogen red GD (face Expect red 168) and the thunder Austria's green 2YS of Nore (pigment green 36) etc. (it should be noted that the digitized representation pigment rope in above-mentioned () Quotation marks (C.I.)).
In addition, the pigment being used in mixed way for other, if represented with No. C.I., can enumerate for example：C.I. yellow Pigment 20,24,86,93,109,110,117,125,137,138,147,148,153,154 and 166, C.I. orange pigment 36, 43rd, 51,55,59 and 61, C.I. red pigment 9,97,122,123,149,168,177,180,192,215,216,217,220, 223rd, 224,226,227,228 and 240, C.I. violet pigment 19,23,29,30,37,40 and 50, C.I. blue pigment 15,15: 1、15:4th, 22,60 and 64, C.I. viridine green 7 and C.I. brown 23,25 and 26 etc..
In addition, as the black color material that can be used alone, can enumerate for example：White carbon black, acetylene black, lampblack, bone black, stone Ink, iron oxide black, nigrosine, match be peaceful black and titanium is black etc..
In the case of the color material of black, in these colors material (a), from the viewpoint of shading rate, picture characteristics, excellent Choosing uses white carbon black.As the example of white carbon black, shown white carbon black can be listed below.
Mitsubishi chemical Co., Ltd's system：MA7、MA77、MA8、MA11、MA100、MA100R、MA220、MA230、MA600、# 5、#10、#20、#25、#30、#32、#33、#40、#44、#45、#47、#50、#52、#55、#650、#750、#850、#950、# 960、#970、#980、#990、#1000、#2200、#2300、#2350、#2400、#2600、#3050、#3150、#3250、# 3600th, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B
Degussa company system：Printex (registered trade mark, similarly hereinafter) 3, Printex3OP, Printex30, Printex30OP、Printex40、Printex45、Printex55、Printex60、Printex75、Printex80、 Printex85、Printex90、Printex A、Printex L、Printex G、Printex P、Printex U、Printex V、PrintexG、SpecialBlack550、SpecialBlack350、SpecialBlack250、SpecialBlack100、 SpecialBlack6、SpecialBlack5、SpecialBlack4、Color Black FW1、Color Black FW2、 Color Black FW2V、Color Black FW18、Color Black FW18、Color Black FW200、Color Black S160 and Color Black S170
Cabot company system：Monarch (registered trade mark, similarly hereinafter) 120, Monarch280, Monarch460, Monarch800、Monarch880、Monarch900、Monarch1000、Monarch1100、Monarch1300、 Monarch1400, Monarch4630, REGAL (registered trade mark, similarly hereinafter) 99, REGAL99R, REGAL415, REGAL415R, REGAL250、REGAL250R、REGAL330、REGAL400R、REGAL55R0、REGAL660R、BLACK PEARLS480、 PEARLS130, VULCAN (registered trade mark.Similarly hereinafter.) XC72R and ELFTEX (registered trade mark) -8
Colombiyan Carbon company system：RAVEN (registered trade mark, similarly hereinafter) 11, RAVEN14, RAVEN15, RAVEN16、RAVEN22RAVEN30、RAVEN35、RAVEN40、RAVEN410、RAVEN420、RAVEN450、RAVEN500、 RAVEN780、RAVEN850、RAVEN890H、RAVEN1000、RAVEN1020、RAVEN1040、RAVEN1060U、 RAVEN1080U、RAVEN1170、RAVEN1190U、RAVEN1250、RAVEN1500、RAVEN2000、RAVEN2500U、 RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750 and RAVEN7000
White carbon black can also be using white carbon black obtained from resin-coating.Using white carbon black obtained from resin-coating When, there is raising with respect to the adaptation of glass substrate and the effect of volumetric resistivity value.Obtain as using resin-coating White carbon black, preferably using white carbon black described in for example in Japanese Unexamined Patent Publication 09-71733 publication etc..
As carrying out coating the white carbon black processing, the preferably total content of Na and Ca is below 100ppm.Its reason is as follows.That is, White carbon black generally contains ash with % magnitude, and described ash is the raw oil or fuel oil (or gas), reaction stopping water when manufacturing Or the ash consisting of Na, Ca, K, Mg, Al or Fe etc. being mixed in the stove material of pelletize water or reacting furnace etc..Wherein, Na and Ca generally contains hundreds of more than ppm respectively, if this is because, they exist in a large number, may be impregnated with to transparency electrode (ITO) or other electrode and the reason become electrical short.
As the method for the content of these ash comprising Na or Ca reducing in white carbon black, can be set forth in tight during manufacture white carbon black Lattice select the content of these ash material as few as possible to stop water as raw oil and fuel oil (or gas) and reaction, and The method reducing the addition of alkaloid substance of adjustment structure as far as possible.As other methods, can enumerate by making to from stove White carbon black washed using water or hydrochloric acid etc. and so that Na or Ca is dissolved thus the method that is removed.
Example as other black pigments, it is possible to use titanium is black, nigrosine, iron oxide black pigment and will be red Color, green and blue trichroism organic pigment mixing and as black pigment.
In addition, as pigment, can also be using barium sulfate, lead sulfate, titanium oxide, lead and yellow-collation, iron oxide red or chromium oxide etc..
Multiple combination in above-mentioned various pigment can also be used.For example, in order to adjust colourity, can be by green face Material is applied in combination with yellow uitramarine or is applied in combination blue pigment with violet pigment.
<The particle diameter of color material (a)>
For as the average primary particle diameter of the pigment of color material (a) used in the present invention, make light filter In the case of chromatograph, as long as being obtained in that desired color development is just not particularly limited the kind although also according to the pigment being used Class and different, but preferably in the range of 10～100nm, more preferably in the range of 10～70nm, further preferably 20～ In the range of 60nm.By making the average primary particle diameter of this pigment in above range, can be using the photonasty tree of the present invention Oil/fat composition and the chromatic characteristic of image display device that manufactures reaches high-quality.In addition, pigment is flat in the case of white carbon black All primary particle diameter be preferably below 100nm, more preferably below 80nm, further preferred below 60nm, particularly preferred 50nm with Under.In addition, pigment is preferably more than the 20nm of the average primary particle diameter in the case of white carbon black, is more preferably more than 24nm, especially It is preferably more than 27nm.
Below for above-mentioned higher limit, exist and make to become good based on the capture to pigment of polyurethane dispersant (b-1) Well, the tendency of resistance to alkali-developable and thermostability raising.On the other hand, by more than for above-mentioned lower limit, exist can suppress because The tendency that the dispersibility that the necessary amount of dispersant (b) increases and leads to reduces.
It should be noted that the average primary particle diameter of above-mentioned pigment can be using at the beginning of electron micrograph direct measurement The level method of size of particle and obtain.Specifically, measure minor axis diameter and the major diameter of each primary particle, and by its Meansigma methodss are as the particle diameter of its particle.Then, the particle for more than 100, be approximately the calculated cuboid of particle diameter and Obtain the volume (weight) of each particle, obtain volume average particle size, and using this volume average particle size as average primary particle diameter. It should be noted that as ultramicroscope, using any type of electronic display in transmission-type (TEM) or sweep type (SEM) Micro mirror all can obtain identical result.
The photosensitive polymer combination of the present invention preferably comprises pigment colour material (a), in addition it is also possible to will not be to the present invention Effect impact in the range of be applied in combination dyestuff.As the dyestuff that can be applied in combination, can enumerate for example：Azo contaminates Material, anthrone class dyestuff, phthalocyanines dye, quinone imides dyestuff, quinolines dyestuff, nitro class dyestuff, carbonyl class dyestuff and methine Class dyestuff etc..
As azo dyes, can enumerate for example：C.I. acid yellow 11, C.I. acid orange 7, C.I. Xylene Red 37, C.I. Acid red 18 0, C.I. acid blue 29, C.I. directly red 28, C.I. directly red 83, C.I. directly yellow 12, C.I. direct orange 26, C.I. direct green 28, C.I. direct green 59, C.I. reactive yellow 2, C.I. active red 17, C.I. active red 120, C.I. reactive black 5, C.I. disperse orange 5, C.I. disperse red 58, C.I. disperse blue 165, C.I. alkali blue 41, C.I. Basic Red 18, C.I. medium red 7, C.I. medium Huang 5 and C.I. Mordant Black 7 etc..
As anthrone class dyestuff, can enumerate for example：C.I. Vat blue 4, C.I. Acid Blue 40, C.I. ACID GREEN 25, C.I. Active blue 19, C.I. reactive blue 49, C.I. disperse red 60, C.I. Disperse Blue-56 and C.I. disperse blue 60 etc..
As phthalocyanines dye, can enumerate for example：C.I. vat blue 5 etc..As quinone imides dyestuff, can enumerate for example： C.I. alkali blue 3 and C.I. alkali blue 9 etc..
As quinolines dyestuff, can enumerate for example：C.I. solvent yellow 33, C.I. quinoline yellow and C.I. dispersion yellow 64 etc..Make For nitro class dyestuff, can enumerate for example：C.I. Indian yellow 1, C.I. acid orange 3 and C.I. Disperse Yellow 42 etc..
[photopolymerization monomer]
Preferably comprise photopolymerization monomer from the aspects such as sensitivity, the photosensitive polymer combination of the present invention.
As photopolymerization monomer used in the present invention, intramolecular can be enumerated at least there is 1 ethylenically unsaturated group Compound (hereinafter also referred to " olefinic type monomers ").
Specifically can enumerate for example：(methyl) acrylic acid, (methyl) alkyl acrylate, acrylonitrile, styrene, there is 1 Monoesters of the carboxylic acid of ethylenic unsaturated bond and polynary or 1 yuan of alcohol etc..
In the present invention, particularly preferably using the multifunctional olefinic in 1 molecule with two or more ethylenically unsaturated group Monomer.
As such multifunctional olefinic type monomers, can enumerate for example：Aliphatic polyhydroxy compound and unsaturated carboxylic acid shape The ester becoming；The ester that aromatic polyhydroxy compounds are formed with unsaturated carboxylic acid；Aliphatic polyhydroxy compound, aromatic polyhydric The multi-hydroxy compound such as compound and unsaturated carboxylic acid and polybasic carboxylic acid are through ester obtained from esterification etc..
The ester being formed with unsaturated carboxylic acid as above-mentioned aliphatic polyhydroxy compound, can enumerate for example：Ethylene glycol dipropyl Olefin(e) acid ester, triethylene glycol diacrylate, trimethylolpropane trimethacrylate, methylolethane triacrylate, season penta Tetrol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol tetraacrylate, two The third of the aliphatic polyhydroxy compounds such as tetramethylolmethane five acrylate, dipentaerythritol acrylate and glyceryl acrylate Olefin(e) acid ester and by the acrylate of these example compound replace with methacrylate methacrylate, with The acrylate of above-mentioned example compound is replaced with the itaconate of itaconate, replaces with crotonatess and form by sample ground Crotonatess and replace with maleate of maleate etc..
The ester being formed with unsaturated carboxylic acid as aromatic polyhydroxy compounds, can enumerate for example：Hydroquinone two propylene Acid esters, hydroquinone dimethylacrylate, resorcinol diacrylate, resorcinol dimethylacrylate and adjacent benzene three The acrylate of the aromatic polyhydroxy compounds such as phenol triacrylate and methacrylate etc..
As polybasic carboxylic acid and unsaturated carboxylic acid and multi-hydroxy compound through ester obtained from esterification, not necessarily It is single substance, as its representational concrete example, can enumerate：The condensation substance of acrylic acid, phthalic acid and ethylene glycol, propylene The condensation substance of acid, maleic acid and diethylene glycol, the condensation substance of methacrylic acid, p-phthalic acid and tetramethylolmethane and propylene Condensation substance of acid, adipic acid, butanediol and glycerol etc..
In addition, as olefinic type monomers multifunctional used in the present invention, for example：Make polyisocyanate compound and hydroxyl (methyl) acrylate or polyisocyanate compound and polyhydric alcohol and ammonia obtained from hydroxyl (methyl) acrylate reactions Carbamate (methyl) esters of acrylic acid；Polynary epoxide is acrylic acid with hydroxyl (methyl) acrylate or (methyl) to be added Become such Epoxy Acrylates of reactant；The acrylic amides such as ethylenebisacrylamide；Dially phthalate Deng pi-allyl esters；It is useful that phthalic acid divinyl ester etc. contains vinyl compound etc..
Further, as olefinic type monomers multifunctional used in the present invention, such as intramolecular has caprolactone structure and 2 In the compound (hereinafter also referred to " the multi-functional monomer containing caprolactone structure ") of above ethylenically unsaturated group and the present invention The polyurethane dispersant (b-1) using is compatible well, can improve the effect based on these dispersants further, thus be to have , preferably use.
