CN109154748A - Black interval column, which is formed, uses photosensitive resin composition, black interval column and image display device - Google Patents

Black interval column, which is formed, uses photosensitive resin composition, black interval column and image display device Download PDF

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Publication number
CN109154748A
CN109154748A CN201780032105.7A CN201780032105A CN109154748A CN 109154748 A CN109154748 A CN 109154748A CN 201780032105 A CN201780032105 A CN 201780032105A CN 109154748 A CN109154748 A CN 109154748A
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methyl
resin
structural unit
interval column
resin composition
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CN109154748B (en
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柳正义
川口恭章
木下健宏
原司
仓本拓树
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Lishennoco Co ltd
Resonac Holdings Corp
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Showa Denko KK
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

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  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nonlinear Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The present invention provides a kind of black interval column formation photosensitive resin composition, it is characterized in that, contain resin (A), solvent (B), Photoepolymerizationinitiater initiater (C) and colorant (D), wherein, the resin (A) is with selected from least one of the group being made of the structural unit (a) with carboxyl, the structural unit (b-1) with (methyl) acryloxy and the structural unit (b-2) with the functional group reacted with carboxyl structural unit；Resin (A) is preferably further containing the structural unit (c) with fragrant ring skeleton.

Description

Black interval column is formed to be shown with photosensitive resin composition, black interval column and image Device
Technical field
The present invention relates to black interval column formation photosensitive resin composition, black interval column and image display devices.
Background technique
In the image display devices such as liquid crystal display device, organic EL display device, in order to keep two certain plate bases Between interval (box thick) and spacer is utilized.In recent years it has been proposed that various form spacer using photosensitive resin composition Method.This method is coated with photosensitive resin composition on substrate, forms resin layer, across defined exposure mask to the resin layer into After row exposure, develop, forms the spacer of column etc..It in the method, can be only in the rule in addition to pixel display portion Fixed part forms spacer.It has been further proposed that by using the photosensitive tree for being added to the opacifiers such as organic black pigments Oil/fat composition forms the black interval column (referring to patent document 1 and 2) with light-proofness.
Especially for the height of black interval column, it is desirable that higher dimensional accuracy.In addition, scheming in liquid crystal display device etc. As in display device, using substrates such as the TFT substrates for being formed with element on substrate the case where is also more.Using such base When plate, it is sometimes desirable on the element for be formed in substrate or with the pairs of substrate of substrate for being formed with element, with element phase Pair part on form black interval column.At this point, considering the height of element, in the part and other parts for being formed with element, need Change the height of black interval column.It, can be according to the position for forming black interval column by being exposed across intermediate tone mask It sets and changes light exposure, the primary black interval column for forming different height.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2015-191234 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2014-146029 bulletin
Summary of the invention
The technical problem to be solved in the present invention
However, due to the photosensitive resin composition for being used to form black interval column optical density (OD) (Optical with higher Density:OD), therefore in exposure stage, light can not arrive the lower part for reaching resin layer, it is difficult to be solidified.Therefore, existing In technology, after being exposed, developing to form the segment difference of black interval column, heat cure then is carried out in the rear baking stage, from And form pattern.At this point, the segment difference of black interval column, which forms nargin, becomes very narrow, existing can not be uniform in substrate entire surface The problem of maintaining height (the obtaining excellent development nargin) of each segment difference.Further, since the lower part of resin layer mainly passes through heat Solidify and solidified, therefore there are problems that being unable to fully obtain required chemical resistance.Further, by Organic Black When color pigment is used as opacifier, compared with when using the inorganic black pigments such as carbon black, exists and easily cause institute in spacer patterns The metal ion and organic black pigments contained dissolves out this solvent resistance into solvent used in subsequent preparation engineering The problem of.The problem of being lower accordingly, there exist the reliability of the black interval column contacted with liquid crystal.
The present invention is in order to solve the above-mentioned technical problem to complete, its purpose is to provide a kind of colorant dispersibility, Development nargin, solvent resistance and elastic restoration ratio it is excellent black interval column formation use photosensitive resin composition.
Solve the technological means of technical problem
That is, shown in the present invention [1] for example below~[12].
[1] a kind of black interval column, which is formed, uses photosensitive resin composition, which is characterized in that containing resin (A), solvent (B), Photoepolymerizationinitiater initiater (C) and colorant (D), wherein the resin (A) is with selected from by structural unit (a), tool with carboxyl It is made of the structural unit (b-1) of (methyl) acryloxy and the structural unit (b-2) with the functional group reacted with carboxyl At least one of group structural unit.
[2] the black interval column according to [1], which is formed, uses photosensitive resin composition, which is characterized in that the resin (A) Further containing the structural unit (c) with fragrant ring skeleton.
[3] the black interval column according to [1] or [2], which is formed, uses photosensitive resin composition, which is characterized in that the tree Structural unit (d) of the rouge (A) further containing the bridge-type alicyclic type hydrocarbon for being 7~20 with carbon atom number.
[4] the black interval column according to [2], which is formed, uses photosensitive resin composition, which is characterized in that the aromatic rings Skeleton is selected from least one of the group being made of biphenyl backbone, naphthalene skeleton and anthracene skeleton.
[5] the black interval column according to any one of [1]~[4], which is formed, uses photosensitive resin composition, and feature exists In, the functional group reacted with carboxyl be oxetanylmethoxy (oxetanyl group), in epoxy group or isocyano extremely A kind of few functional group.
[6] the black interval column according to any one of [1]~[5], which is formed, uses photosensitive resin composition, and feature exists In the carboxyl is the carboxyl from unsaturated carboxylic acid, the carboxyl from polyacid or the carboxyl from multi-anhydride.
[7] the black interval column according to any one of [1]~[6], which is formed, uses photosensitive resin composition, and feature exists In the unsaturated group equivalent of the resin (A) is 200~2000g/ moles.
[8] the black interval column according to any one of [1]~[7], which is formed, uses photosensitive resin composition, and feature exists In the colorant (D) contains inorganic black pigments and organic black pigments.
[9] the black interval column according to any one of [1]~[8], which is formed, uses photosensitive resin composition, and feature exists In, the solvent (B) of the resin (A), 50~94 mass % containing 1~20 mass %, 0.01~5 mass % it is described The colorant (D) of Photoepolymerizationinitiater initiater (C) and 3~30 mass %.
[10] the black interval column according to [9], which is formed, uses photosensitive resin composition, which is characterized in that further contains The reactive diluent (E) of 1~20 mass %.
[11] a kind of black interval column, which is characterized in that the black interval column as described in any one of [1]~[10] is formed Solidified with photosensitive resin composition.
[12] a kind of image display device, which is characterized in that have black interval column described in [11].
Invention effect
In accordance with the invention it is possible to which it is excellent to provide a kind of dispersed colorant, development nargin, solvent resistance and elastic restoration ratio Black interval column formation use photosensitive resin composition.Solidified by black interval column formation photosensitive resin composition of the invention Made of black interval column colorant dispersibility, solvent resistance and elastic restoration ratio it is excellent.
Specific embodiment
<black interval column, which is formed, uses photosensitive resin composition>
Hereinafter, black interval column formation of the invention is described in detail with photosensitive resin composition.
Black interval column formation photosensitive resin composition of the invention contains resin (A), solvent (B), photopolymerization initiation Agent (C) and colorant (D), wherein the resin (A) with selected from by with carboxyl structural unit (a), have (methyl) third In the group of the structural unit (b-1) of alkene acyloxy and structural unit (b-2) composition with the functional group reacted with carboxyl extremely A kind of few structural unit.
In addition, in the present specification, " (methyl) acryloxy " refers to selected from acryloxy and methacryloxypropyl At least one of base, " (methyl) acrylic acid " refer to selected from least one of acrylic acid and methacrylic acid, " (methyl) third Olefin(e) acid ester " refers to selected from least one of acrylate and methacrylate.
<resin (A)>
Resin used in the present invention (A) with selected from by with carboxyl structural unit (a), have (methyl) acryloyl At least one in the group of the structural unit (b-1) of oxygroup and structural unit (b-2) composition with the functional group reacted with carboxyl Kind structural unit.In the present specification, " structural unit " refers to form the monomeric unit of resin (A) main chain.Further, to formation Monomeric unit addition other monomers of resin (A) main chain and when forming side chain by the monomeric unit of main chain and form the list of side chain Body unit is incorporated as one " structural unit ".It therefore, also include a structural unit in resin (A) used in the present invention In with carboxyl and (methyl) acryloxy structural unit.In addition, in the present specification, having in a structural unit When carboxyl and (methyl) acryloxy, it is denoted as structural unit (a, b-1) sometimes.
Structural unit (a) has carboxyl.Carboxyl can be used as acid anhydride and have.Structural unit (a) can usually pass through following two Kind method is directed into resin (A).
First method are as follows: used by using polymerizable monomer containing carboxyl as when preparing resin (A) by copolymerization Polymerizable monomer, the method (being set as from polymerizable monomer containing carboxyl) to be imported.As the list of polymerism containing carboxyl Body, such as (methyl) acrylic acid, 2- (methyl) acryloyl-oxyethyl succinic acid, 2- (methyl) acryloxy second can be enumerated Base hexahydrophthalic acid, α-bromine (methyl) acrylic acid, β-furyl (methyl) acrylic acid, crotonic acid, propiolic acid, cinnamic acid, Alpha-cyano cinnamic acid, monomethyl maleate, ethyl maleate, maleic acid list isopropyl ester, monomethyl fumarate, itaconic acid list second Unsaturated carboxylic acids such as ester etc..These polymerizable monomers containing carboxyl can be used alone or using two or more.Wherein, from the difficulty obtained Easily degree and reactive angle are set out, preferably (methyl) acrylic acid.