As the multi-functional monomer containing caprolactone structure, can enumerate and for example can be synthesized by following known method Multifunctional (methyl) acrylate containing 6-caprolactone structure, described known method includes：6-caprolactone is made to add by open loop Become reaction and trimethylolethane, double trimethylolethane, trimethylolpropane, double trimethylolpropane, tetramethylolmethane, two It is bonded open loop skeleton on the polyhydric alcohol such as tetramethylolmethane, tripentaerythritol, glycerol, two glycerol or trimethylol melamine, make out The terminal hydroxyl of ring skeleton is reacted with (methyl) acryloyl chloride or with (methyl) acrylic acid, esterification occurs, thus importing (first Base) acryloyl group.
Such multi-functional monomer containing caprolactone structure includes commercially available monomer as described below.For example, as making With dipentaerythritol as polyhydric alcohol and make this polyhydric alcohol, acrylic acid and 6-caprolactone be esterified obtained from monomer, can arrange Lift by Japanese chemical medicine (strain) as KAYARAD DPCA series and commercially available DPCA-20, DPCA-30, DPCA-60 and DPCA-120 Deng the preferably photopolymerization monomer of the photosensitive polymer combination as the present invention.
In addition, the commercially available product of 6-caprolactone modification isocyanuric acid three (2- acryloyl-oxyethyl) ester compounds, including new The A-9300-1CL (having 1 mole of 6-caprolactone structure in 1 mole of compound) of chemical industry Co., Ltd. of middle village, 1 Mole compound in there is 0.1～9 mole, the monomer more preferably with 1～3 mole of these 6-caprolactone structure also preferable The photopolymerization monomer of the photosensitive polymer combination as the present invention.
In addition, the terminal hydroxyl after being used tetramethylolmethane as polyhydric alcohol and making this polyhydric alcohol and 6-caprolactone are esterified There is the monomer of esterification further with acrylic acid, it also may be preferable for the photopolymerization of the photosensitive polymer combination as the present invention Property monomer.These monomers are preferably the monomer in 1 mole of compound with 0.1～20 mole of 6-caprolactone structure, more excellent Choosing has 1～12 mole of 6-caprolactone structure, particularly preferably has 1～4 mole of 6-caprolactone structure.
These photopolymerization monomers can be used alone a kind it is also possible to be applied in combination two or more.
[thio-alcohol]
In order to realize high-sensitivity, improve with respect to substrate adaptation, in the photosensitive polymer combination of the present invention Further preferably contain thio-alcohol.
As the species of thio-alcohol, can enumerate for example：Ethanthiol, the last of the ten Heavenly stems two mercaptan, 1,4- dimethyl sulfydryl benzene, dimercapto Propanoic acid butanediol ester, dimercapto acetic acid butanediol ester, glycol dimercaptosuccinate, trimethylolpropane tris mercaptoacetate, Dimercapto propanoic acid butanediol ester, trimethylolpropane tris mercaptopropionic acid ester, trimethylolpropane tris mercaptoacetate, tetramethylolmethane Double (the 3- mercaptobutyric acid of four mercaptopropionic acid esters, tetramethylolmethane four mercaptoacetate, tri-thiol propanoic acid trihydroxy ethyl ester, ethylene glycol Ester), propylene glycol double (3- mercaptobutylate) (referred to as PGMB), butanediol double (3- mercaptobutylate), double (the 3- sulfydryl fourth of 1,4- Acyloxy) butane [trade name；Karenz (registered trade mark.Similarly hereinafter) MT BD1, Showa electrician (strain) system], butanediol trihydroxy methyl Propane three (3- mercaptobutylate), tetramethylolmethane four (3- mercaptobutylate) (trade name；Karenz MT PE1, Showa electrician (strain) makes), tetramethylolmethane three (3- mercaptobutylate), ethylene glycol double (3- mercaptoisobutanoic acid esters), double (the 3- mercaptoisobutanoic of butanediol Acid esters), trimethylolpropane tris (3- mercaptoisobutanoic acid esters), trimethylolpropane tris (3- mercaptobutylate) (referred to as TPMB), trimethylolpropane tris (2- mercaptoisobutanoic acid esters) (referred to as TPMIB) and 1,3,5- tri- (3- sulfydryl butoxy second Base) -1,3,5- triazine -2,4,6 (1H, 3H, 5H)-triketone (trade name；Karenz MT NR1, Showa electrician (strain) system) etc., this A little thio-alcohols can be used in mixed way using independent a kind in various or by two or more.
Preferably above-mentioned PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, Karenz MT NR1 etc. are many Functional thiols, wherein, further preferred Karenz MT BD1, Karenz MT PE1, Karenz MT NR1, particularly preferably Karenz MT PE1.
These thio-alcohols can be used alone a kind it is also possible to be applied in combination two or more.
[solvent (e)]
The photosensitive polymer combination of the present invention is generally caused with alkali soluble resin (d), photopolymerization monomer, photopolymerization Agent (c), color material (a), dispersant (b) and the various materials using as desired are dissolved or dispersed in the state in solvent (e) And use.
As solvent (e) used in the present invention, preferably select boiling point (under conditions of pressure 1013.25 [hPa], below, With regard to boiling point, all identical) 100～300 DEG C of scopes organic solvent.More preferably there is 120～280 DEG C of the having of boiling point Machine solvent.
As such organic solvent, the organic solvent of such as described below can be enumerated.
Ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol list Methyl ether, propylene glycol monoethyl, propylene glycol list n-butyl ether, propylene glycol t-butyl ether, diethylene glycol monomethyl ether, diethyl two Alcohol list ethylether, diethylene glycol list n-butyl ether, methoxy amylalcohol, dihydroxypropane single-ethyl ether, dipropylene glycol monomethyl Ether, 3- methyl -3- methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and tripropylene glycol methyl ether are so Glycol monoalkyl ethers；
Ethylene glycol dimethyl ether, ethylene glycol, diethylene glycol dimethyl ether, diethylene glycol ether, diethylene glycol dipropyl Base ether, diethylene glycol dibutyl ether and dipropylene glycol dimethyl ether such glycol dialkyl ether class；
Ethylene glycol single methyl ether acetass, ethylene glycol monomethyl ether acetate, ethylene glycol list n-butyl ether acetass, the third two Alcohol monomethyl ether acetate, propylene glycol monoethyl acetass, propylene glycol monopropyl ether acetass, glycol monobutyl ether acetic acid Ester, methoxy butyl acetate, acetic acid 3- methoxybutyl, acetic acid methoxyl group pentyl ester, diethylene glycol monomethyl ether acetass, diethyl Glycol list monoethyl ether acetate, diethylene glycol list n-butyl ether acetass, DPGME acetass, triethylene glycol list Methylether acetate, triethylene glycol monoethyl ether acetic acid ester and the such glycol alkyl ether of acetic acid 3- methyl -3- methoxybutyl Acetate esters；
The glycol diacetates such as ethylene acetate, 1,3 butylene glycol diacetate esters and 1,6-HD diacetate esters Class；
The acetate alkyl esters such as adnoral acetate；
Amyl ether, ether, dipropyl ether, Di Iso Propyl Ether, dibutyl ethers, diamyl ether, ethyl isobutyl ether, hexyl ether Such ethers；
Acetone, butanone, methyl amyl ketone, methyl isopropyl Ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl Ketone, methyl iso-butyl ketone (MIBK), Ketohexamethylene, ethyl pentyl group ketone, methyl butyl ketone, methyl hexyl ketone., methyl nonyl ketone and methoxy methyl The such ketone of base pentanone；
Ethanol, propanol, butanol, hexanol, Hexalin, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, three Ethylene glycol, methoxy amylalcohol, glycerol and the such monohydric alcohol of benzylalcohol or polyalcohols；
Pentane, normal octane, diisobutylene, normal hexane, hexene, isoprene, cinene and the such fat of dodecane Race's hydro carbons；
Hexamethylene, hexahydrotoluene, methylcyclohexene and bicyclohexyl such ester ring type hydro carbons；
Benzene,toluene,xylene and isopropylbenzene are such aromatic hydrocarbon；
Amyl formate, Ethyl formate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, methyl isobutyrate, second two Alcohol acetic ester, ethyl propionate, propyl propionate, butyl butyrate, isobutyl isobutyrate (IBIB), methyl isobutyrate, ethyl caprate, stearic acid fourth Ester, ethyl benzoate, 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, 3- methoxy methyl propionate, 3- methoxypropionic acid Ethyl ester, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester and the such chain of gamma-butyrolacton or ring-type esters；
3- methoxypropionic acid and 3- ethoxy-propionic acid such alkoxyl carboxylic acidss；
The such halogenated hydrocarbon of chlorobutane, chloropentane；
Methoxy pentanone such ether ketone；
Such nitrile of acetonitrile, benzonitrile etc..
As meeting above-mentioned commercially available solvent, can enumerate for example：Mineral spirits (Mineral spirit), Varsol# 2nd, Apco#18solvent, Apco thinner, Socal solvent No.1 and No.2, Solvesso#150, Shell (" cellosolve (cellosolve) " is note for TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve Volume trade mark.Similarly hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methylcellosolve acetate and diethylene glycol dimethyl ether (diglyme) (be trade name) etc..
These organic solvents may be used alone, or two or more kinds may be used in combination.
Form pixel or the black matrix" of light filter using photoetching process in the case of, as organic solvent, preferably select boiling O'clock 100～200 DEG C of scopes organic solvent.More preferably there is the organic solvent of 120～170 DEG C of boiling point.
In above-mentioned organic solvent, the dissolving of the constituent from the balance of coating, surface tension etc. is good, compositionss Spend higher aspect to set out, preferred diol alkylether acetates class.
In addition, glycol alkyl ether acetate esters be can be used alone it is also possible to be used with other organic solvent combination.As The organic solvent being applied in combination, particularly preferably glycol monoalkyl ethers.Wherein, the dissolving of the constituent from compositionss Property consider, particularly preferred propylene glycol monomethyl ether.
It should be noted that the polarity of glycol monoalkyl ethers is high, if its addition is excessive, there is the color material such as pigment A () is susceptible to condense and leads to the viscosity of the photosensitive polymer combination subsequently obtaining the inclining of storage stability decline such as to rise To therefore, the ratio of the glycol monoalkyl ethers in solvent (e) is preferably 5～30 mass %, more preferably 5～20 mass %.
In addition, as solvent (e), the organic solvent being further preferably applied in combination the boiling point with more than 150 DEG C (is also referred to as below For " high boiling solvent ").By being applied in combination such high boiling solvent although photosensitive polymer combination can be led to be difficult to do Dry, but have and prevent due to being drastically dried and the effect of the homogeneously dispersed state of color material (a) in destroying compositions.That is, have For example prevent from producing the effect of foreign body defect in slit spray nozzle front end because of precipitation, the solidification of color material (a) etc..
From the aspect of such effect is significant, in above-mentioned various solvents, particularly preferred diethylene glycol list normal-butyl Ether, diethylene glycol list n-butyl ether acetass and TC acetass.
The content ratio of the high boiling solvent in solvent (e) be preferably 3～50 mass %, more preferably 5～40 mass %, Particularly preferred 5～30 mass %.If the amount of high boiling solvent is very few, exist for example in slit spray nozzle front end because of color material (a) Deng precipitation, solidification and cause the probability of foreign body defect, in addition, if the amount of high boiling solvent is excessive, then compositionss is dry Dry slow, exist cause in the light filter manufacturing process being described below drying under reduced pressure technique productive temp bad, pre- The hidden danger of the such problem of pin-and-hole vestige of baking (pre-bake).
It should be noted that the high boiling solvent of more than 150 DEG C of boiling point can be glycol alkyl ether acetate esters, in addition, Can also be glycol monoalkyl ethers, should in the case of it is also possible to the not other high boiling solvent containing more than 150 DEG C of boiling point.
As preferred high boiling solvent, in for example aforesaid various solvents, diethylene glycol list n-butyl ether can be enumerated Acetass, TC acetass, dipropylene glycol methyl ether acetass, 1,3 butylene glycol diacetate esters, 1,6- are own Glycol diacetate and glycerol triacetate etc..
[other gradation compositions of photosensitive polymer combination]
In the photosensitive polymer combination of the present invention in addition to mentioned component, can suitably coordinate closely sealed improving agent, painting Cloth improving agent, development modifying agent, UV absorbent, antioxidant, silane coupler, surfactant, pigment derivative, poly- Close accelerator, photoacid generator, cross-linking agent, plasticizer, preserving stabilizer, surface protectant, organic carboxyl acid, organic carboxyl acid acid anhydride, show Shadow modifying agent or thermal polymerization preventing agent etc..
<Closely sealed improving agent>
In order to improve the adaptation with substrate it is also possible to contain closely sealed improvement in making the photosensitive polymer combination of the present invention Agent.As closely sealed improving agent, can enumerate for example：Silane coupler, the closely sealed improving agent of phosphoric acid class and other closely sealed improving agent etc..
As the species of silane coupler, can be even by various to epoxiess, (methyl) acrylic compounds or amino etc. silane Connection agent is used alone a kind, or two or more is used in mixed way.
As preferred silane coupler, can enumerate for example：3- methacryloyloxypropyl methyl dimethoxysilane And (methyl) acryloxy silane class, the 2- (3,4- epoxycyclohexyl) such as 3- methacryloxypropyl trimethoxy silane Ethyl trimethoxy silane, 3- glycidoxy-propyltrimethoxy silane, 3- glycidoxypropyl diethoxy silane and Ureido silane class and the 3- such as the epoxy silane classes such as 3- epoxypropoxy triethoxysilane, 3- urea propyl-triethoxysilicane The isocynate silane class such as isocyanatopropyl triethoxysilane.The silane coupler of particularly preferred epoxy silane class.
As the closely sealed improving agent of phosphoric acid class, preferably contain the phosphoric acid ester of (methyl) acryloxy, wherein more preferably following The phosphoric acid ester containing (methyl) acryloxy shown in formula (g1), (g2) or (g3).
[chemical formula 89]
In above-mentioned formula (g1), (g2) and (g3), R51Represent hydrogen atom or methyl, l and l ' is 1～10 integer, m is 1, 2 or 3.
As other closely sealed improving agent, can enumerate for example：TEGO*Add Bond LTH (Evonik company system) etc..
These closely sealed improving agent of phosphoric acid class and other closely sealed improving agent also both can be used alone a kind it is also possible to combination makes Use two or more.
<Surfactant>
In order to improve coating it is also possible to contain surfactant in making the photosensitive coloring composition of the present invention.
As surfactant, such as anionic, cationic, nonionic, amphoteric surfactant etc. can be enumerated Various surfactants.Wherein, from various characteristics are brought the low this respect of dysgenic probability consider, preferably use non-from Subtype surfactant, wherein, from coating aspect, the surfactant of fluorine class or silicon class is effective.
As such surfactant, can enumerate for example：TSF4460 (GE Toshiba organosilicon Co. Ltd. system), DFX- 18 (NEOS company systems), BYK-300, BYK-325, BYK-330 (BYK-Chemie company system), KP340 (SHIN-ETSU HANTOTAI's organosilicon strain formula Commercial firm's system), F-470, F-475, F-478, F-559 (DIC company system), SH7PA (Toray Silicone company system), DS-401 (Daikin Co., Ltd's system), L-77 (Nippon Unicar Co. Ltd.'s system) and FC4430 (Sumitomo 3M company system) etc..
These surfactants can be using a kind it is also possible in any combination and ratio combine uses two or more.
<Pigment derivative>
In order to improve dispersibility, keeping quality it is also possible to derive containing pigment in making the photosensitive coloring composition of the present invention Dispersant (b) and pigment derivative particularly, from the aspect improving dispersibility, are preferably applied in combination by thing.
As pigment derivative, can enumerate for example：Azo, phthalocyanines, quinoline azone class, benzimidazole ketone, quinophthalone Class, isoindoline ketone, twoPiperazine class, anthrone class, indanthrone kinds, perylene kinds, pyrene ketone, diketopyrrolo-pyrrole class And twoThe derivant of piperazine class etc..Wherein, preferably phthalocyanines or quinophthalone class.
As the substituent group of pigment derivative, can enumerate for example：Sulfonic group, sulfoamido and its quaternary salt, phenyl-diformyl are sub- Amine methyl, dialkyl aminoalkyl, hydroxyl, carboxyl or amide groups etc., these groups can be directly or via alkyl, aryl or heterocycle Base etc. is bonded on pigment skeleton, preferably sulfonic group.Multiple these are had to take alternatively, it is also possible to replace on a pigment skeleton Dai Ji.
As the concrete example of pigment derivative, can enumerate：The sulfonic acid of phthalocyanine, the sulfonic acid of quinophthalone, anthracene The sulfonic acid of ketone, the sulfonic acid of quinoline azone, the sulfonic acid of diketopyrrolo-pyrrole and twoThe sulfnic acid derivatives of piperazine Biology etc..
These pigment derivative can be used alone a kind it is also possible to be applied in combination two or more.
[the components matching amount in photosensitive polymer combination]
In the photosensitive polymer combination of the present invention, the content ratio of color material (a) is with respect in photosensitive polymer combination All solids component amount, usually more than 1 mass %, be preferably more than 5 mass %, more than more preferably 10 mass %, enter one Step be preferably more than 20 mass %, be still more preferably more than 30 mass %, more than particularly preferably 40 mass %, in addition, It is usually below 70 mass %, be preferably below 65 mass %, be more preferably below 60 mass %.By for above-mentioned lower limit with On, there is the gap control being prevented from because of during the liquid crystal cells obtaining given color density and thickening thickness and cause The harmful effect of system etc., in addition, by below for above-mentioned higher limit, there is the tendency being readily available sufficient image formative.
As previously described, the photosensitive polymer combination of the present invention can be used in various uses, but the sense based on the present invention The excellent image formative of photosensitive resin composition is especially effective in the formation for light filter black matrix".
In the case that the photosensitive polymer combination of the present invention is used for the formation of black matrix", as color material (a), use Aforesaid white carbon black or the black color material such as titanium is black or the plurality of color material mixing beyond black is adjusted to after black using. Wherein, from the viewpoint of light-proofness, particularly preferably using white carbon black.
The effect of the photosensitive polymer combination based on the present invention is particularly in the scope that the pigment concentration of black pigment is big Interior effectively played.As previously described, in recent years, need to improve obscurity to improve black pigment concentration, but From the viewpoint of having the tendency significantly producing effect of the present invention, the content ratio of black pigment is with respect to photoresist The all solids composition of compositionss is preferably more than 40 mass %, is more preferably more than 45 mass %, further preferred 48 matter More than amount more than %, particularly preferred 50 mass %.
In the photosensitive polymer combination of the present invention, by containing black pigment within the above range, exist and be obtained in that The tendency of the high photosensitive composition of light-proofness (optical density (OD), OD value).Specifically, by making black pigment Content ratio is more than 45 mass % with respect to all solids composition of photosensitive polymer combination, exists and can use the present invention Photosensitive polymer combination and the optical density (OD) in the case of forming the black matrix" of 1 μm of thickness be more than 4.0 the inclining of value To.This optical density (OD) more preferably more than 4.2.
In general, in the case of light-proofness height, ultraviolet is difficult to be transmitted through the deep of film, particularly in substrate with carefully , there is the tendency dying down based on the crosslinking of photopolymerization in the closely sealed part of line, but employing the photosensitive resin composition of the present invention In the case of thing, even if pigment concentration height is it is also possible to significantly confirm the effect of the present invention.Photonasty tree as the present invention The pigment concentration of oil/fat composition, is effective particularly when being 40～65 mass % with respect to solid constituent.
It should be noted that the photosensitive polymer combination of the present invention is not limited to the high situation of pigment concentration, even if It is also possible to show the effect of the present invention in the case that pigment concentration is low.Pigment is only changed in photosensitive polymer combination In the case of concentration, the difference according to pigment concentration is it is also possible to lead to, during heat cure process after development, thermal deformation occurs And cause fine rule live width more or less thicker or attenuate, but by adjusting photopolymerization monomer, optical polymerism initiator etc. Component amount or adjustment light exposure, can obtain expecting the fine rule of live width.
The content ratio of the dispersant (b) in the photosensitive polymer combination of the present invention is not particularly limited, in photonasty In all solids composition of resin combination, usually below 50 mass %, it is preferably below 30 mass %, more preferably 20 matter Below amount below %, more preferably 15 mass %, in addition, usually more than 1 mass %, be preferably more than 3 mass %, more It is preferably more than 5 mass %, be more preferably more than 8 mass %.
In addition, with respect to color material (a) 100 mass parts, the content ratio of dispersant (b) is usually more than 5 mass parts, preferably For more than 10 mass parts, more than more preferably 15 mass parts, usually below 200 mass parts, it is preferably below 80 mass parts, more Below preferably 50 mass parts, below more preferably 40 mass parts, below particularly preferably 30 mass parts.By making dispersion The content ratio of agent (b) is more than above-mentioned lower limit, there is the easy tendency obtaining sufficient dispersibility, by for above-mentioned higher limit Hereinafter, there is the content ratio that can relatively substantially ensure that other compositions, be readily available desired color density, desired spirit The tendency of sensitivity, desired film property etc..
It should be noted that from more effectively obtaining by the effect of the present invention brought using polyurethane dispersant (b-1) From the viewpoint of, in dispersant (b), the ratio shared by polyurethane dispersant (b-1) is preferably more than 50 mass %, is more preferably More than 60 mass %, more than further preferred 70 mass %, more than still more preferably 80 mass %, particularly preferred 90 mass % More than, in addition, usually below 100 mass %.
In the photosensitive polymer combination of the present invention, polyurethane dispersant (b-1) is with respect to alkali soluble resin (d) The content ratio of 100 mass parts be usually more than 2 mass parts, be preferably more than 5 mass parts, more than more preferably 10 mass parts, More than further preferred 20 mass parts, more than still more preferably 30 mass parts, more than particularly preferred 40 mass parts.In addition, it is logical It is often below 500 mass parts, be preferably below 300 mass parts, be more preferably below 100 mass parts, further preferred 80 mass Below part, below particularly preferred 60 mass parts.
With respect to all solids composition of the photosensitive polymer combination of the present invention, the photosensitive polymer combination of the present invention In the content ratio of Photoepolymerizationinitiater initiater (c) be usually more than 0.1 mass %, be preferably more than 0.5 mass %, more preferably More than 0.7 mass, more than more preferably 1 mass %, be still more preferably more than 3 mass %, particularly preferably 5 matter Amount more than %, in addition, usually below 30 mass %, be preferably below 20 mass %, below more preferably 15 mass %, enter one Step is preferably below 10 mass %.By making the content ratio of Photoepolymerizationinitiater initiater (c) for more than above-mentioned lower limit, existing and can obtain Sufficient sensitivity tendency, in addition, by below for above-mentioned higher limit, existing and can suppress unexposed portion in developer solution Deliquescent reduction, easily prevent the tendency of poor visualization.
Particularly, in Photoepolymerizationinitiater initiater (c), the ratio shared by oxime ester Photoepolymerizationinitiater initiater (c-1) is usually 10 mass % Above, it is preferably more than 50 mass %, be more preferably more than 90 mass %, in addition, below usual 100 mass %.By making oxime The content ratio of ester Photoepolymerizationinitiater initiater (c-1) is more than above-mentioned lower limit, can make they used in the present invention In the combining of agent (b-1) and alkali soluble resin (d), after ultraviolet irradiates, with respect to the patience of alkaline developer or high-temperature process Become more good, so that the formative of high fine fine rule improves.
In addition, total amount 100 matter with respect to polyurethane dispersant (b-1), alkali soluble resin (d) and photopolymerization monomer Amount part, the content ratio of Photoepolymerizationinitiater initiater (c) is usually more than 1 mass parts, is preferably more than 2 mass parts, more preferably 3 mass More than part.In addition, usually below 100 mass parts, being preferably below 60 mass parts, below more preferably 40 mass parts.
While using Photoepolymerizationinitiater initiater (c) using accelerator in the case of, the content ratio of accelerator with respect to The all solids composition of the photosensitive polymer combination of the present invention is usually more than 0 mass %, is preferably more than 0.02 mass %, It is usually below 10 mass %, be preferably below 5 mass %, with respect to Photoepolymerizationinitiater initiater (c), preferably with 0.1～50 matter Measure %, more preferably accelerator used with the ratio of 0.1～10 mass %.
In addition, in the case of using sensitizing dyestuff, contained sensitizing dyestuff in the photosensitive polymer combination of the present invention Content ratio is usually 0～20 mass % in all solids composition of photosensitive polymer combination, is preferably 0～15 matter Amount %, more preferably 0～10 mass %.
With respect to all solids composition of the photosensitive polymer combination of the present invention, the photosensitive polymer combination of the present invention In alkali soluble resin (d) content ratio be usually more than 5 mass %, be preferably more than 10 mass %, more preferably 15 More than quality %, more than more preferably 20 mass %, usually below 85 mass %, it is preferably below 80 mass %, more Be preferably below 70 mass %, below more preferably 60 mass %, be still more preferably below 50 mass %, especially excellent Elect below 40 mass % as, be most preferably below 30 mass %.