Second method are as follows: use (methyl) acrylate containing epoxy group as resin (A) is prepared by copolymerization before The polymerizable monomer used when driving body carries out addition reaction by the carboxyl and the epoxy group that make carboxyl group-containing monomer, makes epoxy group Open loop, to the hydroxyl addition polyacid or multi-anhydride generated at this time, thus the method for importing carboxyl.As containing epoxy group (methyl) acrylate, such as (methyl) glycidyl acrylate, 2- glycidol ether oxygroup ethyl (methyl) can be enumerated Acrylate, 3,4- epoxycyclohexylmethyl (methyl) acrylate with ester ring oxygroup, its lactone addition product (example Such as, Daicel Corporation manufacture サ イ Network ロ マ ー (registered trademark) A200, M100), 3,4- expoxycyclohexyl Methyl -3 ', the epoxy of (methyl) acrylic monoester of 4 '-epoxycyclohexane carboxylates, (methyl) acrylic acid dicyclopentenyl ester Compound, epoxides of (methyl) acrylic acid dicyclopentenyl oxygroup ethyl ester etc..These (methyl) acrylate containing epoxy group It can be used alone or using two or more.Wherein, from the difficulty and reactive angle obtained, preferably (methyl) propylene Acid glycidyl ester.In addition, maying be used at the unsaturated carboxylic acid enumerated in above-mentioned first method as carboxyl group-containing monomer.Its In, from reactive angle, preferred (methyl) acrylic acid.As polyacid, tetrahydrophthalic acid, hexahydro can be enumerated Phthalic acid, 4- methylhexahydrophthaacid acid, succinic acid etc..As multi-anhydride, the acid anhydride of above-mentioned polyacid can be enumerated. These polyacids and multi-anhydride can be used alone or using two or more.Wherein, from the angle for improving developability, preferably Tetrabydrophthalic anhydride.In second method, can import into resin (A) has carboxyl and (methyl) acryloxy Structural unit (a, b-1).
Structural unit (b-1) can be usually directed into resin (A) by following two method.
First method are as follows: use (methyl) acrylate containing epoxy group as resin (A) is prepared by copolymerization before The polymerizable monomer used when driving body, by containing carboxyl (methyl) acrylate to the epoxy group addition, thus imported Method.Above-mentioned (methyl) acrylate containing epoxy group can be used in (methyl) acrylate containing epoxy group.As containing carboxyl (methyl) acrylate, such as (methyl) acrylic acid, 2- (methyl) acryloyl-oxyethyl succinic acid, 2- (methyl) can be enumerated Acryloyl-oxyethyl hexahydrophthalic acid, α-bromine (methyl) acrylic acid, β-furyl (methyl) acrylic acid etc..
Second method are as follows: what is used when using carboxyl group-containing monomer as the presoma for preparing resin (A) by copolymerization is poly- Conjunction property monomer, (methyl) acrylic acid by (methyl) acrylate to the carboxyl addition containing epoxy group or containing isocyano Ester, thus the method imported.As carboxyl group-containing monomer, it can be used and above-mentioned enumerated as polymerizable monomer containing carboxyl Unsaturated carboxylic acid.As (methyl) acrylate containing epoxy group, above-mentioned (methyl) acrylate containing epoxy group can be used.Make For (methyl) acrylate containing isocyano, (methyl) acrylic acid -2- isocyanato ethyl etc. can be enumerated.
As the functional group reacted possessed by structural unit (b-2) with carboxyl, it is not particularly limited, can usually arranges Enumerate epoxy group, oxetanylmethoxy, isocyano etc., particularly preferred epoxy group.By using containing the function reacted with carboxyl The polymerizable monomer of group is as the polymerizable monomer used when preparing resin (A) by copolymerization, thus guiding structure unit (b-2) The method of (being set as from the polymerizable monomer containing the functional group reacted with carboxyl).As containing the functional group reacted with carboxyl Polymerizable monomer can enumerate (methyl) acrylic acid oxa- ring other than above-mentioned (methyl) acrylate containing epoxy group Butyl ester, (methyl) acrylic acid (3- methy oxetane -3- base) methyl esters, (methyl) acrylic acid (3- Ethyloxetane -3- Base) methyl esters, (methyl) acrylic acid (3- methy oxetane -3- base) ethyl ester, (methyl) acrylic acid (3- ethyl oxa- ring fourth Alkane -3- base) ethyl ester, (methyl) acrylic acid (3- chloromethyl oxetanes -3- base) methyl esters, (methyl) acrylic acid (oxa- ring fourth Alkane -2- base) methyl esters, (methyl) acrylic acid (2- methy oxetane -2- base) methyl esters, (methyl) acrylic acid (2- ethyl oxa- Cyclobutane-2- base) methyl esters, (1- methyl-1-oxetanylmethoxy-2- phenyl)-3- (methyl) acrylate, (1- methyl-1-oxa- Cyclobutyl)-2- trifluoromethyl-3- (methyl) acrylate, (1- methyl-1-oxetanylmethoxy)-4- trifluoromethyl-2- (methyl) (methyl) acrylate of the oxygen heterocycle butyl such as acrylate；(methyl) acrylic acid -2- isocyanato ethyl etc. contains isocyanide (methyl) acrylate of acid group etc..
To the structural unit (a) imported in resin (A) with carboxyl, with the structural unit of (methyl) acryloxy (b-1), the method for the structural unit (b-2) with the functional group reacted with carboxyl, can pass through appropriately combined importing above structure Unit (a), structural unit (b-1), structural unit (b-2) method and imported.Preferred method are as follows: polymerize using containing carboxyl Make when property monomer and the polymerizable monomer for containing the functional group reacted with carboxyl are as the presoma for preparing resin (A) by copolymerization Polymerizable monomer, to (methyl) acrylic acid of a part of addition containing epoxy group of the carboxyl from the polymerizable monomer containing carboxyl Ester or (methyl) acrylate containing isocyano.As other methods, by using (methyl) propylene containing epoxy group The polymerizable monomer used when acid esters is as the presoma for preparing resin (A) by copolymerization, and a part of the epoxy group is added At carboxyl (methyl) acrylate is contained, make epoxy ring-opening, to a part of addition multi-anhydride of the hydroxyl generated at this time. That is, as the structural unit for being directed into resin (A), can be enumerated with the functional group reacted with carboxyl in latter example Structural unit (b-2), the structural unit (b-1) with (methyl) acryloxy and there is carboxyl and (methyl) acryloyl-oxy The structural unit (a, b-1) of base.
Resin used in the present invention (A) can further contain the structural unit (c) with fragrant ring skeleton as needed, This makes it possible to obtain the superior resins (A) of colorant dispersibility.It is used as by using the polymerizable monomer containing aromatic rings by altogether Gather the polymerizable monomer used when preparing resin (A), guiding structure unit (c) (is set as from the polymerism list containing aromatic rings Body).As the polymerizable monomer containing aromatic rings, for example, can enumerate styrene, α-methylstyrene, adjacent vinyltoluene, Vinyltoluene, to vinyltoluene, ortho-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, first Oxygroup styrene, to methoxy styrene, p-nitrophenyl ethylene, to aromatic series such as cyano styrene, acetparaminosalol styrene Vinyl compound；(methyl) benzyl acrylate, (methyl) acrylic acid rosin ester, (methyl) phenyl acrylate, (methyl) propylene Sour isopropyl phenyl ester, (methyl) phenoxyethyl acrylate, phenoxy group-polyethylene glycol (methyl) acrylate (product name: Lightacrylate P-200A, KYOEISYA CHEMICAL CO., LTD. manufacture), Nonylphenoxy polyethyleneglycol (first Base) acrylate, (methyl) acrylic acid neighbour's phenoxy group benzyl ester, (methyl) acrylic acid m-phenoxy benzyl ester, (methyl) acrylic acid pair Phenoxy group benzyl ester, (methyl) acrylic acid -4- phenoxy group phenyl ester, (methyl) acrylic acid biphenylyloxy ethyl ester, ethoxylation neighbour's phenyl Phenolic group (methyl) acrylate, (methyl) acrylic acid naphthalene ester, (methyl) acrylic acid anthracene ester etc..Wherein, from the angle of elastic restoration ratio Degree sets out, and the structural unit with the skeleton containing multiple aromatic rings is preferably imported into the resin (A) that the present invention uses, more excellent Choosing, which imports, has the structural unit selected from least one of the group being made of biphenyl backbone, naphthalene skeleton and anthracene skeleton.
Resin used in the present invention (A) can be as needed further containing the bridge-type rouge for being 7~20 with carbon atom number The structural unit (d) of ring type alkyl, this makes it possible to obtain the superior resins of elastic restoration ratio (A).By using with carbon atom The polymerizable monomer for the bridge-type alicyclic type hydrocarbon that number is 7~20 is as the polymerism list used when preparing resin (A) by copolymerization Body, so that guiding structure unit (d) (is set as the polymerism list from the bridge-type alicyclic type hydrocarbon for being 7~20 with carbon atom number Body).Bridge-type ester ring type hydrocarbon, which refers to, has structure represented by following formula (1) or (2) with adamantane, norbornane etc. for representative Substance.Bridge-type alicyclic type hydrocarbon refers to the base for being equivalent to and eliminating the remainder in these structures after a part of hydrogen atom Group.
[chemical formula 1]
In formula (1), A1And B1Each independently represent linear chain or branched chain alkylidene (may include ring), R4Indicate hydrogen atom or Methyl.A1And B1In, A1And B1Branch can be connected with each other to become ring-type.
[chemical formula 2]
In formula (2), A2、B2And L each independently represents linear chain or branched chain alkylidene (may include ring), R5Indicate hydrogen atom Or methyl.A2、B2And in L, A2、B2And the branch of L can be connected with each other to become ring-type.
In the monomer with above structure, (the first for the bridge-type alicyclic type hydrocarbon for being preferably 7~20 with carbon atom number Base) acrylate, more preferable (methyl) acrylic acid Buddha's warrior attendant alkyl ester and (methyl) propylene with structure represented by following formula (3) Acid esters.
[chemical formula 3]
In formula (3), R6~R8Each independently represent hydrogen atom or methyl.R9And R10For hydrogen atom or methyl, or can phase Mutually bonding is to form saturated or unsaturated ring (preferably five-membered ring or hexatomic ring).In formula (3), * expression is bonded in (first Base) associative key on acryloxy.
As the polymerizable monomer for the bridge-type alicyclic type hydrocarbon for being 7~20 with carbon atom number, such as (first can be enumerated Base) acrylic acid dicyclopentenyl ester, (methyl) dicyclopentanyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid gold Rigid alkyl ester etc..Wherein, from the angle of resistance to pyrolytic and resistance to thermochromism, preferably two ring pentyl ester of methacrylic acid.These Polymerizable monomer can be used alone or using two or more.
In addition, Norbornene derivative represented by following formula (4) also is used as the preferred of guiding structure unit (d) Polymerizable monomer.
[chemical formula 4]
In formula (4), X and the linear chain or branched chain alkyl that Y each independently represents hydrogen atom or carbon atom number is 1~4, R1 And R2Each independently represent the alkyl (may include substituent group) that hydrogen atom, carboxyl or carbon atom number are 1~20.R1And R2It can phase Mutually bonding is to form cyclic structure.
Wherein, the concrete example for the linear chain or branched chain alkyl for being 1~4 as carbon atom number can enumerate methyl, ethyl, just Propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl.In addition, the concrete example for the alkyl for being 1~20 as carbon atom number, can arrange Enumerate methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, tertiary pentyl, stearyl, lauryl, 2- second The alkyl of the linear chain or branched chains such as base hexyl；The aryl such as phenyl；Cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, the tricyclic last of the ten Heavenly stems The ester ring types groups such as base, isobornyl, adamantyl, 2- methyl -2- adamantyl.As the concrete example of substituent group, can enumerate The alkoxies such as methoxyl group, ethyoxyl out；The aryl such as phenyl.
As the concrete example of Norbornene derivative, norbornene (bicyclic [2.2.1] hept-2-ene"), 5- first can be enumerated Bicyclic [2.2.1] hept-2-ene" of base, bicyclic [2.2.1] hept-2-ene" of 5- ethyl, Fourth Ring [4.4.0.12,5.17,10] 12-3- Alkene, 12-3- alkene of 8- methyl Fourth Ring [4.4.0.12,5.17,10], 12-3- of 8- ethyltetracyclo [4.4.0.12,5.17,10] Alkene, bicyclopentadiene, ten -8- alkene of tricyclic [5.2.1.02,6], ten -3- alkene of tricyclic [5.2.1.02,6], tricyclic [4.4.0.12, 5] 11-3- alkene, 11-9- alkene of tricyclic [6.2.1.01,8], 11-4- alkene of tricyclic [6.2.1.01,8], Fourth Ring [4.4.0.12,5.17,10.01,6] 12-3- alkene, 12-3- alkene of 8- methyl Fourth Ring [4.4.0.12,5.17,10.01,6], 12-3- alkene of 8- ethylidene Fourth Ring [4.4.0.12,5.17,12], 8- ethylidene Fourth Ring [4.4.0.12,5.17,10.01,6] ten Two-3- alkene, five rings [6.5.1.13,6.02,7.09,13] 15-4- alkene, five rings [7.4.0.12,5.19,12.08,13] ten Five -3- alkene etc..Wherein, from the angle of resistance to pyrolytic and resistance to thermochromism, preferably norbornene and bicyclopentadiene.This A little Norbornene derivatives can be used alone or using two or more.
Resin used in the present invention (A) can as needed with it is in addition to above structure unit, from have olefinic The structural unit of the free radical polymerization monomer of carbon-to-carbon double bond.By using with the free-radical polymerised of olefinic carbon-to-carbon double bond Monomer is as the polymerizable monomer used when preparing resin (A) by copolymerization, to import from olefinic carbon-to-carbon double bond The structural unit of free radical polymerization monomer.As the free radical polymerization monomer with olefinic carbon-to-carbon double bond, such as can enumerate The diolefin compounds such as butadiene, isoprene, chlorobutadiene out；(methyl) methyl acrylate, (methyl) ethyl acrylate, (first Base) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (first Base) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (first Base) acrylic methyl cyclohexyl, (methyl) acrylic acid ethyl cyclohexyl, 1,4 cyclohexane dimethanol list (methyl) acrylate, (methyl) acrylic acid norbornyl ester, (methyl) acrylic acid -5- methyl norbornyl ester, (methyl) acrylic acid -5- ethyl norbornyl ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid -1,1,1- trifluoro ethyl ester, (methyl) perfluoroethyl ethyl ester, (first Base) perfluoroethyl n-propyl, (methyl) perfluoroethyl isopropyl ester, 3- (N, N- dimethylamino) propyl (methyl) acrylic acid Ester, (methyl) acrylic acid triphenylmethyl, (methyl) acryloyloxyethyl isocyanate (i.e. (methyl) acrylic acid -2- isocyanic acid Root closes ethyl ester) with the reaction products of epsilon-caprolactams, (methyl) acryloyloxyethyl isocyanate and propylene glycol monomethyl ether Reaction product etc. (methyl) acrylate compounds；(methyl) acrylamide, (methyl) acrylic acid N, N- dimethylformamide, (methyl) acrylic acid N, N- diethylamide, (methyl) acrylic acid N, N- dipropyl amide, (methyl) acrylic acid N, N- diisopropyl (methyl) acrylamides such as base amide, (methyl) acrylic acid anthryl amide；(methyl) acryloyl aniline, (methyl) acrylonitrile, third Olefine aldehydr, vinyl chloride, vinylidene chloride, ethylene fluoride, vinylidene fluoride, n-vinyl pyrrolidone, vinylpyridine, acetic acid second The vinyl compounds such as enester, vinyltoluene；Citraconic acid diethylester, diethyl maleate, diethyl fumarate, itaconic acid two The unsaturated dicarboxylics diester compound such as ethyl ester；N-phenylmaleimide, N- N-cyclohexylmaleimide, N- lauryl Malaysia The list maleimide compound such as acid imide, N- (4- hydroxy phenyl) maleimide.
For obtain resin used in the present invention (A) copolyreaction or for obtain carry out addition reaction before tree Reaction condition in the copolyreaction of rouge (A) presoma, is appropriately configured according to conventional methods.Copolyreaction such as one While the polymerizable monomer and polymerization initiator for copolymerization are added dropwise in solvent, on one side preferably with 50~150 DEG C, more preferably with 60 ~140 DEG C are reacted 1~12 hour.Addition reaction to resin (A) presoma is added into solvent for before resin (A) Drive body and carry out the monomer of addition reaction with it, further add addition reaction catalyst, preferably with 50~150 DEG C, more preferably It is reacted 3~12 hours with 80~130 DEG C.In addition, in the addition reaction, even if containing for before obtaining resin (A) Driving solvent used in the copolyreaction of body, also there is no problem.Therefore, for obtaining the copolyreaction knot of resin (A) presoma Shu Hou can not remove solvent and continue addition reaction.
Shown in the ratio of the preferred structure unit of resin used in the present invention (A) for example following (I)~(IV).
(I) containing the structural unit (a) with carboxyl and the structural unit (b-1) with (methyl) acryloxy In resin (A), the structural unit (b-1) of structural unit (a) and 10~80 moles of % preferably with 10~70 moles of % is more excellent Select the structural unit (b-1) of structural unit (a) and 15~70 moles of % with 20~60 moles of %.
(II) containing the structural unit (a) with carboxyl and the structural unit (b- with the functional group reacted with carboxyl 2) in resin (A), the structural unit (b-2) of structural unit (a) and 10~70 moles of % preferably with 10~80 moles of %, The structural unit (b-2) of structural unit (a) and 15~60 moles of % more preferably with 20~70 moles of %.
(III) in the structural unit (b-1) for containing the structural unit (a) with carboxyl, there is (methyl) acryloxy And in the resin (A) of the structural unit (b-2) with the functional group reacted with carboxyl, preferably with the structure of 10~70 moles of % The structural unit (b-2) of unit (a), the structural unit (b-1) of 10~70 moles of % and 10~50 moles of % more preferably has 20 The structural unit of the structural unit (a) of~60 moles of %, the structural unit (b-1) of 20~60 moles of % and 20~40 moles of % (b-2)。
(IV) containing the structural unit (a, b-1) with carboxyl and (methyl) acryloxy, there is (methyl) propylene In the resin (A) of the structural unit (b-1) of acyloxy and the structural unit (b-2) with the functional group reacted with carboxyl, preferably Structural unit (a, b-1) with 10~80 moles of %, the structural unit (b-1) of 10~80 moles of % and 1~10 mole of % Structural unit (b-2), the structural unit of structural unit (a, b-1), 15~70 moles of % more preferably with 20~70 moles of % (b-1) and the structural unit of 1~5 mole of % (b-2).