By making the content ratio of alkali soluble resin (d) for more than above-mentioned lower limit, existing and can suppress unexposed portion Deliquescent reduction in developer solution, easily prevent poor visualization generation tendency.In addition, by for above-mentioned higher limit with Under, exist and developer solution can be held in low-level tendency with respect to the impregnability of exposure portion, there is easy raising pixel Clarity or the tendency of adaptation.
It should be noted that as described above, in the photosensitive polymer combination of the present invention, as alkali soluble resin (d), Preferably comprise aforesaid epoxy (methyl) acrylate (D1-1), epoxy (methyl) acrylate (D1-2), (D2- 1) at least one in resin, (D2-2) resin, (D2-3) resin and (D2-4) resin, more preferably comprises epoxy (methyl) propylene Acid ester resin (D1-1), epoxy (methyl) acrylate (D1-2) resin, (D2-1) resin, (D2-3) resin, especially excellent Choosing comprises epoxy (methyl) acrylate (D1-1) and/or epoxy (methyl) acrylate (D1-2).
Alkali soluble resin (d) comprise these preferred resins beyond other alkali soluble resins in the case of, it contains Ratio is usually below 20 mass %, is preferably below 10 mass % with respect to the total amount of alkali soluble resin (d), and usually 0 More than quality %.
It should be noted that in the photosensitive polymer combination of the present invention, alkali soluble resin (d) is with respect to color material (a) The amount of 100 mass parts is usually more than 20 mass parts, is preferably more than 30 mass parts, is more preferably more than 40 mass parts, in addition, Be usually below 500 mass parts, be preferably below 300 mass parts, below more preferably 200 mass parts, more preferably 100 Below mass parts, still more preferably for below 80 mass parts, below particularly preferably 50 mass parts.By making with respect to color material A the content ratio of the alkali soluble resin (d) for () is more than above-mentioned lower limit, exist and can suppress unexposed portion in development Deliquescent reduction in liquid, be prevented from poor visualization generation tendency, in addition, by below for above-mentioned higher limit, depositing In the tendency being readily available desired pixel thickness.
With respect to all solids composition of the photosensitive polymer combination of the present invention, the photosensitive polymer combination of the present invention In the content ratio of photopolymerization monomer be usually below 90 mass %, be preferably below 80 mass %, more preferably 70 matter Below amount below %, more preferably 50 mass %, be still more preferably below 30 mass %, particularly preferably 20 matter Amount below %.By making the content of photopolymerization monomer below the above-mentioned upper limit, there is the leaching making developer solution with respect to exposure portion Permeability becomes appropriateness, can obtain the tendency of good image.
The lower limit of the content of photopolymerization monomer is usually more than 1 mass %, is preferably more than 5 mass %.By for upper State more than lower limit, exist and can make to improve, also make alkali-developable become good inclining simultaneously based on the photocuring that ultraviolet irradiates To.
In addition, the photopolymerization of total amount 100 mass parts with respect to polyurethane dispersant (b-1) and alkali soluble resin (d) Property monomer content ratio be usually 2 mass parts more than, be preferably 4 mass parts more than, more than more preferably 6 mass parts.In addition, it is logical It is often below 500 mass parts, be preferably below 300 mass parts, below more preferably 200 mass parts.
By making polyurethane dispersant (b-1) with respect to alkali soluble resin, photopolymerization monomer, Photoepolymerizationinitiater initiater C the amount of () is more than above-mentioned lower limit, in the solution of photosensitive polymer combination, there are following tendencies：Divided based on polyurethane The compatibility of powder (b-1) and alkali soluble resin (d) and improve color material (a) with respect to cohesion space bit resistive, thus Dispersibility is made to improve, or, when making light filter, by polyurethane dispersant (b-1), alkali soluble resin (d) and ultraviolet Line irradiates, and the bridging property of the composition with ethylenically unsaturated group that can crosslink under Photoepolymerizationinitiater initiater (c) effect enters One step strengthens, and thus makes to improve with respect to the patience of alkaline developer and high-temperature process as effect of the present invention, thus easy shape Become high fine fine rule.
In addition, by making to have the bad polyurethane dispersant (b-1) of tendency of the dissolubility in alkaline developer, light gathers Conjunction property monomer, the amount of Photoepolymerizationinitiater initiater (c) are below above-mentioned higher limit, exist and can make the unexposed portion of ultraviolet in alkali development Dissolubility in liquid improves thus reducing the tendency of the development residue on substrate.
In addition, using in the case of aforesaid thio-alcohol, consolidating with respect to the whole of photosensitive polymer combination of the present invention Body composition, the content ratio of thio-alcohol is usually more than 0.1 mass %, is preferably more than 0.3 mass %, is more preferably More than 0.5 mass %, usually below 10 mass %, it is preferably below 5 mass %.If the content of thio-alcohol is very few, can The improvement of sensitivity decrease can be led to not enough, if excessively, storage stability may be led to be deteriorated.
In the case of making to contain pigment derivative in the photosensitive polymer combination of the present invention, photosensitive with respect to the present invention Property resin combination all solids composition, the content ratio of pigment derivative is usually more than 0.1 mass %, and usually 10 Below quality %, it is preferably below 5 mass %.
In addition, using in the case of surfactant, its content ratio is whole solid with respect to photosensitive polymer combination Body composition is usually more than 0.001 mass %, is preferably more than 0.005 mass %, is more preferably more than 0.01 mass %, enters one Step is preferably more than 0.03 mass %, in addition, usually below 10 mass %, be preferably below 1 mass %, more preferably 0.5 Below quality %, below more preferably 0.3 mass %.By the content ratio that makes surfactant within the above range, Existing easily makes the flatness of coated film, uniformity become sufficiently to be inclined to.
It should be noted that the photosensitive polymer combination of the present invention can be using the solvent (e) above describing, so that it is solid Body constituent concentration is usually more than 5 mass %, is preferably below 10 mass %, is in addition usually below 50 mass %, is preferably The mode of 30 mass % makes solution.Become good by within the above range, there is the coating making photosensitive polymer combination Good tendency.
[manufacture method of photosensitive polymer combination]
The photosensitive polymer combination (hereinafter also referred to " resist ") of the present invention can conventionally manufacture.
Typically for color material (a), preferably in advance using paint shaker, sand mill, ball mill, roller mill, burrstone mill, Airflow milling, homogenizer etc. carry out decentralized processing.By decentralized processing, color material (a) can occur micronized, the therefore coating of resist Characteristic improves.In addition, be used black color material as color material (a) in the case of, be favorably improved light shielding ability.
Decentralized processing is generally preferably to be applied in combination color material (a), dispersant (b), solvent (e) and alkali as needed The all or part of system of soluble resin (d) carries out (below, to be also used for the mixture of decentralized processing and through at this Compositionss obtained from reason are referred to as " ink " or " dispersible pigment dispersion ").In this decentralized processing, by using the poly- ammonia of the present invention Ester dispersant (b-1), can suppress gained ink and resist through when thickening (dispersion stabilization is excellent), therefore preferably.
It should be noted that carrying out to the liquid containing the whole compositions in photosensitive polymer combination to be engaged to point Dissipate in the case of processing, the heat release producing during due to decentralized processing, the composition that may result in high response occurs modification.Cause This, preferably carry out decentralized processing with the system comprising mentioned component.
In the case of making color material (a) scattered using sand mill, preferably use diameter 0.1～8mm about bead or Zirconium oxide bead.For decentralized processing condition, temperature is usually 0 DEG C～100 DEG C, is preferably the scope of room temperature～80 DEG C.Just divide For the scattered time, composition according to liquid and the size of decentralized processing device etc. are different and there are different suitable times, therefore Suitably adjusted.
Scattered substantially standard is：The gloss of control ink is, make 20 degree of mirror surface luster [JIS Z8741 of resist (1997)] reach 100～200 scope.In the case that the glossiness of resist is low, decentralized processing is insufficient, most cases Lower can remain coarse pigment (color material) particle, exist and lead to developability, adaptation, resolution etc. to become insufficient possibility Property.In addition, if carrying out decentralized processing to glossiness to exceed above range, then pigment can be led to crush and produce a large amount of ultra microns , therefore there is the impaired tendency of dispersion stabilization on the contrary in son.
Then, by the above-mentioned other composition mixing included in the ink being obtained by above-mentioned decentralized processing and resist, Make uniform solution.In the manufacturing process of resist, it is mixed in liquid due to having fine dust in many cases, Therefore for gained resist, carry out filtration treatment preferably by filter etc..
[solidfied material]
Solidified by making the photosensitive polymer combination of the present invention, can get the solidfied material of the present invention.Sense by the present invention The solidfied material of photosensitive resin composition solidification preferably uses as black matrix" or coloring distance piece.
[black matrix"]
Hereinafter, for the black matrix" of the photosensitive polymer combination employing the present invention, carry out according to its manufacture method Explanation.
(1) supporter
As the supporter for forming black matrix", as long as having the intensity of appropriateness, to its material not especially Limit.As supporter, mainly using transparency carrier.As material, can enumerate for example：Polyethylene terephthalate etc. is gathered The thermoplastic resins such as the polyolefin resins such as esters resin, polypropylene, polyethylene, Merlon, polymethyl methacrylate, polysulfones Heat-curing resin piece or the various glass such as fat film-making, epoxy resin, unsaturated polyester resin, poly- (methyl) acrylic resin Glass etc..Wherein, from the viewpoint of thermostability, preferably glass, heat-resistant resin.
In addition, also there being the situation of the transparency electrode in substrate surface film forming ITO or IZO etc..In addition to transparency carrier, Can be formed on tft array.
In order to improve the surface physical properties such as cementability it is also possible to as needed Corona discharge Treatment, ozone be carried out to supporter Thin film formation process of the various resins such as process, silane coupler or polyurethane based resin etc..
The thickness of supporter is usually 0.05～10mm, is preferably the scope of 0.1～7mm.In addition, carrying out various resins Thin film formation process in the case of, its thickness is usually 0.01～10 μm, is preferably 0.05～5 μm of scope.
(2) black matrix"
In order to form the black matrix" of the present invention by the photosensitive polymer combination of the above-mentioned present invention, in transparency carrier Deng the photosensitive polymer combination of the present invention being coated with supporter and being dried, then photomask is placed on this film, every This photomask and carry out image exposure, development, and carry out heat cure or photocuring further as desired, thus can be formed black Colour moment battle array.
(3) formation of black matrix"
(3-1) coating of photosensitive polymer combination
Coating on the supporters such as transparency carrier for the photosensitive polymer combination of black matrix" can pass through spin-coating method, line Excellent (Wire bar) method, flow coat method, die coating method, rolling method or spraying process etc. are carrying out.Wherein, according to die coating method, can significantly cut Subtract coating fluid usage amount, and the impact of the fog adhering to when not adopting spin-coating method completely etc., foreign body can be suppressed to produce etc., from It is preferred from the viewpoint of synthesis.
If the thickness of film is blocked up, pattern development becomes difficult, and sometimes in liquid crystal cells chemical industry sequence between Gap adjustment becomes difficult, if the thickness of film is excessively thin, is difficult to improve pigment concentration, sometimes can not show desired face Color.The thickness of film with dried film thickness gauge it is usually preferred to 0.2～10 μm scope, more preferably in 0.5～6 μm of model Enclose, further preferably in 1～4 μm of scope.
(3-2) drying of film
The drying of the film after supporter photosensitive resin coating compositionss preferably by using hot plate, IR baking oven or The seasoning of convection oven is carrying out.The condition being dried can be according to the property of the species of above-mentioned solvent composition, the drying machine of use Energy etc. suitably selects.Drying time according to the species of solvent composition, the performance of drying machine that uses etc., generally at 40～200 DEG C Temperature, in the range of 15 seconds～5 minutes select, preferably 50～130 DEG C temperature, in the range of 30 seconds～3 minutes Select.
Baking temperature is higher, more can improve the cementability that film is with respect to supporter, but if baking temperature is too high, then have When alkali soluble resin can decompose and cause thermal polymerization, and then occur poor visualization.It should be noted that this film is dry Drying process can also be the hypobaric drying method not improving temperature and being dried in decompression interior.
(3-3) expose
Image exposure is the mask pattern overlapping minus on the film of photosensitive polymer combination, and across this mask artwork The light source of case irradiation ultraviolet radiation or luminous ray is carrying out.Now, in order to prevent the sensitivity of optical polymerism layer being caused by oxygen Reduce it is also possible to be exposed after forming the oxygen barrier layer such as polyvinyl alcohol layer on the film of optical polymerism as needed.