If the structural unit (a) with carboxyl is 10 moles of % or more, developability becomes well, so it is preferred that.It is another Aspect, if the structural unit (a) with carboxyl ratio be the upper limit value hereinafter, if can prevent development when residual film ratio Decline, so it is preferred that.
If the structural unit (b-1) with (methyl) acryloxy is 10 moles of % or more, solvent resistance, developability Become good, so it is preferred that.On the other hand, if the ratio of the structural unit (b-1) with (methyl) acryloxy is described Upper limit value hereinafter, be then able to suppress the generation of residue when development, so it is preferred that.
If the structural unit (b-2) with the functional group reacted with carboxyl is 10 moles of % or more, solvent resistance becomes Well, so it is preferred that.On the other hand, if having the ratio of the structural unit (b-2) for the functional group reacted with carboxyl is on described Limit value hereinafter, then storage stability becomes well, so it is preferred that.
Can be as needed, the structure with fragrant ring skeleton is imported into the resin (A) of (I), (II), (III) and (IV) The structural unit (d) or structure list in addition to this of unit (c), the bridge-type alicyclic type hydrocarbon for being 7~20 with carbon atom number Member.
When importing the structural unit (c) with fragrant ring skeleton, preferably 0 mole of % of the structural unit of resin (A) ~50 moles of %, more preferably 0 mole of %~40 mole %.
When importing that have carbon atom number be the structural unit (d) of 7~20 bridge-type alicyclic type hydrocarbon, preferably resin (A) 0 mole of %~40 mole % of structural unit, more preferably 0 mole of %~30 mole %.
When importing structural unit in addition to this, 0 mole of %~60 of the preferably structural unit of resin (A) are rubbed You are %, more preferably 0 mole of %~50 mole %.
It as the solvent that can be used in copolyreaction, is not particularly limited, well known solvent can be suitably used.As solvent Concrete example, glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl can be enumerated Glycol list positive propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, propylene glycol monomethyl ether, the third two Alcohol list ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol list positive propyl ether, dipropylene glycol mono-n-butyl ether, 3 third (poly-) the alkylene glycol monoalky lethers such as glycol monomethyl ether, tripropylene glycol list ether；Ethylene glycol monomethyl ether acetate, ethylene glycol list second Ether acetic acid ester, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate etc. (poly-) alkylene glycol monoalkyl ether acetate；Two Other ether compounds such as glycol dimethyl ether, diethylene glycol Methyl ether, diethylene glycol diethyl ether, tetrahydrofuran；Methylethyl The ketone compounds such as ketone, cyclohexanone, 2-HEPTANONE, 3- heptanone；2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, 2- hydroxy-2-methyl Methyl propionate, 2- hydroxy-2-methyl ethyl propionate, 3- methoxy methyl propionate, 3- methoxypropionate, 3- ethoxy-propionic acid Methyl esters, 3- ethoxyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2- hydroxy-3-methyl butyric acid methyl esters, 3- first Base -3- methoxybutyl acetic acid esters, 3- methyl -3- methoxybutyl propionic ester, ethyl acetate, n-butyl acetate, acetic acid positive third Ester, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, butyric acid second Ester, butyric acid n-propyl, butyric acid isopropyl ester, butyric acid N-butyl, methyl pyruvate, ethyl pyruvate, pyruvic acid n-propyl, acetyl second The ester compounds such as sour methyl esters, ethyl acetoacetate, 2- oxo butyric acid ethyl ester；The aromatic hydrocarbon compounds such as toluene, dimethylbenzene；N- first Carboxylic acid amide compounds such as base pyrrolidones, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide etc..These solvents can be independent Using or using two or more.
Wherein, preferably (poly-) the alkylene glycol monoalky lether such as propylene glycol monomethyl ether and propylene glycol methyl ether acetate etc. (poly-) Alkylene glycol monoalkyl ether acetate, i.e., preferred gylcol ether solvent.
The usage amount of the solvent of copolyreaction is not particularly limited, but the total amount of the additive amount of monomer is being set as 100 When mass parts, usually 30~1000 mass parts, preferably 50~800 mass parts.If the usage amount of solvent is 1000 mass parts Hereinafter, caused by capable of then effectively inhibiting because of chain transfer resin (A) molecular weight decline, and can be by resin (A) Viscosity is controlled in suitable range, so it is preferred that.On the other hand, if the usage amount of solvent is 30 mass parts or more, can prevent Exception is only generated in copolyreaction, can stablize carry out copolyreaction, so it is preferred that.Additionally it is possible to prevent resin (A) Color or gelation.
It is not particularly limited as the polymerization initiator that can be used in copolyreaction, can be suitably used and use well known polymerization Initiator.As the concrete example of polymerization initiator, azodiisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide can be enumerated And peroxidating 2 ethyl hexanoic acid tert-butyl ester etc..These polymerization initiators can be used alone or using two or more.Polymerization initiator Usage amount be not particularly limited, when the total addition level of monomer is set as 100 mass parts, usually 0.5~20 mass parts, excellent It is selected as 0.7~15 mass parts, more preferably 1~10 mass parts.
The type of addition reaction catalyst for making monomer carry out addition reaction with resin (A) presoma does not limit especially It is fixed, it can suitably select as needed.As addition reaction catalyst, such as tertiary amine as triethylamine, triethyl group can be enumerated Quaternary ammonium salt as benzyl ammonium chloride, phosphorus compound as triphenylphosphine, chelate of chromium etc..These addition reaction catalysts It can be used alone or using two or more.The usage amount of addition reaction catalyst is not particularly limited, by resin (A) presoma Amount when being set as 100 mass parts, usually 0.01~5 mass parts, preferably 0.1~2 mass parts, more preferably 0.2~1 mass Part.
When making monomer and resin (A) presoma carries out addition reaction, the polymerization inhibitor for preventing gelation is preferably added. The type of polymerization inhibitor is not particularly limited, and can select as needed.As polymerization inhibitor, for example, can enumerate quinhydrones, methylnaphthohydroquinone, Hydroquinone monomethyl ether, butylated hydroxytoluene etc..These polymerization inhibitors can be used alone or using two or more.The usage amount of polymerization inhibitor does not have It is particularly limited to, when the amount of resin (A) presoma is set as 100 mass parts, usually 0.01~5 mass parts, preferably 0.1 ~2 mass parts, more preferably 0.2~1 mass parts.
Obtained from being converted according to gel permeation chromatography (GPC) with polystyrene of resin used in the present invention (A) Weight average molecular weight is preferably 1000~50000, and more preferably 3000~40000.If weight average molecular weight is 1000 or more, in alkali Property development after do not generate the missing of pattern, so it is preferred that.On the other hand, if weight average molecular weight be 50000 hereinafter, if developing time For appropriateness time, it is more practical in terms of usability, so it is preferred that.In addition, from the angle of elastic restoration ratio, resin (A) Weight average molecular weight be preferably 3000~30000.
As long as playing required effect of the invention, acid value (the JIS K6901 of resin (A) used in the present invention 5.3) it is not particularly limited, but usually 20~300KOHmg/g, preferably 30~200KOHmg/g.If acid value is 20KOHmg/ G or more, then developability becomes well, so it is preferred that.On the other hand, if acid value be 300KOHmg/g hereinafter, if exposed portion (light Cured portion) it is difficult to be dissolved in alkaline-based developer, so it is preferred that.In addition, from the angle of elastic restoration ratio, resin (A) Acid value is preferably 30~200KOHmg/g.
As long as playing required effect of the invention, the unsaturated group equivalent of resin (A) used in the present invention It is not particularly limited, but usually 100~4000g/ moles, preferably 200~2000g/ moles, more preferably 300~500g/ Mole.If unsaturated group equivalent is 100g/ moles or more, Physical properties of coating film and alkali development can and be effectively improved, So it is preferred that.On the other hand, if unsaturated group equivalent be 4000g/ moles hereinafter, if can further and effectively improve spirit Sensitivity, so it is preferred that.In addition, from the angle of elastic restoration ratio, the unsaturated group equivalent of resin (A) is preferably 200~ 2000g/ moles.In addition, unsaturated group equivalent refers to that every 1 mole of unsaturated bond (olefinic carbon-to-carbon double bond) in resin (A) is right The quality for the resin (A) answered.Unsaturated group equivalent can by with the quality of resin (A) divided by the unsaturated group in resin (A) It rolls into a ball number and finds out (g/ moles).In addition, in the present specification, unsaturated group equivalent is by making for importing unsaturated group The additive amount of raw material and calculated theoretical value.
As long as playing required effect of the invention, the epoxide equivalent of resin (A) used in the present invention does not have Especially limitation, but usually 100~4000g/ moles, preferably 200~2000g/ moles, more preferably 300~500g/ rub You.If epoxide equivalent is 100g/ moles or more, Physical properties of coating film and storage stability can and be effectively improved, so it is excellent Choosing.On the contrary, if epoxide equivalent be 4000g/ moles hereinafter, if can further and effectively improve solvent resistance.In addition, institute State the quality that epoxide equivalent refers to the corresponding polymer of every 1 epoxy molecule of polymer.The value can be by with polymer Quality finds out (g/ moles) divided by the epoxy base unit weight of polymer.In the present specification, " epoxide equivalent " is by for importing Epoxy group and the additive amount of raw material that uses and calculated theoretical value.
<solvent (B)>
As long as can dissolving resin (A) and be the non-active solvent that react with resin (A), it is of the invention used in it is molten Agent (B) is not particularly limited, and can arbitrarily be selected.In addition, solvent (B) preferably has and reactive diluent described hereinafter Compatibility.As solvent (B), solvent identical with the solvent that can be used when preparing resin (A) can be used.As solvent (B), preferred (poly-) the alkylene glycol monoalky lether such as propylene glycol monomethyl ether and propylene glycol methyl ether acetate etc. (poly-) alkylene glycol Monoalkyl ether acetate.
Target resin (A) can be separated from resin (A) solution for complete copolyreaction, and to the resin being separated (A) solvent (B) is properly added in.However, being not necessarily required to separate target resin (A) from resin solution.It can also be altogether Contained solvent is not separated from resin (A) solution at the end of poly- reaction, solvent is directly used as solvent (B).It can be according to need Other solvents are added into resin (A) solution.In addition it is also possible to which black interval column formation photosensitive resin composition will be prepared When the other compositions that use in the solvent that contains be directly used as solvent (B).
<Photoepolymerizationinitiater initiater (C)>
Photoepolymerizationinitiater initiater (C) used in the present invention is not particularly limited, such as can enumerate benzoin, benzene idol The benzoins compound such as relation by marriage methyl ether, benzoin ethyl ether, benzoin butyl ether；Acetophenone, 2,2- dimethoxy -2- phenyl acetophenone, 1,1- dichloroacetophenone, 4- (two oxygroup-1- Methylethyl of 1- tert-butyl) acetophenone, 2- methyl-1-[4- (methyl thio) benzene Base] the acetophenones chemical combination such as -2- morpholinyl-propane -1- ketone, 2- benzyl -2- dimethylamino -1- (4- morpholinyl phenyl) butanone -1 Object；The anthraquinone compounds such as 2-methylanthraquinone, 2- amyl anthraquinone, 2- tert-butyl anthraquinone, 1- chloroanthraquinone；Xanthone, thio-xanthene-one, The xanthenes ketone compounds such as 2,4- dimethyl thio xanthone, 2,4- diisopropyl thio-xanthene-one, 2- chlorine thio-xanthene-one；Benzene second The ketal compounds such as ketone dimethyl ketal, benzyl dimethyl ketal；Benzophenone, 4- (two oxygroup -1- methyl second of 1- tert-butyl Base) benzophenone, 3,3 ', the benzophenone cpds such as 4,4 '-four (two Epoxide carbonyl of tert-butyl) benzophenone；Acylphosphine oxide Compound etc..These Photoepolymerizationinitiater initiaters can be used alone or using two or more.
<colorant (D)>
As long as being dissolved or dispersed in solvent (B), colorant (D) used in the present invention is not particularly limited, such as can Enumerate dyestuff and pigment.Dyestuff and pigment can be used alone, it is possible to use and it is two or more, or can also be by dyestuff and pigment group It closes and uses.When forming black interval column of the invention, from the dissolubility and other compositions to solvent (B) and alkaline-based developer Interaction and the angle of light-proofness set out, the formation of black interval column preferably comprises black pigment with photosensitive resin composition and makees For colorant (D).
As black pigment, inorganic black pigments and organic black pigments can be enumerated, specifically, aniline can be enumerated It is black, Palio root is black, titanium is black, Cyanine Black, lignin are black, lactams Organic Black, RGB are black, carbon black.These black pigments can be single Solely using or using two or more.From the angle of optical density (OD), preferably simultaneously using inorganic black pigments and organic black Pigment, more preferably simultaneously using carbon black and lactams Organic Black.
It, can be in black interval cylindricality from the angle for the dispersibility for improving pigment when pigment is used as colorant (D) At the dispersing agent well known to being blended in photosensitive resin composition.Due to macromolecule dispersing agent through when dispersion stabilization it is excellent, because This is preferably used as dispersing agent.Macromolecule dispersing agent can be selected arbitrarily, for example, can enumerate urethane esters dispersing agent, Polyethyleneimine amine dispersing agent, polyoxyethylene alkyl ether class dispersing agent, two esters dispersing agent of polyoxyethylene glycol, sorbitan fatty Race's esters dispersing agent, aliphatic modified esters dispersing agent etc..As such macromolecule dispersing agent, can be used with EFKA (registration Trade mark, BASF Japan Ltd. manufacture), Disperbyk (registered trademark, BYK Japan KK. manufacture), DISPARLON (note Volume trade mark, Kusumoto Chemicals, Ltd. manufacture), SOLSPERSE (registered trademark, AstraZeneca K.K. manufacture) Etc. product names carry out commercially available macromolecule dispersing agent.The blended amount of dispersing agent is suitably set according to the type of the pigment used etc. ?.
Black interval column of the invention is formed to be caused with the resin (A) in photosensitive resin composition, solvent (B), photopolymerization The amount of preferably being blended with of agent (C) and colorant (D) is as follows.
Relative to photosensitive resin composition entirety, the blended amount of resin (A) is preferably 1~20 mass %, more preferably 5~ 15 mass %.If the blended amount of resin (A) is 1 mass % or more, there is good photo-curable, so it is preferred that.Another party Face, if resin (A) blended amount be 20 mass % hereinafter, if having good coating, so it is preferred that.
Relative to photosensitive resin composition entirety, the blended amount of solvent (B) is preferably 50~94 mass %, and more preferably 60 ~90 mass %.If the blended amount of solvent (B) is 50 mass % or more, there is good coating, so it is preferred that.Another party Face, if solvent (B) blended amount be 94 mass % hereinafter, if can make film have sufficient film thickness, so it is preferred that.
Relative to photosensitive resin composition entirety, the blended amount of Photoepolymerizationinitiater initiater (C) is preferably 0.01~5 mass %, More preferably 0.1~2 mass %.If the blended amount of Photoepolymerizationinitiater initiater (C) is 0.01 mass % or more, protective layer can be made With curability, so it is preferred that.On the other hand, if the blended amount of Photoepolymerizationinitiater initiater (C) be 5 mass % hereinafter, if developing After be difficult to generate residue, so it is preferred that.
Relative to photosensitive resin composition entirety, the blended amount of colorant (D) is preferably 3~30 mass %, and more preferably 5 ~20 mass %.If the blended amount of colorant (D) is 3 mass % or more, there is light-proofness, so it is preferred that.On the other hand, if The blended amount of colorant (D) is 30 mass % hereinafter, being then difficult to generate residue after development, so it is preferred that.
From the angle of viscosity adjustment and the adjustment of sensitivity, black interval column formation photosensitive resin group of the invention Reactive diluent (E) can further be contained by closing object.
<reactive diluent (E)>
Reactive diluent (E) is compound in the molecule at least one ethylenically unsaturated group.Wherein, preferably Compound with multiple ethylenically unsaturated groups.Reactive diluent (E) is not black interval column formation photosensitive resin The neccessary composition of composition.However, passing through while using reactive diluent (E) and resin (A), can be improved by black interval The film-strength for the film that column formation is formed with photosensitive resin composition or adaptation to substrate.
As the monofunctional monomer as reactive diluent (E), such as (methyl) acrylamide, hydroxyl first can be enumerated Base (methyl) acrylamide, methoxy (methyl) acrylamide, ethoxyl methyl (methyl) acrylamide, propoxy methyl (methyl) acrylamide, butoxymethoxy methyl (methyl) acrylamide, (methyl) methyl acrylate, (methyl) acrylic acid second Ester, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) propylene Sour 2- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxybutyl, 2- phenoxy group -2- hydroxypropyl (methyl) acrylate, 2- (first Base) acryloxy -2- hydroxypropyl phthalate, glycerol list (methyl) acrylate, (methyl) acrylic acid tetrahydro chaff Base ester, (methyl) glycidyl acrylate, (methyl) acrylic acid -2,2,2- trifluoro ethyl ester, (methyl) acrylic acid -2,2,3,3- Partly (methyl) acrylate compounds such as (methyl) acrylate of tetrafluoro propyl ester, derivates；Styrene, Alpha-Methyl The aromatic ethenyl compounds such as styrene, α -1-chloro-4-methyl-benzene, vinyltoluene；Vinyl acetate, vinyl propionate etc. Carboxylate etc..These monofunctional monomers can be used alone, it is possible to use two or more.
As the polyfunctional monomer as reactive diluent (E), such as ethylene glycol two (methyl) propylene can be enumerated Acid esters, diethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylic acid Ester, polypropylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, glycerol two (methyl) acrylate, Pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, Bis- (4- (methyl) the acryloxy diethoxy phenyl) propane of dipentaerythritol six (methyl) acrylate, 2,2-, 2,2- are bis- (4- (methyl) acryloxypolyethoxyphenyl) propane, 2- hydroxyl -3- (methyl) acryloxypropyl (methyl) propylene Acid esters, ethylene glycol diglycidylether two (methyl) acrylate, diethylene glycol diglycidyl glycerin ether two (methyl) acrylate, Phthalic acid 2-glycidyl ester two (methyl) acrylate, glycerol tri-acrylate, glycerine polyglycidyl ether are poly- (methyl) Acrylate, urethanes (methyl) acrylate (that is, toluene di-isocyanate(TDI)), tri-methyl hexamethylene diisocyanate Reactant, three (hydroxyethyl) isocyanuric acids with (methyl) acrylic acid 2- hydroxy methacrylate such as ester and hexamethylene diisocyanate (methyl) acrylate compounds such as three (methyl) acrylate of ester；Divinylbenzene, diallyl phthalate, diene The aromatic ethenyl compounds such as propylbenzene phosphonate ester；The dicarboxylate compounds such as vinyl hexanediacetate；Triallyl cyanogen urea Acid esters, di-2-ethylhexylphosphine oxide (methyl) acrylamide, (methyl) acrylamide methylene ether, polyalcohol and N- methylol (methyl) acryloyl The condensation product of amine.These polyfunctional monomers can be used alone, it is possible to use two or more.