Used in above-mentioned image exposure, light source is not particularly limited.As light source, can enumerate for example：Xenon lamp, halogen Lamp, tungsten lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, metal halide lamp, middle medium pressure mercury lamp, low pressure mercury lamp, carbon arc and fluorescence The lamp source such as lamp and argon laser, YAG laser, excimer laser, N_2 laser, helium cadmium laser and semiconductor laser etc. swash Radiant etc..In the case of irradiating and use the light of specific wavelength, it is possible to use optical filter.
(3-4) develop
The black matrix" of the present invention can make as follows：Using above-mentioned light source to the painting being formed by photosensitive polymer combination Film carries out image exposure, then using organic solvent or comprise surfactant and the aqueous solution of alkali compoundss is shown Shadow, thus forms image on substrate.This aqueous solution can further include machine solvent, buffer agent, chelating agent, dyestuff or face Material.
As alkali compoundss, can enumerate for example：Sodium hydroxide, potassium hydroxide, Lithium hydrate, sodium carbonate, potassium carbonate, carbon Sour hydrogen sodium, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, dibastic sodium phosphate, potassium hydrogen phosphate, di(2-ethylhexyl)phosphate The inorganic alkaline compounds such as hydrogen sodium, potassium dihydrogen phosphate and ammonium hydroxide and monoethanolamine, diethanolamine or triethanolamine, list Methyl amine, dimethyl amine or Trimethylamine, MEA, diethylamide or triethylamine, single isopropylamine or diisopropylamine, N-butylamine, monoisopropanolamine, diisopropanolamine (DIPA) or triisopropanolamine, aziridine, ethylene diimine, Tetramethylammonium hydroxide And the organic basic compound such as choline (TMAH).These alkali compoundss can also be mixture of more than two kinds.
As surfactant, can enumerate for example：Polyoxyethylene alkyl ether class, polyoxyethylene alkylaryl ether class, polyoxy Nonionic surfactant, the alkylbenzenes such as vinyl alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters The anionics such as Sulfonateses, alkyl naphthalene sulfonic acid salt, alkylsurfuric acid salt, alkyl sulfonates and sulfosuccinate ester salt class The amphoteric surfactant such as surfactant and alkyl betaines bases and amino acidses.
As organic solvent, can enumerate for example：Isopropanol, benzylalcohol, ethyl cellosolve, butyl cellosolve, ethylene glycol monophenyl ether, Propylene glycol and DAA etc..Organic solvent be can be used alone it is also possible to be applied in combination with aqueous solution.
The condition of development treatment is not particularly limited, generally can make development temperature 10～50 DEG C scope, preferably exist 15～45 DEG C, particularly preferably at 20～40 DEG C, developing method can adopt immersion development method, spray development method, magnetic brush development method Or any means in supersonic wave development method etc..
(3-5) heat cure is processed
For the supporter after development, implement heat cure process or photocuring is processed, be preferable to carry out heat cure and process.Now Heat cure treatment conditions can select in the scope of 100～280 DEG C of temperature, preferably in the range of 150～250 DEG C, the time Can select in the range of 5～60 minutes.
The width of the bottom of the black matrix" being formed as described above is usually 3～50 μm, is preferably 4～30 μm, especially For being in the case of high fine rule, preferably 4～8 μm, height is usually 0.5～5 μm, is preferably 1～4 μm.In addition, volume Resistivity is 1 × 1013More than Ω cm, be preferably 1 × 1014More than Ω cm, relative dielectric constant is less than 6, is preferably 5 Below.Further, the corresponding optical concentration (OD) of every 1 μ m thick is usually more than 3.0, is preferably more than 3.5, more preferably More than 4.0, particularly preferably more than 4.2.
[formation of other colour filter pictures]
The supporter be provided with black matrix" is coated with containing red using with above-mentioned (3-1)～(3-5) identical technique Color, one of the green and blue photosensitive polymer combination of color material of color after being dried, overlap on film Photomask, carries out image exposure, development across this photomask, and forms pixel map as needed by heat cure or photocuring Picture, thus can make dyed layer.Photosensitive polymer combination for three kinds of red, green and blue colors carries out this respectively Operation, thus can form colour filter picture.Their order is not exposed to above-mentioned restriction.
[coloring distance piece]
The photosensitive polymer combination of the present invention, in addition to can act as black matrix", is also used as colouring distance piece Use resist.In the case that distance piece is used for TFT type LCD, in the presence of the light on inciding TFT, sometimes as switch The TFT of element can occur misoperation, and coloring distance piece is just used to prevent this situation from using, for example, in Japanese Unexamined Patent Publication Record in 8-234212 publication and made distance piece be light-proofness.For coloring distance piece, except using coloring distance piece with covering Beyond mould, it is possible to use the method same with aforesaid black matrix" is formed.
[formation of transparency electrode]
Light filter can form the transparency electrode such as ITO under keeping original state on image, and as color display, A part for the part of liquid crystal indicator etc., but in order to improve surface smoothness and durability it is also possible to exist as desired The top coat such as polyamide or polyimides is arranged on image.In addition, also some is in planar orientation type type of drive (IPS mould Formula) etc. do not form transparency electrode in purposes.
[image display device]
The image display device of the present invention is that possess the black matrix" being formed by the photosensitive polymer combination of the present invention Image display device, as long as the device of display image or image is not then subject to particular determination, can enumerate for example described below Liquid crystal indicator and organic el display etc..
[liquid crystal indicator]
The liquid crystal indicator of the present invention is to be made using the black matrix" of the above-mentioned present invention, colour element or black The formation order of colour moment battle array or forming position etc. are not subject to particular determination.
Liquid crystal indicator is generally as follows to be made：It is formation alignment films on light filter, take distance piece is dispersed in this After on film, fit with counter substrate and form liquid crystal cells, inject liquid crystal in the liquid crystal cells being formed, with opposite electrode Line and complete liquid crystal indicator.
As alignment films, the preferably resin film of polyimides etc..The formation of alignment films generally can using woodburytype and/ Or flexographic printing process, the thickness of alignment films can be number 10nm.Fire the cured carrying out alignment films by heat after, pass through Ultraviolet irradiation or be surface-treated based on the process of friction cloth, thus being processed into the table of the deflection of adjustable liquid crystal Surface state.
As distance piece, can be using the distance piece of the size in gap (gap) being suitable for and counter substrate between, generally It is preferably 2～8 μm of distance piece.The photosensitive interval of transparent resin film can also be formed by photoetching process on filter substrate Part (PS), and this photosensitive distance piece (PS) of effectively utilizes is replacing distance piece.As counter substrate, array base generally can be used Plate, particularly preferred TFT (thin film transistor (TFT)) substrate.
Different according to the purposes of liquid crystal indicator with the gap fitted of counter substrate, but generally in 2～8 μm of scope Interior selection.After fitting with counter substrate, for the part beyond liquid crystal injecting port, entered using encapsulants such as epoxy resin Row sealing.Encapsulant irradiated by ultraviolet (UV) and/or heating and solidify, thus by liquid crystal cells peripheral sealing.
Periphery be have passed through to the liquid crystal cells of sealing, after being cut into panel unit, reduced pressure in vacuum interior, will Above-mentioned liquid crystal injecting port impregnated in liquid crystal, then by vacuum interior release pressure, thus injects liquid crystal in liquid crystal cells.
Degree of decompression in liquid crystal cells is usually 1 × 10-2～1 × 10-7Pa, preferably 1 × 10-3～1 × 10-6Pa.Separately Outward, during decompression, preferred pair liquid crystal cells are heated, and warm temperature is usually 30～100 DEG C, more preferably 50～90 DEG C.
Heating during decompression keeps being typically set to the scope of 10～60 minutes, then impregnated in liquid crystal.For being filled with Liquid crystal injecting port is sealed, thus completing liquid crystal indicator (face by the liquid crystal cells of liquid crystal by making UV solidified resin solidify Plate).
The species of liquid crystal is not particularly limited, and can be that the fragrant same clan, aliphatic category or polycyclic compound etc. were in the past public The liquid crystal known, can be any type in lysotropic liquid crystal, thermotropic liquid crystal etc..In thermotropic liquid crystal it is known to nematic crystal, Smectic crystal and cholesteryl liquid crystal etc., can be any types therein.
[organic el display]
Organic el display can make as follows：As shown in figure 1, be produced on first in transparent support substrate 10 formed by Pattern [that is, the pixel 20 and be arranged at the resin black matrix between neighbor 20 that photosensitive polymer combination is formed (not shown)] light filter, across organic of lamination of organic protection layer 30 and inorganic oxide film 40 on this light filter Body of light 500, thus makes organic EL element 100.
It should be noted that in pixel 20 and resin black matrix, at least black matrix" is the photonasty using the present invention Resin combination and make.As the laminating method of organic luminorphor 500, can enumerate for example：Shape successively on light filter Become transparent anode 50, hole injection layer 51, hole transmission layer 52, the method for luminescent layer 53, electron injecting layer 54 and negative electrode 55, And；And make the organic luminorphor 500 being formed on another substrate be fitted in method on inorganic oxide film 40 etc..
Can be using such organic EL element 100 making, using for example《Organic el display》(Ohmsha,Ltd.、 August in 2004 distribution on the 20th, former quiet scholar, Anda thousand wave vector, village Tian Yingxing write) described in method etc. and make organic EL and show Show device.
It should be noted that the light filter of the present invention is applicable to the organic el display of passive matrix mode, also can fit Organic el display for active drive mode.
Embodiment
Hereinafter, in conjunction with the embodiments and comparative example carries out more specific detail to the present invention, but without departing from the present invention's In the range of main points, it is not limited to following examples.
<Dispersant 1>
Dispersant 1 will be used as through following (operation 1-1)～urethanes 1 obtained from (operation 1-9).
Compound A：DODECANOL, 1-
Compound B：6-caprolactone
Compound C：Butanol Zr catalyst
Compound D：Toluene di-isocyanate(TDI) (TDI)
Compound E：Diethanolamine
Tertiary amino compound 1：3- (diethylamino) -1,2- propylene glycol
Polyether compound 1：Poly- (propylene glycol) single-butyl ether (Mn=1100)
(operation 1-1) make compound A (114.6 mass parts) and compound B (912.3 mass parts) in nitrogen atmosphere, in 150 DEG C are mixed and are reached homogenization.
In the mixture that (operation 1-2) obtains in (operation 1-1) add compound C (4.0 mass parts), and make its in 180 DEG C are reacted 20 hours.
The reactant obtaining in (operation 1-2) is cooled to room temperature by (operation 1-3), obtains wax-like petchem 1.
Compound D (83.46 mass parts) is added reaction vessel in nitrogen atmosphere and is heated to 50～60 by (operation 1-4) ℃.
The petchem 1 that (operation 1-5) obtains in 50 DEG C of (operations 1-3) making 800 mass parts melts, and spends 2 Hour adds it in the compound D being heated to 50～60 DEG C obtaining in (operation 1-4).
The mixed liquor obtaining in (operation 1-5) is stirred 1 hour, so that it is reacted simultaneously in 60 DEG C by (operation 1-6).
The reactant obtaining in (operation 1-6) is cooled to 20 DEG C by (operation 1-7), adds compound E (50.37 mass Part) so as to carry out reaction until there is not residual isocyanate in 35 DEG C, obtain petchem 2.
Compound D (26.68 mass parts) is added reaction vessel in nitrogen atmosphere by (operation 1-8), then, adds 131 The solvent propylene glycol methylether acetate of mass parts, tertiary amino compound 1 (17.12 mass parts), (operation of 57.68 mass parts The above-mentioned petchem 2 obtaining in 1-7), is heated to 70 DEG C while being stirred.
(operation 1-9):Polyether compound 1 (17.00 mass are added further in the mixed liquor obtaining in (operation 1-8) Part), in 70 DEG C of reactions 2 hours, until there is not residual isocyanate, thus obtain showing weight average molecular weight in gpc analysis (Mw) be 22000 and number-average molecular weight (Mn) be 8800 urethanes 1.
<Dispersant 2>
It is used through following (operation 2-1)～urethanes 2 obtained from (operation 2-13) as dispersant 2.
Compound D：Toluene di-isocyanate(TDI) (TDI)
Compound E：Diethanolamine
Compound F：Dimethylamino propylamine
Compound G：Acrylic acid 2- hydroxy methacrylate
Compound H：2,6 di tert butyl 4 methyl phenol
Polyether compound 1：Poly- (propylene glycol) single-butyl ether (Mn=1100)
Petchem 1：The petchem obtaining in above-mentioned (operation 1-3).
Petchem 2：The petchem obtaining in above-mentioned (operation 1-7).
(operation 2-1) is by compound F (100 mass parts), compound G (113.8 mass parts) and compound H (0.29 mass Part) in 70 DEG C together stirring 48 hours, until Michael addition reaction complete, obtain tertiary amino compound 2.
(operation 2-2) filling compound D (25.0 mass parts) in the stirring reaction container be heated to 50 DEG C.