When blending reactive diluent (E), relative to photosensitive resin composition entirety, blended amount is preferably 1~20 Quality %, more preferably 2~10 mass %.If the blended amount of reactive diluent (E) is 1 mass % or more, have good Curability, so it is preferred that.On the other hand, if the blended amount of reactive diluent (E) be 20 mass % hereinafter, if be difficult to aobvious Movie queen generates residue, so it is preferred that.
Further, as long as within the scope of the effect of the invention, black interval column of the invention is formed with photosensitive tree Oil/fat composition can contain additive well known to coupling agent, levelling agent, thermal polymerization inhibitor etc..As long as not damage effect of the present invention Range, the blended amount of these additives is just not particularly limited.
Black interval column formation photosensitive resin composition of the invention can be by using well known mixing arrangement, in mixing Each ingredient stated, to be prepared.In addition, can also be according to requiring, in the previously prepared group containing resin (A) and solvent (B) After closing object, Photoepolymerizationinitiater initiater (C), colorant (D) and the reactive diluent (E) as any ingredient is further added, It is mixed, to be prepared.
<black interval column>
Then, black interval column of the invention is described in detail.
Black interval column of the invention is solidified by above-mentioned black interval column formation photosensitive resin composition.Specifically For, firstly, the painting black spacer column formation photosensitive resin composition on substrate, to form resin layer (coated film). Then, the intermediate tone mask across defined pattern is exposed resin layer, and exposed portion is made to carry out photocuring.Then, make Developed with alkaline-based developer to unexposed portion and half-exposure portion, to form black interval column.Then right as needed Black interval column dries after carrying out.
The material of substrate is not particularly limited, such as can enumerate glass substrate, silicon substrate, polycarbonate substrate, polyester Substrate, polyamide substrate, polyamideimide-based plate, polyimide substrate, aluminum substrate, printed circuit board, array substrate etc..
The coating method of black interval column formation photosensitive resin composition is not particularly limited, such as can enumerate silk screen Print process, rolling method, curtain coating processes, spray coating method, spin-coating method etc..In addition, in painting black spacer column formation photosensitive resin After composition, it can be heated as needed using heating methods such as circulating baking oven, infrared heater, heating plates, thus The solvent (B) contained in resin layer is set to volatilize.Heating condition is not particularly limited, as long as being formed according to the black interval column used It is suitably set with the composition of photosensitive resin composition.Generally preferably 30 seconds~30 points are heated with 50 DEG C~120 DEG C of temperature Clock.
The exposure method of resin layer is not particularly limited, such as can enumerate irradiation ultraviolet light, excimer laser isoreactivity Energy-ray.The energy-ray amount of irradiation is suitably set i.e. according to the composition of black interval column formation photosensitive resin composition It can.Such as preferably 30~2000mJ/cm2, but it is not limited to the range.It is not particularly limited as the light source for exposure, It can arbitrarily select using low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, xenon lamp, metal halide lamp etc..
Alkaline-based developer for development is not particularly limited, such as can enumerate sodium carbonate, potassium carbonate, calcium carbonate, hydrogen The aqueous solution of sodium oxide molybdena, potassium hydroxide etc.；The aqueous solution of the aminated compounds such as ethamine, diethylamine, dimethylethanolamine；Tetramethyl Ammonium, 3- methyl -4- amino-N, N- diethylaniline, 3- methyl -4- amino-N- ethyl-N- beta-hydroxy ethyl aniline, 3- methyl - 4- amino-N- ethyl-N- β-Methanesulfonamide ethyl aniline, 3- methyl -4- amino-N- ethyl-N- 'beta '-methoxy ethyl aniline And the aqueous solution etc. of the oxidations such as their sulfate, hydrochloride or tosilate.In addition, can be according to need Defoaming agent, surfactant etc. are added into these alkaline-based developers.In addition, after using alkaline-based developer development, preferably It is cleaned and is made it dry.
By to by alkaline development and the black interval column that is formed carry out after dry, the solidification of resin can be pushed further into. The condition dried afterwards is not particularly limited, and can arbitrarily be selected.As long as according to black interval column formation photosensitive resin composition Composition, select optimum condition simultaneously heated.For example, 130 DEG C~250 DEG C at a temperature of preferably carry out 10 points The heating of clock~4 hour more preferably carries out heating in 20 minutes~2 hours.
The black interval column prepared through the above way colorant dispersibility, solvent resistance and elastic restoration ratio it is excellent.
<image display device>
Image display device of the invention is the image display device for having above-mentioned black interval column.It is shown as image The concrete example of device can enumerate liquid crystal display device, organic EL display device etc..When preparing image display device, in addition to It is formed other than above-mentioned black interval column, there is no limit can be prepared according to conventional methods.
Embodiment
Hereinafter, referring to embodiment, the present invention is described in detail, but the present invention is not limited by these embodiments.
<synthesis example 1>
The work of 139g is added into the flask for having agitating device, dropping funel, condenser, thermometer and gas introduction tube For the propylene glycol methyl ether acetate of solvent, it is stirred while to nitrogen displacement is carried out in flask, is warming up to 120 DEG C.
Then, in addition prepare in the methacrylic acid tricyclodecyl by 22.0g (0.1 mole), 70.0g (0.4 mole) The peroxidating 2- of 6.6g is added in the monomer mixture of the methacrylic acid of benzyl acrylate and 43.0g (0.5 mole) composition The mixture of ethylhexanate (polymerization initiator, NOF Corporation manufacture, Perbutyl (registered trademark) O).From The mixture of the monomer and polymerization initiator was added dropwise in dropping funel into flask with 2 hours.After completion of dropwise addition, at 120 DEG C It futher stirs 2 hours, carries out copolyreaction, the presoma of synthetic resin (A).Then, air will be replaced into flask, upwards The glycidyl methacrylate of 21.3g (0.15 mole), the triphenyl of 0.5g are added in resin (A) precursor solution stated The butylated hydroxytoluene (polymerization inhibitor) of phosphine (catalyst) and 0.5g.Then, the reaction was continued at 110 DEG C 10 hours, obtains resin (A) solution.Using the resin as " resin (A-1) ".The acid value of the resin (A-1) contained in the resin solution is 126KOHmg/g, weight average molecular weight 10000, unsaturated group equivalent are 1100.
Propylene glycol methyl ether acetate is further added into the resin solution, prepares resin (A-1) solution of synthesis example 1 (solid component concentration is 40 mass %).In addition, solid component refers to adding after heating 2 hours at 130 DEG C to resin solution Hot residual component, resin (A-1) and polymerization initiator are principal component.
<synthesis example 2>
The work of 140g is added into the flask for having agitating device, dropping funel, condenser, thermometer and gas introduction tube For the propylene glycol methyl ether acetate of solvent, it is stirred while to nitrogen displacement is carried out in flask, is warming up to 120 DEG C.
Then, in addition prepare in the methacrylic acid tricyclodecyl by 66.0g (0.3 mole), 31.2g (0.3 mole) The mistake of 7.3g is added in the monomer mixture of the glycidyl methacrylate of styrene and 56.8g (0.4 mole) composition Aoxidize the mixed of the 2 ethyl hexanoic acid tert-butyl ester (polymerization initiator, NOF Corporation manufacture, Perbutyl (registered trademark) O) Close object.From the mixture that the monomer and polymerization initiator was added dropwise in dropping funel into flask with 2 hours.After completion of dropwise addition, It is futher stirred at 120 DEG C 2 hours, carries out copolyreaction, generate the presoma of resin (A).Then, sky will be replaced into flask Triphenylphosphine (the catalysis of the acrylic acid, 0.6g of 28.8g (0.4 mole) is added into above-mentioned resin (A) precursor solution for gas Agent) and 0.6g butylated hydroxytoluene (polymerization inhibitor).Then, the reaction was continued at 110 DEG C 10 hours.Then, add into flask Add the tetrabydrophthalic anhydride of 38.0g (0.25 mole), the reaction was continued at 110 DEG C 3 hours, obtains the solution of resin (A). Using the resin as " resin (A-2) ".The acid value of the resin (A-2) contained in the resin solution is 65KOHmg/g, Weight-average molecular Amount is 9400, and unsaturated group equivalent is 600.Propylene glycol methyl ether acetate is added identically as synthesis example 1, prepares synthesis example 2 resin (A-2) solution (solid component concentration is 40 mass %).
<synthesis example 3>
The work of 191g is added into the flask for having agitating device, dropping funel, condenser, thermometer and gas introduction tube For the propylene glycol methyl ether acetate of solvent, it is stirred while to nitrogen displacement is carried out in flask, is warming up to 100 DEG C.
Then, in addition prepare in the methacrylic acid tricyclodecyl by 22.0g (0.1 mole), 50.0g (0.5 mole) The Glycidyl methacrylate of methyl methacrylate, the methacrylic acid of 21.5g (0.25 mole) and 21.3g (0.15 mole) is sweet The mixture of the azodiisobutyronitrile of 12.6g is added in the monomer mixture of grease composition.From dropping funel with 2 hours to The mixture of the monomer and polymerization initiator is added dropwise in flask.It after completion of dropwise addition, futher stirs 2 hours, carries out at 100 DEG C Copolyreaction obtains the solution of resin (A).Using the resin as " resin (A-3) ".Resin (the A- contained in the resin solution 3) acid value is 100KOHmg/g, weight average molecular weight 8400.Propylene glycol methyl ether acetate is added identically as synthesis example 1, Prepare resin (A-3) solution of synthesis example 3 (solid component concentration is 40 mass %).
<synthesis example 4>
The work of 226g is added into the flask for having agitating device, dropping funel, condenser, thermometer and gas introduction tube For the propylene glycol methyl ether acetate of solvent, it is stirred while to nitrogen displacement is carried out in flask, is warming up to 70 DEG C.
Then, in addition prepare in the methacrylic acid tricyclodecyl by 22.0g (0.1 mole), 50.0g (0.5 mole) Methyl methacrylate, the methacrylic acid of 21.5g (0.25 mole) and methacrylic acid -2- isocyanato ethyl and ε-oneself The 2,2 '-azos that 13.0g is added in the monomer mixture of the reaction product composition of the 40.2g (0.15 mole) of lactams are double (2,4- methyl pentane nitrile) (polymerization initiator, Wako Pure Chemical Industries, Ltd. manufacture, V-65) mixes Close object.From the mixture that the monomer and polymerization initiator was added dropwise in dropping funel into flask with 2 hours.After completion of dropwise addition, It is futher stirred at 70 DEG C 2 hours, carries out copolyreaction, obtain the solution of resin (A).Using the resin as " resin (A-4) ". The acid value of the resin (A-4) contained in the resin solution is 85KOHmg/g, weight average molecular weight 8800.Identically as synthesis example 1 It adds propylene glycol methyl ether acetate, prepares resin (A-4) solution of synthesis example 4 (solid component concentration is 40 mass %).
<synthesis example 5>
In addition to using methacrylic acid tricyclodecyl, the methyl-prop of 24.6g (0.14 mole) by 41.8g (0.19 mole) (polymerization causes the peroxidating 2 ethyl hexanoic acid tert-butyl ester of olefin(e) acid benzyl ester, the methacrylic acid of 57.6g (0.67 mole) and 12.4g Agent, NOF Corporation manufacture, Perbutyl (registered trademark) O) composition mixture as monomer and polymerization initiator Mixture, and the additive amount of glycidyl methacrylate is changed to other than 42.6g (0.3 mole), with 1 phase of synthesis example Same mode obtains the solution of resin (A).Using the resin as " resin (A-5) ".The resin (A-5) contained in the resin solution Acid value be 124KOHmg/g, weight average molecular weight 10000, unsaturated group equivalent be 600.It adds identically as synthesis example 1 Propylene glycol methyl ether acetate prepares resin (A-5) solution of synthesis example 5 (solid component concentration is 40 mass %).
<synthesis example 6>
Ethyoxyl in addition to using methacrylic acid tricyclodecyl by 52.8g (0.24 mole), 53.6g (0.2 mole) Change o-phenyl phenol acrylate, 48.2g (0.56 mole) methacrylic acid and 5.7g the tertiary fourth of peroxidating 2 ethyl hexanoic acid The mixture of ester (polymerization initiator, NOF Corporation manufacture, Perbutyl (registered trademark) O) composition as monomer and The mixture of polymerization initiator, and the additive amount of glycidyl methacrylate is changed to other than 24.1g (0.17 mole), The solution of resin (A) is obtained in a manner of identical with synthesis example 1.Using the resin as " resin (A-6) ".Contain in the resin solution The acid value of some resins (A-6) is 125KOHmg/g, and weight average molecular weight 9200, unsaturated group equivalent is 1100.With synthesis Example 1 adds propylene glycol methyl ether acetate in the same manner, and (solid component concentration is 40 matter to resin (A-6) solution of preparation synthesis example 6 Measure %).
<synthesis example 7>
In addition to by the peroxidating 2 ethyl hexanoic acid tert-butyl ester, (polymerization initiator, NOF Corporation are manufactured, Perbutyl (registered trademark) O) additive amount be changed to other than 4.7g, the solution of resin (A) is obtained in a manner of identical with synthesis example 2.It will The resin is used as " resin (A-7) ".The acid value of the resin (A-7) contained in the resin solution is 65KOHmg/g, weight average molecular weight It is 15000, unsaturated group equivalent is 600.
<synthesis example 8>
In addition to by the peroxidating 2 ethyl hexanoic acid tert-butyl ester, (polymerization initiator, NOF Corporation are manufactured, Perbutyl (registered trademark) O) additive amount be changed to other than 2.3g, the solution of resin (A) is obtained in a manner of identical with synthesis example 2.It will The resin is used as " resin (A-8) ".The acid value of the resin (A-8) contained in the resin solution is 65KOHmg/g, weight average molecular weight It is 30000, unsaturated group equivalent is 600.
<synthesis example 9>
In addition to using methacrylic acid tricyclodecyl, the methyl-prop of 57.0g (0.57 mole) by 39.6g (0.18 mole) E pioic acid methyl ester, the methacrylic acid of 7.7g (0.09 mole), 22.7g (0.16 mole) glycidyl methacrylate and The mixture of the azodiisobutyronitrile composition of 14.0g as other than the mixture of monomer and polymerization initiator, with 3 phase of synthesis example Same mode obtains the solution of resin (A).Using the resin as " resin (A-9) ".The resin (A-9) contained in the resin solution Acid value be 30KOHmg/g, weight average molecular weight 8500.
<synthesis example 10>
In addition to using methacrylic acid tricyclodecyl, the methyl-prop of 42.0g (0.42 mole) by 22.0g (0.1 mole) E pioic acid methyl ester, the 2-EHA of 11.0g (0.06 mole), 22.4g (0.26 mole) methacrylic acid, 22.7g The mixture of the azodiisobutyronitrile composition of the glycidyl methacrylate and 13.2g of (0.16 mole) as monomer and gathers Other than the mixture for closing initiator, the solution of resin (A) is obtained in a manner of identical with synthesis example 3.Using the resin as " resin (A-10)".The acid value of the resin (A-10) contained in the resin solution is 100KOHmg/g, weight average molecular weight 8700.
<comparing synthesis example 1>
(1) preparation of copolymer
It will be sweet by the Glycidyl methacrylate of the methacrylic acid of the N-phenylmaleimide of 64.1g, 18.8g, 10.3g The styrene of grease and 6.8g composition monomer mixture, 300g as the propylene glycol methyl ether acetate of solvent and the work of 2g It is added for the 2,2 '-azos bis- (2,4- methyl pentane nitriles) of radical polymerization initiator equipped with reflux cooler and blender In 500mL round-bottomed flask.Temperature is risen to 70 DEG C, will be stirred 5 hours for the mixture to be polymerized for generating copolymer. The acid value of the copolymer generated through the above way is 80KOHmg/g, weight average molecular weight 11000.
(2) with the compound of xanthene skeleton structure
Into the round-bottomed flask of 3000mL be added 125.4g -3 ', 6 '-glycol of spiral shell [fluorenes -9,9 '-xanthene] and The tert-butyl ammonium bromide of 0.1386g, and mixed.The epichlorohydrin for further adding 78.6g, heats the mixture to 90 DEG C, To implement to react.It is completely consumed being analyzed to identify -3 ', 6 '-glycol of spiral shell [fluorenes -9,9 '-xanthene] by liquid chromatography After falling, reactant is cooled to 30 DEG C, is slowly added 50% NaOH aqueous solution (3 equivalent).Passing through liquid chromatography point Analysis confirms after epichlorohydrin is completely consumed, and uses methylene chloride, extracts reactant, cleans 3 times.Had using magnesium sulfate drying Machine layer, distillation removes methylene chloride under reduced pressure.Using the mixture solvent (50:50, v/v) of methylene chloride and methanol, make thick Product crystallization.
Relative to the epoxy compounds of 1 equivalent obtained through the above way, the tert-butyl bromination of 0.004 equivalent is added The acrylic acid of ammonium, the 2,6- diisobutyl phenol of 0.001 equivalent and 2.2 equivalents.Then, the propylene glycol of 8.29g is further added Methyl ether acetate is mixed.Be blown into air into the solution prepared through the above way with 25mL/ minutes, by solution plus Heat is to 90~100 DEG C, to dissolve reactant.When solution is white and is muddy, temperature is set to rise to 120 DEG C, so that reactant It is completely dissolved.The acid value of solution is measured when solution went clear, viscosity increase, agitating solution is until acid value is less than 1.0KOHmg/ g.Continue stirring 11 hours until acid value reaches target value (0.8KOHmg/g).After reaction, the temperature decline of reactor To room temperature, colorless and transparent solid is obtained.
The solid product of 43g obtained through the above way, the acrylic acid of 33.6g, 0.04g are added into reaction flask 2,6-di-tert-butyl p-cresol, the tetrabutyl ammonium acetate of 0.21g and the propylene glycol methyl ether acetate of 18g, at 120 DEG C will Mixture stirs 13 hours.Then, reactant is cooled to room temperature, adds the propylene glycol methyl ether acetate of 24g and the amber of 10g Then amber acid anhydrides stirs mixture 3 hours at 100 DEG C.The bisphenol Z glycidol ether of 8g is further added to mixture, It stirs the mixture at 120 DEG C 4 hours, is stirred 3 hours at 90 DEG C, stir 2 hours at 60 DEG C, then stirred at 40 DEG C It mixes 5 hours.The reprecipitation in water and ethyl alcohol is carried out, and final resin is obtained with the state of powder.Then, so that solid at Point concentration is that the mode of 48 mass % adds propylene glycol methyl ether acetate.The acid value of the resin obtained through the above way is 105KOHmg/g, weight average molecular weight 5500.