(operation 2-3) fills polyether compound 1 (125.0 mass parts, be about 0.8 molar equivalent with respect to TDI) to dripping Liquid funnel, the temperature between keeping 50～60 DEG C, spend and drop within 4 hours above-mentioned stirring reaction container.
The reactant obtaining in (operation 2-3) is kept 60 minutes by (operation 2-4) in 70 DEG C.
(operation 2-5) determines completing of reaction according to the titration of residual isocyanate, and its reactant mixture is cooled to 20℃.
(operation 2-6) add in the reactant mixture that (operation 2-5) obtains compound E (24.14 mass parts, with respect to TDI is about 1.6 molar equivalents), keep at room temperature, until there is not the Carbimide. that can determine by infrared spectroscopic analysis The residual of ester.
(operation 2-7) (this mixture contains diethanolamine and TDI's by the mixture of the product obtaining in (operation 2-6) Diadduct) it is dissolved in ether, and carry out eluting using silicagel column.
The chromatographic column that (operation 2-8) will carry out eluting in (operation 2-7) utilizes ether to wash 3 times, fraction is merged, so Remove solvent in a vacuum afterwards, obtain the solid product of the polyether compound 2 of 90 mass parts.
The diadduct of diethanolamine and TDI can be removed in above-mentioned (operation 2-7) and (operation 2-8).
Compound D (26.68 mass parts) is added reaction vessel in nitrogen atmosphere by (operation 2-9).
(operation 2-10) adds the acetic acid methoxyl group propyl ester as solvent in the reactor comprising above-claimed cpd D (130.87 mass parts), petchem 2 (15.23 mass parts) and polyether compound 2 (10.68 mass parts) and tertiary amino Compound 2 (28.30 mass parts).
(operation 2-11) is heated to 70 DEG C while the mixture obtaining in (operation 2-10) is stirred.
Petchem 1 (26.09 mass parts) is added the reactant mixture of (operation 2-11) by (operation 2-12), in 70 DEG C Keep 2 hours.
(operation 2-13) confirms there is not residual isocyanate in the reactant mixture obtaining in (operation 2-12), obtains Show in gpc analysis weight average molecular weight (Mw) be 20000 and number-average molecular weight (Mn) be 8000 urethanes 2.
<Dispersant 3>
Dispersant 3 will be used as through following urethanes 3 obtained from (operation 3-1).
Compound I：Chlorotoluene
(content of urethanes 1 is for reactant liquor 200 mass parts that (operation 3-1) to above-mentioned (operation 1-9) obtains 94.97 mass parts) in add compound I (tertiary amine in 2.35 mass parts, the urethanes 1 being equivalent in reactant liquor The amount of the molal quantity of the 20% of molal quantity), stir 20 hours with 70 DEG C, thus obtain one of the tertiary amine in urethanes 1 Part there occurs quaternized urethanes 3.
<Dispersant 4>
Dispersant 4 will be used as through following urethanes 4 obtained from (operation 4-1).
Compound E：Diethanolamine
(operation 4-1) in above-mentioned (operation 1-8), replace tertiary amino compound 1 (17.12 mass parts, 0.12 mole) and Add the compound E (diethanolamine, 12.62 mass parts, 0.12 mole) of identical molal quantity, in addition, with (operation 1-1) ～(operation 1-9) is similarly carried out, and obtains urethanes 4.
<Dispersant 5>
Dispersant 5 will be used as through following urethanes 5 obtained from (operation 5-1).
Compound J：1,6-HD
(operation 5-1) in above-mentioned (operation 1-8), replace tertiary amino compound 1 (17.12 mass parts, 0.12 mole) and Add the compound J (14.18 mass parts, 0.12 mole) of identical molal quantity, in addition, with (operation 1-1)～(operation 1- 9) similarly carry out, obtain urethanes 5.
<Dispersant 6>
Dispersant 6 will be used as through following urethanes 6 obtained from (operation 6-1).
Compound K：Trimethylolpropane
(operation 6-1), in above-mentioned (operation 1-8), compound D increment for 28.04 mass parts and is added compound K (0.52 mass parts, 0.004 mole), in above-mentioned (operation 1-9), polyether compound 1 increment are 21.26 mass parts, except this In addition, carry out in the same manner as (operation 1-1)～(operation 1-9), obtaining weight average molecular weight (Mw) is 23000 and number-average molecular weight (Mn) be 9200 urethanes 6.
The element of dispersant 1～6 is as shown in table 1.
<Carbon-loaded inks 1>
Allocate pigment, dispersant, dispersing aid, solvent according to following composition, and be prepared for charcoal using following method Black ink 1.
First, the solid constituent of pigment, dispersant, dispersing aid is allocated to following degree.
Pigment SB350 (white carbon black that Degussa company manufactures)：100 mass parts
Dispersant agent 1：20 mass parts (are converted into solid constituent)
(Lubrizol company system, the phthalocyanine color with acidic-group spread out dispersing aid (pigment derivative) S12000 Biological)：2 mass parts
Solvent propylene glycol monomethyl ether acetate：226.6 mass parts
Above-mentioned each composition is sufficiently stirred for, thus being mixed.
Then, carry out 6 hours decentralized processings using paint shaker in 25～45 DEG C of scope, obtain dispersion liquid.Make For pearl, employ the zirconium oxide bead of diameter 0.5mm, add dispersion liquid 60 mass parts and pearl 180 mass parts.Dispersion terminates Afterwards, using filter, pearl is separated with dispersion liquid, be prepared for the carbon-loaded inks 1 of solid constituent 35 mass %.
<The preparation of carbon-loaded inks 2～14>
The species of the dispersant of carbon-loaded inks 1 and pigment is changed to the dispersant described in table 2 and pigment, utilizes and charcoal Black ink 1 identical method has carried out the decentralized processing stirring, mixing, utilize paint shaker, is prepared for solid constituent 35 matter The carbon-loaded inks 2～14 of amount %.
Table 2
That Details as Follows is described for each composition in table 2.
·SB350：The charcoal blacks average primary particle diameter that Degussa company manufactures：31nm
·MA77：The charcoal blacks average primary particle diameter that Mitsubishi chemical Co., Ltd manufactures：23nm
·Disperbyk-161：The dispersant that BYK-Chemie company manufactures has will be by first using skeleton link group The high molecular weight dispersant of the structure that the polyurethane skeleton that phenylene diisocyanate polymer is formed links.There is alkaline sense Group.
·Disperbyk-167：The dispersant that BYK-Chemie company manufactures has will be by first using skeleton link group In the structure that the polyurethane skeleton that phenylene diisocyanate polymer is formed links～low-molecular-weight dispersant.There is alkalescence Functional group.
·Ajisper PB-821：The dispersant that Ajinomoto Fine-Techno Co., Ltd. manufactures has polyethylene Imines or the alkaline graft polymers of polyethylene/polyamine backbone.
·Floren KDG-2400：The dispersant that Kyoeisha Chemical Co., Ltd. manufactures has poly- the third of basic functionality Alkene acrylic grafting polymer.
·HIPLAAD ED-701：The dispersant that this chemical conversion of nanmu Co., Ltd. manufactures have polyethyleneimine or polyethylene/ The alkaline graft polymers of polyamine backbone.
·Disperbyk-2000：The quaternized ammonium salt modified propylene of the dispersant tertiary amine that BYK-Chemie company manufactures Acrylic block copolymers.
·Disperbyk-2001：The sour modified acrylic acid block of the dispersant tertiary amine that BYK-Chemie company manufactures Copolymer.
<Alkali soluble resin (1)：Epoxy (methyl) acrylate (D1-2)>
[chemical formula 90]
By epoxide (epoxide equivalent 264) 50g of said structure, acrylic acid 13.65g, methoxy butyl acetate 60.5g, triphenylphosphine 0.936g and p methoxy phenol 0.032g add the flask being provided with thermometer, agitator, condensing tube In, so that it is reacted in 90 DEG C while being stirred and reach below 5mgKOH/g to acid number.Reaction needs 12 hours, has obtained ring Oxypropylene acid esters solution (1).
By above-mentioned epoxy acrylic ester solution (1) 25 mass parts, trimethylolpropane (TMP) 0.76 mass parts, biphenyl four Carboxylic acid dianhydride (BPDA) 3.3 mass parts and the addition of tetrabydrophthalic anhydride (THPA) 3.5 mass parts are provided with thermometer, stir Mix in the flask of device, condensing tube, so that it is to slowly warm up to 105 DEG C and be reacted.
When resin solution reaches transparent, it is diluted using methoxy butyl acetate, solid constituent is adjusted to 50 matter Amount %, has obtained acid number 115mgKOH/g, has been 2600 using the weight average molecular weight (Mw) being converted into polystyrene that GPC measures Alkali soluble resin (1).
<Alkali soluble resin (2)：Epoxy (methyl) acrylate (D1-2)>
In the same manner as in manufacture with alkali soluble resin (1), make epoxide (epoxide equivalent 264), acrylic acid, acetic acid Methoxybutyl, triphenylphosphine and p methoxy phenol reaction, have obtained epoxy acrylic ester solution (2).
By above-mentioned epoxy acrylic ester solution (2) 25 mass parts, trimethylolpropane (TMP) 0.37 mass parts, biphenyl four Carboxylic acid dianhydride (BPDA) 4.76 mass parts and tetrabydrophthalic anhydride (THPA) 1.02 mass parts add be provided with thermometer, In agitator, the flask of condensing tube, it while being stirred, is made to be to slowly warm up to 105 DEG C and be reacted.
When resin solution reaches transparent, it is diluted using methoxy butyl acetate, solid constituent is adjusted to 50 matter Amount %, has obtained acid number 100mgKOH/g, has been 10000 using the weight average molecular weight (Mw) being converted into polystyrene that GPC measures Alkali soluble resin (2).
<Alkali soluble resin (3)：Epoxy (methyl) acrylate (D1-1)>
Japanese chemical medicine (strain) is made " XD1000 ", and (the poly epihydric alcohol base ether of Dicyclopentadiene-phenol polymer, epoxy are worked as Amount 252) 300 mass parts, methacrylic acid 104 mass parts, p methoxy phenol 0.2 mass parts, triphenylphosphine 5 mass parts and Propylene glycol monomethyl ether 255 mass parts are dosed in reaction vessel, are stirred reaching until acid number in 100 DEG C 3.0mg-KOH/g.Then, add tetrabydrophthalic anhydride 145 mass parts further, carry out reaction in 4 hours in 120 DEG C, obtain Solid constituent 50 mass %, acid number 106mg-KOH/g, the weight average molecular weight being converted into polystyrene measuring using GPC are arrived (Mw) 1580 alkali soluble resin (3).
<Photoepolymerizationinitiater initiater (1)>
(two ketoboidies)
Ethyl carbazole (5g, 25.61mmol) and adjacent naphthoyl chloride (5.13g, 26.89mmol) are dissolved in the dichloro of 30ml Methane, is cooled to 2 DEG C using ice-water bath and is stirred, with the addition of AlCl3(3.41g、25.61mmol).Further in room temperature The 15ml dichloromethane solution of crotonyl chloride (2.81g, 26.89mmol) is added in the backward reactant liquor of stirring stirring in 3 hours, and Add AlCl3(4.1g, 30.73mmol), continues to have stirred 1 hour 30 minutes.Reactant liquor is added in frozen water 200ml, adds Add methylene chloride 200ml, and organic layer is divided liquid.After the organic layer reclaiming being dried using anhydrous magnesium sulfate, reduced pressure down Concentrate, obtained two ketoboidies of white solid (10g).
(oxime body)
Two ketoboidies (3.00g, 7.19mmol), NH is mixed in isopropanol 30ml2OH·HCl(1.09g、15.81mmol)、 And sodium acetate (1.23g, 15.08mmol), carry out backflow in 3 hours.After reaction terminates, concentration of reaction solution, add to residue obtained Enter ethyl acetate 30ml, washed using saturated sodium bicarbonate aqueous solution 30ml, saturated aqueous common salt 30ml, and utilize anhydrous sulfur Sour magnesium is dried.After filtration, under reduced pressure organic layer is concentrated, obtained solid 1.82g.Post is utilized to this solid Chromatograph carries out purification, has obtained the oxime body of faint yellow solid 2.22g.
(oxime ester body)
Oxime body (2.22g, 4.77mmol) and chloroacetic chloride (1.34g, 17.0mmol) are added in dichloromethane 20ml simultaneously Carry out ice bath cooling, Deca triethylamine (1.77g, 17.5mmol), and keep this state to carry out reaction in 1 hour.Using thin layer After chromatograph confirms that raw material disappears, water is added to terminate reaction.Reactant liquor is utilized saturated sodium bicarbonate aqueous solution 5ml to wash 2 times, washed 2 times using saturated aqueous common salt 5ml, and be dried using anhydrous sodium sulfate.After filtration, under reduced pressure to organic Layer is concentrated, and carries out purification to residue obtained utilization column chromatography (ethyl acetate/hexane=2/1), has obtained the yellowish of 0.79g The Photoepolymerizationinitiater initiater (1) of color solid.Photoepolymerizationinitiater initiater (1)1The chemical shift of H-NMR is as follows.