By make solid component than for 6:4 in a manner of mix there is xanthene obtained in copolymer obtained in (1) and (2) The resin solution of synthesis example 1 is compared in the compound of skeleton structure, preparation.
<measuring method of physics value>
Acid value, unsaturated group equivalent and the weight average molecular weight recorded in synthesis example are to be obtained by the method for following record The value arrived.
(1) acid value: it is according to JIS K6901 5.3.2, using the mixed indicator of bromthymol blue and phenol red The acid value of the resin (A) of measurement.It is the milligram of potassium hydroxide needed for the acid ingredient contained in the resin (A) for neutralize 1g Number.
(2) unsaturated group equivalent: it is the quality of the corresponding polymer of every mole of polymerized unsaturated bond, for based on list The usage amount of body and the calculated value calculated.
(3) weight average molecular weight (Mw): referring to using gel permeation chromatography (GPC), and the standard measured with following conditions The weight average molecular weight of polystyrene conversion.
Chromatographic column: Shodex (registered trademark) LF-804+LF-804 (Showa Denko K.K. manufacture)
Chromatogram column temperature: 40 DEG C
Sample: 0.2% tetrahydrofuran solution of copolymer
Eluent: tetrahydrofuran
Detector: differential refractometer (Shodex (registered trademark) RI-71S) (Showa Denko K.K. manufacture)
Flow velocity: 1mL/min
<Examples 1 to 10 and comparative example 1~2>
Using synthesis example 1~10, compare the resin solution and commercially available resin solution of synthesis example 1, according to following table 1 and 2 Blended amount (quality % benchmark) preparation Examples 1 to 10 and comparative example 1~2 black interval column formation use lightsensitive resin composition Object.Comparative example 1 is the example corresponding to patent document 2.In addition, not containing and being used in the amount of resin (A) in following blended amounts Solvent when preparation.The amount of the solvent contained in the solution of resin (A) is aggregated in as in the solvent (B) for blending ingredient.In table 1 And in 2, V259ME is fluorenes type ring oxygroup type acrylate/acid anhydrides polymer adduct propylene glycol methyl ether acetate solution (tree The 56.5 mass % such as rouge ingredient), be NIPPON STEEL&SUMIKIN CHEMICAL CO., LTD. manufacture V259ME, PGMEA is propylene glycol methyl ether acetate, and OXE 01 is 1,2- acetyl caproyl, 1- [4- (phenyl)-, 2- (O- benzoyl Oxime)], for the IRGACURE OXE 01 of BASF AG's manufacture, mill base 1 is to contain lactams Organic Black (BASF AG's manufacture) Mill base, pigment concentration is 18 mass %, and mill base 2 is the mill base containing carbon black, and pigment concentration is 25 mass %, and DPHA was two seasons Penta tetrol, six acrylate, is SHIN-NAKAMURA CHEMICAL CO., and the A-DPH of LTD. manufacture, KBM-403 are 3- ring Oxygen the third oxygen propyl group triethoxysilane, for the KBM-403 of Shin-Etsu Silicone Co., Ltd. manufacture.
[table 1]
[table 2]
<evaluation of colorant dispersibility>
According to method evaluation colorant dispersibility as shown below.
Firstly, by make film with a thickness of 1.5 μm in a manner of, by Examples 1 to 10 and the black interval of comparative example 1~2 Column formation is spin-coated on the IZO substrate of 10cm × 10cm with photosensitive resin composition.Then, 3 minutes are heated at 90 DEG C, thus Solvent is set to volatilize.Then, the more light ML-251D/B and illumination optics unit PM25C-100 manufactured using Ushio inc. are to painting The entire surface of film is exposed (light exposure 50mJ/cm2), make its photocuring.Then, using the potassium hydroxide water of 0.2 mass % It is solution development 120 seconds, further rear at 230 DEG C to dry 30 minutes, obtain target cured coating film.By using penetrating concentration meter (361T, X-lite company), the optical density (OD) (Optical Density:OD) of the cured coating film of 1 μm of thickness of measurement.By result It is shown in table 2.Optical density (OD) is higher, it can be said that colorant dispersibility is more excellent.
<evaluation of development nargin>
In method identical with optical density (OD), 2.5 μm of film is made on substrate, uses Kosaka Laboratory Ltd. the contact pin type segment difference meter T4000M manufactured, the slip of the coating thickness between measurement developing time 100 seconds~150 seconds. Show the result in table 2.The slip of coating thickness is bigger, it can be said that having superior development nargin.
<evaluation of solvent resistance>
Black interval column sample used in evaluation in optical density (OD) is removed from substrate, is cut to 1cm × 1cm's Size, being put into addition has in the vial of N-Methyl pyrrolidone of 5mL, after being placed 15 minutes in 100 DEG C of baking oven, root According to following benchmark evaluations, whether there is or not decolorations.Show the result in table 2.
Zero: when visually being observed, absolutely not decolourizing.
×: when visually being observed, decolourize very more.
<evaluation of elastic restoration ratio>
According to determination condition below, using elasticity measurement device (DUH-W201S, Shimadzu Corporation), The compression displacement and elastic restoration ratio of the black interval column made in the evaluation of development nargin are measured at 25 DEG C.
The flat pressing body of the diameter with 50 μm is used to scheme as extruding to carry out load-unloaded method to load The pressing body of case.Apply the test of 300mN load using in order to obtain identifiable result between the group being compared, surveys Determine elastic restoration ratio.3gf/ seconds load speeds and 3 seconds retention times are maintained to fix.For elastic restoration ratio, to flat Pressing body applies fixed load 3 seconds, and the reality of the pattern before and after load is then measured by using Three-dimensional thickness measurement device Elastic restoration ratio.Elastic restoration ratio refers to fixed relative to being applied in the distance restored after 10 minutes recovery times The ratio of compressed distance (compression displacement), is indicated by following formula when power.
Elastic restoration ratio (%)=[(restoring distance/compression displacement) × 100]
Show the result in table 3 and table 4.
[table 3]
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Optical density (OD) 2.6 2.3 2.4 2.3 2.6 2.6
Film thickness reduction rates (%) 95 97 92 91 97 98
Solvent resistance ○ ○ ○ ○ ○ ○
Elastic restoration ratio (%) 94 96 99 93 96 95
[table 4]
Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Comparative example 1 Comparative example 2
Optical density (OD) 2.4 2.5 2.3 2.5 2.3 2.0
Film thickness reduction rates (%) 98 99 91 94 96 90
Solvent resistance ○ ○ ○ ○ ○ ×
Elastic restoration ratio (%) 94 92 95 91 Material breakage 92
From the above results, the black interval column of Examples 1 to 10 forms the colorant point with photosensitive resin composition It is excellent to dissipate property, development nargin, solvent resistance and elastic restoration ratio.On the other hand, the black interval column of comparative example 1 is formed with photosensitive When resin combination applies load in elastic restoration ratio test, spacer column is damaged, and the physical property of spacer column is poor.In addition, comparative example 2 Black interval column formation photosensitive resin composition solvent resistance evaluation result be decoloration it is more.

Claims (12)

1. a kind of black interval column, which is formed, uses photosensitive resin composition, which is characterized in that poly- containing resin (A), solvent (B), light Close initiator (C) and colorant (D), wherein the resin (A) has the structural unit (a) being selected from by with carboxyl, has The structural unit (b-1) of (methyl) acryloxy and with the functional group reacted with carboxyl structural unit (b-2) composition At least one of group structural unit.
2. black interval column according to claim 1, which is formed, uses photosensitive resin composition, which is characterized in that the resin (A) further containing the structural unit (c) with fragrant ring skeleton.
3. black interval column according to claim 1 or 2, which is formed, uses photosensitive resin composition, which is characterized in that the tree Structural unit (d) of the rouge (A) further containing the bridge-type alicyclic type hydrocarbon for being 7~20 with carbon atom number.
4. black interval column according to claim 2, which is formed, uses photosensitive resin composition, which is characterized in that the aromatic rings Skeleton is selected from least one of the group being made of biphenyl backbone, naphthalene skeleton and anthracene skeleton.
5. black interval column according to any one of claims 1 to 4, which is formed, uses photosensitive resin composition, feature exists In the functional group reacted with carboxyl is at least one of oxetanylmethoxy, epoxy group or isocyano functional group.
6. black interval column according to any one of claims 1 to 5, which is formed, uses photosensitive resin composition, feature exists In the carboxyl is the carboxyl from unsaturated carboxylic acid, the carboxyl from polyacid or the carboxyl from multi-anhydride.
7. black interval column described according to claim 1~any one of 6, which is formed, uses photosensitive resin composition, feature exists In the unsaturated group equivalent of the resin (A) is 200~2000g/ moles.
8. black interval column according to any one of claims 1 to 7, which is formed, uses photosensitive resin composition, feature exists In the colorant (D) contains inorganic black pigments and organic black pigments.
9. black interval column described according to claim 1~any one of 8, which is formed, uses photosensitive resin composition, feature exists In, the solvent (B) of the resin (A), 50~94 mass % containing 1~20 mass %, 0.01~5 mass % it is described The colorant (D) of Photoepolymerizationinitiater initiater (C) and 3~30 mass %.
10. black interval column according to claim 9, which is formed, uses photosensitive resin composition, which is characterized in that further contain There is the reactive diluent (E) of 1~20 mass %.
11. a kind of black interval column, which is characterized in that formed by black interval column according to any one of claims 1 to 10 Solidified with photosensitive resin composition.
12. a kind of image display device, which is characterized in that have black interval column described in claim 11.
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