1H-NMR(CDCl3):σ1.17(d,3H),1.48(t,3H),1.53(s,3H),1.81(s,3H),2.16(s,3H), 2.30(s,3H),3.17-3.32(m,2H),4.42(q,2H),4.78-4.94(br,1H),7.45-7.59(m,5H),7.65 (dd,1H),7.95(m,2H),8.04(m,2H),8.14(dd,1H),8.42(d,1H),8.64(d,1H)
The structure of Photoepolymerizationinitiater initiater (1) is as described below.
[chemical formula 91]
<Embodiment 1>
(preparation of resist 1 (photosensitive polymer combination 1))
Using carbon-loaded inks 1 produced above, in the way of making each composition described in table 3 reach the ratio shown in table 3 Allocated, and be stirred using stirrer so as to dissolve, be prepared for the resist 1 of solid component concentration 15 mass %.
That Details as Follows is described for each composition in table 3.
·PM21：Phosphate ester (Nippon Kayaku K. K's system, KAYAMER (registered trade mark) containing methylacryloyl PM21, closely sealed improving agent).
·SH6040：Epoxy silane coupling agent (Dongli Ltd.'s system, SH6040, closely sealed improving agent)
·F-559：Surfactant (DIC company system, F-559)
<Embodiment 2～7, comparative example 1～9>
(preparation of resist 2～16 (photosensitive polymer combination 2～16))
Using the carbon-loaded inks shown in table 4,5 and 6, the species of each composition of resist 1 is changed in table 4,5 and 6 The each composition recorded, and they are allocated in the way of reaching the ratio shown in table 3, adopt and resist 1 identical side Method, is stirred using stirrer so as to dissolve, and is prepared for the resist 2～16 that solid component concentration is 15 mass % respectively. Wherein, so that the summation of the solid component concentration of IRG907 and DETX-S of resist 15 is caused with the photopolymerization in resist 1 The solid component concentration identical mode of agent (1) is with 4:1 quality ratio mixes and uses.
Table 6
That Details as Follows is described for each composition in table 5 and 6.
·IRG907：IRGACURE 907, Ciba Specialty Chemicals company system, 2- methyl isophthalic acid-[4- (first Sulfenyl) phenyl] -2- morpholinopropane -1- ketone.
·DETX-S：KAYACURE DETX-S, Japanese chemical medicine (strain) system, 2,4- dimethyl thioxanthone.It is in resist 15 Solid constituent in content be 1.6 mass %.
Photoepolymerizationinitiater initiater (2)：OXE02, BASF AG's system.There is following chemical constitution.
[chemical formula 92]
(evaluation of ink)
(1) the viscosity evaluation of carbon-loaded inks
Viscosity using the carbon-loaded inks 1～14 to preparation for the viscometer (Toki Sangyo Co., Ltd.'s system, RE105L) is carried out Measure.The viscosity of all carbon-loaded inks is all in the scope of 10～20mPa s.Determine carbon-loaded inks immediately after preparation (just just After dispersion) and ink after standing 1 week at room temperature viscosity, and be classified judging according to following standard.Result is recorded In table 7.
◎：Even if placing at room temperature 1 week after ink dispersion, there is not thickening yet.
○：Thickening can occur when placing 1 week at room temperature after ink dispersion, but stablize within 20mPa s.
△：When placing 1 week at room temperature after ink dispersion, thickening can persistently occur, more than 20mPa s.
×：Start notable thickening after ink just disperses, i.e. more than 20mPa s within 3 days.
(evaluation of resist)
(1) the viscosity evaluation of resist (photosensitive polymer combination)
Viscosity using the resist 1～15 to preparation for the viscometer (Toki Sangyo Co., Ltd.'s system, RE105L) is carried out Measure.The viscosity of all resists is all in the scope of 2～5mPa s.Determine resist just immediately after preparation, stand at room temperature The viscosity of 1 month resist afterwards, and be classified judging according to following standard.Result is recorded in table 7.
◎：Even if placing at room temperature 1 month after resist preparation, there is not thickening yet.
○：When placing 1 month at room temperature after resist preparation, thickening can occur, but the degree of thickening is in 0.5mPa Within s.
△：When placing 1 month at room temperature after resist preparation, thickening can occur, the degree of thickening is more than 0.5mPa s.
×：Place at room temperature 1 week after resist preparation and thickening occurs, the degree of thickening is more than 0.5mPa s.
The viscosity of resist can cause significant impact in coating, therefore, according to strict as above compared with ink Standard implementation evaluate.
(2) making of black matrix" (BM)
Using spinner, prepared resist 1～16 is coated glass substrate, after carrying out drying under reduced pressure, using heat Plate has carried out drying in 150 seconds in 100 DEG C.Then, for gained drying coating film, using high-pressure mercury-vapor lamp by having pattern Width be 6 μm and 5 μm of peristome exposed mask pattern exposure is carried out with 30mJ after, under room temperature (23 DEG C), using profit The KOH aqueous solution being prepared into 0.04 mass % with ultra-pure water carries out spray development as alkaline developer, removes unexposed portion Afterwards, carried out spray washing using ultra-pure water.Then, carry out baking after 30 minutes using 230 DEG C of baking oven, make thickness about 1 μm of BM.
(3) optical density (OD) (OD value) of BM and the evaluation of thickness
Measure the film that device Alpha-Step-500 (KLA-Tencor company) measures the BM making in (2) using difference in height Thickness, and determine OD using penetrating concentration mensure device GretagMacbeth D200-II (GretagMacbeth company system) Value.Thus obtain every 1 μm corresponding OD value (unit OD value).Resist viscosity evaluation result be ◎ in the case of and be zero In the case of unit OD value be 4.2/ μm.
(4) 6 μm of fine rule evaluations (after development)
Using the exposed mask with multiple 6 μm of openings (width is 6 μm of opening), developing time is set as following bar Part, using being coated, exposing, developing with (2) identical technique, has made BM fine rule.Hereinafter, will be using having 6 μm of openings Exposed mask and the BM fine rule that makes is referred to as " 6 μm of fine rules ".
If the alkali development time is too short, the dissolving residual of alkali soluble resin and the remaining of pigment can occur, substrate Pollution substantially, on the other hand, if long, may lead to BM fine rule bit by bit by alkaline developer etch, peeling-off. In addition, the shortest dissolution time (being able to confirm that the shortest time of the patterning on substrate) represents the alkali of photosensitive polymer combination Development easness.
When carrying out the evaluation of BM fine rule, the shortest dissolution time sometimes not only to be evaluated, also will be to the shortest dissolution time BM live width when several times (for example, 1.5 times, 2 times etc.) are developed is evaluated, but with respect to the shortest dissolution time times Number becomes big, and live width can be tapered, and, alkaline developer can be led to be impregnated with to the substrate part closely sealed with BM fine rule, is formed embedding Enter part, be susceptible to peel off.In addition, diminishing with multiple, easy remaining residue.
Generally, when confirming patterning, affected by the diffraction light from exposed mask, there is BM live width and become Thick tendency, therefore, in order to the live width with target is evaluated, 1.5 times of the shortest dissolution time of developing time is that development is suitable Preferably point.In addition, the shortest dissolution time is different because of the composition of photosensitive polymer combination, but as long as being when with respect to the shortest dissolving Between the value identical of multiple under the conditions of, can reach identical development degree.
The shortest dissolution time of resist (photosensitive polymer combination) 1～16 is respectively 40～60 seconds, therefore, with it Developing time between 60～90 seconds of respective 1.5 times has made several samples, and has carried out following evaluation.
(4-1) the observation evaluation of 6 μm of fine rules
Live width using 3 positions to the sample making in above-mentioned (4) for the optical microscope is determined.And then obtain Its meansigma methods.Result is as shown in table 7.
(4-2) the rectilinearity evaluation of 6 μm of fine rules
Fine rule sometimes due to by alkaline developer or washing spray pressure thereafter unevenly etch etc. and lead to it straight Poor linearity.Rectilinearity using 6 μm of fine rules to 3 positions on substrate for the observation by light microscope is observed, and as follows It is classified describedly.Result is recorded in table 7.
◎：The rectilinearity of whole 6 μm of fine rules is all very good.
○：Can be observed to start by the part of alkaline developer etch, but linear deterioration is inconspicuous.
△：Observe linear deterioration on the whole, also partly observed shortcoming etc..
×：Rectilinearity is all excessively poor on the whole, and shortcoming is also many.
(4-3) pattern of 6 μm of fine rules embeds
Its section obtained from 3 points is cut out for the part from the 6 μm of fine rules making seen using SEM photograph Examine.Observed by section, for substrate and 6 μm of thread patterns composition surface whether by alkaline developer etch, whether there occurs embedding Enter to be observed, and be classified as described below.Result is recorded in table 7.
(embedded evaluation)
A：Observed 3 points are all completely absent embedded, well.
B：Though be completely absent embedded good point and do not develop into embedded but had observed that closed surface start soak The point of erosion is mixed.
C：Though observed 3 points are all not develop into embedded but have had observed that the beginning etch closed surface of closed surface.
D：Though not developing into embedded closed surface but having had observed that the point of beginning etch of closed surface and can be clearly viewed It is mixed to embedded point.
E：Observed 3 points all can be clearly observed embedded.
F：Embedded point can be clearly observed and there occurs that the point embedding on a large scale is mixed.
G：Observed 3 points all there occurs and embed on a large scale.
(5) 6 μm of fine rule evaluations (after heat treatment)
For the BM fine rule having carried out development treatment, for the photonasty tree of overlapping coating red, green, blue further behind Oil/fat composition, needs to carry out heat treatment at high temperature and so that it is solidified.For this reason, carrying out to 6 μm of fine rules at 30 minutes heat in 230 DEG C Reason.By carrying out heat treatment, sometimes because still not sufficiently cured photosensitive polymer combination flows or residual solvent Disengaging etc. is occurred to lead to fine rule to occur thermal deformation, live width thicker.
The live width of 6 μm of fine rules after the heat treatment in 3 Site Determinations.And then obtain its meansigma methods.In addition, after by developing Live width and heat treatment after the difference of live width obtain increase live width and set following evaluation criterion.Result is recorded in table 7.
(live width evaluation (meansigma methodss))
○：In the range of 5.6～6.5 μm.
×：Outside 5.6～6.5 μm of scope.
(increasing live width evaluation)
A：3 points observed are less than 0.1 μm.
B：It is mixed less than 0.1 μm of point and more than 0.1 μm and for less than 0.3 μm of point in 3 points observing.
C：3 points observing all more than 0.1 μm and are 0.3 below μ.
D：It is mixed in 3 points observing and have more than 0.1 μm and for less than 0.3 μm of point and more than 0.3 μm and be Less than 0.4 μm of point.
E：3 points observing all more than 0.3 μm and are less than 0.4 μm.
F：Be mixed in 3 points observing have more than 0.3 μm and be less than 0.4 μm of point and the point more than 0.4 μm.
G：3 points observing are all more than 0.4 μm.
In addition, the part that have passed through the sample of evaluation of live width and increase live width from 6 μm of fine rules after heat treatment is cut Go out at 3 points, carried out SEM observation.The section of fine rule is trapezoidal.By the two ends gone to the bottom corresponding with the contact surface of fine rule and substrate Base angle is referred to as cone angle.According to following standard, this cone angle is evaluated.Result is recorded in table 7.
(cone angle evaluation)
A：3 points observed are more than 73 degree.
B：More than 73 degree of point and 63 degree are mixed less than 73 degree of point.
C：3 points observing are 63 degree less than 73 degree.
D：63 degree are mixed less than 63 degree of point less than 73 degree of point and 59 degree.
E：3 points observing are 59 degree less than 63 degree.
F：59 degree of points less than 63 degree and the point less than 59 degree are mixed.
G：3 points observed are below 59 degree.
As shown in table 7, the rectilinearity of 6 μm of fine rules after the development of embodiment 1～7 is all very good, is completely absent embedding Enter.On the other hand, 6 μm of fine rules after the development of comparative example 1～9 can be observed linear deterioration, at the junction surface with substrate Observed embedded.
In addition, the live width of 6 μm of fine rules after the heat treatment of embodiment 1～7 all falls within the range of 5.6 μm～6.5 μm, energy Enough fine rules forming 6 μm well.Increase live width and all suppress in 0.3 below μ, cone angle is also more than 63 degree, becomes good Fine rule.
On the other hand, 6 μm of fine rules after the heat treatment of comparative example 1～9, increase live width more than 0.3 μm, cone angle also below 63 Degree, live width, more than 6.5 μm, all fail to be formed 5.6～6.5 μm of 6 μm of fine rules.Especially with oxime ester Photoepolymerizationinitiater initiater with The comparative example 9 of outer initiator, after development, all bad after heat treatment.
(6) 5 μm of fine rule evaluations (after development and after heat treatment)
Further, for the BM fine rule (5 μm of fine rules) being made using having the exposed mask of 5 μm of openings, also according to 6 μm same evaluation methodology of fine rule and classification of assessment are evaluated.Result is as shown in table 8.
(live width evaluation (meansigma methodss))
○：In the range of 4.6～5.5 μm.
×：Outside 4.6～5.5 μm of scope.
Table 8
As shown in table 8, as the embodiment containing dispersant 1 and the photosensitive polymer combination of oxime ester Photoepolymerizationinitiater initiater 5 μm of fine rules after 1 development, relatively thin compared with 6 μm of fine rules, therefore affected be more susceptible to alkaline developer or heat treatment, meeting More or less observe the symptom of a trend that rectilinearity reduces, live width can slightly broaden 0.1 μm or cone angle slightly reduces 5 degree, but still be able to good Form well 4.6～5.5 μm of 5 μm of fine rules.
In addition, embodiment 6 is because the primary particle diameter of pigment is less, be 23nm, surface area is big, it is understood that dispersion Agent is easily adsorbed at pigment, with this concomitantly, is adsorbed in the solvophilic group of the dispersant of pigment and alkali soluble resin can have Imitate compatible, as a result, in the same manner as when 6 μm of fine rules, rectilinearity and embedded 5 μm of good fine rules can be formed.
Used in the resist of the present embodiment, polyurethane dispersant, by combining with alkali soluble resin, can make dispersant Solvophilic group and alkali soluble resin compatible well, thus forming good space bit resistance part, viscosity and OD are all good, And dispersibility is also good.
In addition, in an embodiment, employ, in 1 intramolecular, there is ultra-violet absorption position, energy transmission position and freedom The oxime ester Photoepolymerizationinitiater initiater of base generating unit, thus, even if be difficult near the substrate closed surface that arrives in ultraviolet it is also possible to Alkali soluble resin etc. is made effectively to be polymerized.It is believed that thus, alkali soluble resin can be made molten with the parent of polyurethane dispersant Mutual winding between agent portion is more strong, though in the solidification irradiated based on ultraviolet it is also possible to suppression pigment cohesion, Thus keeping good dispersity, as a result, can make equably to show in fine rule from the resistance to alkali-developable of pigment and resistance to Hot, thus obtaining the fine rule that rectilinearity is good, embedded and etch of based on alkaline developer is few.
Further, since used in embodiment 1,2,3 dispersant all pendant types of adsorption group, therefore can recognize For, can improve with the absorption affinity of pigment, reduce amount of free dispersant.It is believed that thus, in heat treatment, free dispersant Can play a role as grease such that it is able to prevent cone angle from declining, live width increases.
On the other hand, the photosensitive polymer combination of comparative example 9 passes through mainly there is free radical generating unit IRG907 initiator and mainly have the DETXS initiator at ultra-violet absorption position and be applied in combination to produce free radical, can recognize For due to employing 2 kinds of Photoepolymerizationinitiater initiaters, therefore free radical generation efficiency is poor, waits purple particularly near substrate closed surface The part that outside line is difficult to arrive at is difficult to be polymerized, and with this concomitantly, leads to create thermal deformation in heat treatment.
In addition, employing the comparative example 1 of the dispersant 5 without adsorption group and employing as polyurethane skeleton The comparative example 4,5 and 6 of the dispersant of graft polymers in addition, the in the resist dispersion of pigment weak with the absorption affinity of pigment Property is insufficient.
It is understood that when manufacturing light filter, pigment and the combination of dispersant in heat treatment can be led to die down, send out The cohesion of raw pigment is it is impossible to fully show resistance to alkali-developable and thermostability from pigment it may occur that thermal deformation.
In addition, employing the comparative example 2 and 3 of the commercially available dispersant with amino-formate bond, due to being by having 3 The polymer by several toluene di-isocyanate(TDI)s of above isocyanates links the skeleton that links of group and several through skeleton Solvophilic group or the dispersant of adsorption group composition, the building-up effect accordingly, with respect to pigment is low, and, due to also can produce Life is sterically hindered with respect to adsorption group, therefore low to the absorption property of pigment.Additionally, the amount of solvophilic group and absorption base The amount of group is all few than polyurethane dispersant used in embodiment, thus is believed that solvophilic group and alkali soluble resin Between compatible insufficient, occur pigment cohesion it is impossible to fully show the resistance to alkali-developable from pigment and thermostability.
Additionally, employing the comparative example 7 and 8 of acrylic compounds AB block dispersant, because adsorption group collects in dispersion The side of agent, it is understood that pigment adsorption group can produce sterically hindered to each other and cannot fully be adsorbed in pigment, Amount of free dispersant is led to increase.It is understood that the substrate that cannot obtain by dispersant between pigment and substrate is closely sealed Power, alkali development patience is low it is difficult to realization patterns.
Using specific embodiment, the present invention is described in detail, but those skilled in the art should understand that It is without departing from the spirit and scope in the present invention, various changes can be carried out and revise.It should be noted that this Apply for that the Japanese patent application (Japanese Patent Application 2014-143279) being proposed based on July 11st, 2014 is completed, entire contents It has been incorporated.

Claims (17)

1. a kind of photosensitive polymer combination, it comprises：
Color material (a),
Dispersant (b),
Photoepolymerizationinitiater initiater (c),
Alkali soluble resin (d) and
Solvent (e),
Wherein, dispersant (b) comprises the polyurethane dispersant (b-1) with solvophilic group and adsorption group,
This polyurethane dispersant (b-1) comprises the part-structure shown in following formula (i),
Photoepolymerizationinitiater initiater (c) comprises oxime ester Photoepolymerizationinitiater initiater (c-1),
In formula (i), RaRepresent and optionally there is the alkylidene of carbon number 1～20 of substituent group, optionally there is the carbon atom of substituent group The arlydene of number 6～20 or the group of the carbon number 7～20 being linked by described alkylidene and described arlydene, * represents Bonding position.
2. photosensitive polymer combination according to claim 1, wherein, described polyurethane dispersant (b-1) comprises：Contain The part-structure containing solvophilic group of described solvophilic group and the part knot containing adsorption group containing described adsorption group Structure,
The part-structure that the part-structure that this contains solvophilic group contains adsorption group with this is tied by the part shown in described formula (i) Structure and link.
3. photosensitive polymer combination according to claim 1 and 2, wherein, described polyurethane dispersant (b-1) has master Chain, this main chain comprises the part-structure shown in described formula (i).
4. the photosensitive polymer combination according to any one of claims 1 to 3, wherein, described solvophilic group comprises At least one of polyether chain and polyester chain.
5. the photosensitive polymer combination according to any one of Claims 1 to 4, wherein, described adsorption group be selected from At least one in the following group：Tertiary amino, quaternary ammonium salt base and nitrogen atom heterocyclic radical.
6. the photosensitive polymer combination according to any one of claim 2～5, wherein, the described portion containing adsorption group Separation structure has the part-structure shown in following formula (1),
In formula (1), R1Represent the alkyl or aryl optionally with substituent group, R2And R3Represent that optionally there is replacement independently of one another The alkylidene of base, arylidene alkylene or arlydene,
* represent bonding position.
7. the photosensitive polymer combination according to any one of claim 2～6, wherein, the described portion containing adsorption group Separation structure has at least one part-structure shown in following formula (2-1)～(2-3),
In formula (2-1), RαAnd RβRepresent the alkyl or aryl optionally with substituent group independently of one another,
Rγ、RδAnd RεRepresent independently of one another optionally have substituent group alkylidene, optionally have substituent group arlydene or by The group that described alkylidene and described arlydene link, wherein, RγFor optionally there is the alkylidene of substituent group or by described In the case of the group that alkylidene and described arlydene link, at least a portion constituting the methylene of described alkylidene is appointed Choosing be selected from ester bond, ehter bond, amino-formate bond, urea bond, amido link, imide bond, thiocarbamate key, thioether bond and At least one key in thioester bond replaces, in addition, RγOptionally former with adjacent at least any one N via-NH- (C=O)-base Son is collectively forming urea bond or optionally forms amido link via carbonyl,
* represent bonding position,
In formula (2-2), RαAnd RβRepresent the alkyl or aryl optionally with substituent group independently of one another,
RγAnd RηRepresent independently of one another and optionally there is the alkylidene of substituent group, optionally there is the arlydene of substituent group or by described The group that alkylidene and described arlydene link, wherein, RγAnd RηIt is each independently the alkylene optionally with substituent group In the case of base or the group that linked by described alkylidene and described arlydene, constitute the methylene of described alkylidene At least a portion is optionally selected from ester bond, ehter bond, amino-formate bond, urea bond, amido link, imide bond, thiocarbamic acid At least one key in ester bond, thioether bond and thioester bond replaces, in addition, RγAnd RηOptionally via-NH- (C=O)-base with adjacent At least any one N atom be collectively forming urea bond or optionally form amido link via carbonyl,
* represent bonding position,
In formula (2-3), RαAnd RβRepresent the alkyl or aryl optionally with substituent group independently of one another,
Rγ’And RδRepresent independently of one another and optionally there is the alkylidene of substituent group, optionally there is the arlydene of substituent group or by institute State the group that alkylidene and described arlydene link, wherein, Rγ’For optionally there is the alkylidene of substituent group or by described In the case of the group that alkylidene and described arlydene link, at least a portion constituting the methylene of described alkylidene is appointed Choosing be selected from ester bond, ehter bond, amino-formate bond, urea bond, amido link, imide bond, thiocarbamate key, thioether bond and At least one key in thioester bond replaces, in addition, Rγ’Optionally it is collectively forming with adjacent N atom via-NH- (C=O)-base Urea bond or optionally form amido link via carbonyl,
Rε’Represent direct key, optionally there is the alkylidene of substituent group, optionally there is the arlydene of substituent group or by described alkylidene The group linking with described arlydene,
RζThe alkyl that represent hydrogen atom, optionally there is substituent group or the aryl optionally with substituent group, wherein, RζFor alkyl or virtue In the case of base, at least one in its hydrogen atom is optionally replaced by tertiary amino or nitrogen atom heterocyclic radical,
* represent bonding position.
8. the photosensitive polymer combination according to any one of claim 1～7, wherein, oxime ester Photoepolymerizationinitiater initiater (c- 1) there is optionally substituted carbazyl.
9. the photosensitive polymer combination according to any one of claim 1～8, wherein, alkali soluble resin (d) contains There is the alkali soluble resin (d-1) of at least one of carboxyl and ethylenically unsaturated group.
10. photosensitive polymer combination according to claim 9, wherein, alkali soluble resin (d-1) is epoxy (methyl) Acrylate.
11. photosensitive polymer combinations according to claim 10, wherein, described epoxy (methyl) acrylate is At least one of following epoxies (methyl) acrylate (D1-1) and epoxy (methyl) acrylate (D1-2),
(1) epoxy (methyl) acrylate (D1-1), it is to make α, β-unsaturated monocarboxylic or the α with carboxyl, β-no Saturation monocarboxylate and epoxy resin addition, then make obtained from itself and the reaction of at least one of polyprotic acid and its anhydride；
(2) epoxy (methyl) acrylate (D1-2), it is to make α, β-unsaturated monocarboxylic or the α with carboxyl, β-no Saturation monocarboxylate and epoxy resin addition, then make itself and polyhydric alcohol and the reaction of at least one of polyprotic acid and its anhydride Obtained from.
12. photosensitive polymer combinations according to any one of claim 1～11, wherein, the average primary of color material (a) Particle diameter is 20～100nm.
13. photosensitive polymer combinations according to any one of claim 1～12, wherein, color material (a) comprises white carbon black.
14. photosensitive polymer combinations according to claim 13, it contains with respect to all solids composition is 40 matter The described white carbon black of amount more than %.
A kind of 15. solidfied materials, it is to make the photosensitive polymer combination any one of claim 1～14 solidify to form 's.
A kind of 16. black matrix"s, it comprises the solidfied material described in claim 15.
A kind of 17. image display devices, it possesses the black matrix" described in claim 16.
CN201580036578.5A 2014-07-11 2015-07-09 Photosensitive resin composition, cured product, black matrix, and image display device Active CN106489100B (en)

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