CN104684994A - Ink-repellent composition, negative photosensitive resin composition, hardened film, partition wall, and optical element - Google Patents

Ink-repellent composition, negative photosensitive resin composition, hardened film, partition wall, and optical element Download PDF

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Publication number
CN104684994A
CN104684994A CN201380049711.1A CN201380049711A CN104684994A CN 104684994 A CN104684994 A CN 104684994A CN 201380049711 A CN201380049711 A CN 201380049711A CN 104684994 A CN104684994 A CN 104684994A
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compound
group
ink composition
partition wall
ink
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CN104684994B (en
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高桥秀幸
松浦启吾
川岛正行
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AGC Inc
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Asahi Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • 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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
    • H10K71/236—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers using printing techniques, e.g. applying the etch liquid using an ink jet printer

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  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

Provided are: an ink-repellent composition exhibiting excellent ink repellency and UV/O3 resistance; a hardened film and partition wall, the upper surfaces of which exhibit excellent ink repellency and are capable of maintaining excellent ink repellency even after undergoing an UV/O3 irradiation treatment; and an optical element in which ink can be evenly applied within dots. The ink-repellent composition includes: a first compound which is a partial hydrolysis condensate of a mixture including a first hydrolysable silane compound comprising a hydrolysable group and a fluoroalkylene group and/or fluoroalkyl group; and a second compound that has a hydrocarbon chain as the main chain, has a side chain containing a fluorine atom, and has a mass-average molecular weight (Mw) of 100-1,000,000.

Description

Refuse ink composition, negative light-sensitive resin combination, cured film, partition wall and optical element
Technical field
The present invention relates to cured film, partition wall and the optical element refusing ink composition, negative light-sensitive resin combination and employ this negative light-sensitive resin combination.
Background technology
For organic EL (Electro-Luminescence, organic electroluminescent) element, there is the method utilizing ink-jet (IJ) method pattern to print the organic layers such as luminescent layer.In the process, the profile along point arranges partition wall, comprises the ink of the material of the layer that will be formed, carry out drying and/or heating etc., thus form the pattern film expected to it to its inner injection.
In aforesaid method, in order to prevent the colour mixture of the ink between consecutive point and be coated with ink equably in point, it is required that partition wall upper surface has and refuses ink, and partition wall side has ink affinity.
Above-mentioned partition wall such as carries out pattern formation by the photolithography employing photosensitive polymer combination.
Such as, comprise in photosensitive polymer combination surface free energy little refuse black agent time, utilizing in the process of the solvent evaporation when making dried coating film that to refuse black agent mobile to air side (upper surface side of film) because of the repulsion worked between itself and other solids component, can give the upper surface of gained partition wall and refuse ink.In described method, importantly, the upper surface movability of black agent is refused.In addition, importantly, residually in point after development black agent is refused.
For organic EL, owing to remaining in the residue of the photosensitive polymer combination a little after development, the organic layers such as luminescent layer become easy deterioration.Thus, in order to remove the development residue a little, usually before injection ink, UV (ultraviolet)/O is carried out to the surface integral of base material 3(ozone) radiation treatment.Therefore, for organic EL, importantly, even if at UV/O 3after radiation treatment, the Mo Xingye that refuses of partition wall upper surface is able to good maintenance.
In the past, as refusing black agent, there will be a known the acrylic polymers (for example, see [embodiment] item of patent documentation 1 ~ 4) of the main chain comprised based on C-C and the side chain with fluorine atom.
But, comprise the resistance to UV/O refusing ink refusing black agent of acrylic polymers 3property is low, and the partition wall purposes as organic EL is insufficient.
Patent Document 5 discloses a kind of negative light-sensitive resin combination, its surface free energy is enough little, and the partition wall formed has at upper surface good refuses ink, and, even if through UV/O 3radiation treatment its refuse Mo Xingye and be able to good maintenance, this negative light-sensitive resin combination comprises silicon-type and refuses black agent, and described silicon-type refuses the hydrolytic condensate that black agent comprises fluorine-containing water-disintegrable silane compound.
Prior art document
Patent documentation
Patent documentation 1: No. 2004/042474th, International Publication
Patent documentation 2: No. 2007/069703rd, International Publication
Patent documentation 3: No. 2011/081151st, International Publication
Patent documentation 4: No. 2010/001976th, International Publication
Patent documentation 5: No. 2010/013816th, International Publication
Summary of the invention
the problem that invention will solve
For organic EL, the live width preferably originally not participating in the partition wall portions shown is thin as far as possible.Even if the live width in order to constriction partition wall also can prevent the colour mixture of the ink between consecutive point well, preferred partition wall upper surface to refuse ink higher.
The object of the invention is to, provide to manufacture and refuse ink and resistance to UV/O thereof 3property good partition wall refuse ink composition and refuse ink composition containing this and possess a little not easily remain refuse the characteristic of ink composition negative light-sensitive resin combination, use this negative light-sensitive resin combination and the cured film that obtains and partition wall.
And then, the object of the invention is to, the optical element with partition wall is provided, described partition wall upper surface have good to refuse in ink, point not easily residual to refuse in black agent, point can even spread black.
for the scheme of dealing with problems
What the invention provides the technical scheme with following [1] ~ [17] refuses ink composition, negative light-sensitive resin combination, cured film, partition wall and optical element.
[1] one refuses ink composition, it is characterized in that, it comprises the first compound and the second compound, and described first compound is the partial hydrolysis condensate of the mixture comprising the first hydrolysable silanes compound with fluorine alkylidene group and/or fluoroalkyl and hydrolization group
The main chain of described second compound is hydrocarbon chain and comprises side chain, the matter average molecular weight (Mw) with fluorine atom is 100 ~ 1,000,000.
[2] according to above-mentioned [1], refuse ink composition, wherein, aforementioned first hydrolysable silanes compound is the compound shown in following formula (cx-1).
(A-R F11) a-Si(R H11) bX 11 (4-a-b)···(cx-1)
(R f11for comprise at least 1 fluorine alkylidene group, the divalent organic group of carbonatoms 1 ~ 16 or comprise the divalent organic group of carbonatoms 2 ~ 16 of etheric oxygen atom.R h11for the alkyl of carbonatoms 1 ~ 6.
X 11for hydrolization group.X 11when existing multiple, they each other can difference also can be identical.
A is 1 or 2, b is 0 or 1, a+b is 1 or 2.
A is the group shown in fluorine atom or following formula (I).
-Si(R H12) cX 12 (3-c)···(I)
(R h12for the alkyl of carbonatoms 1 ~ 6.
C is 0 or 1.
X 12for hydrolization group.X 12when existing multiple, they each other can difference also can be identical.)
A-R f11when existing multiple, they each other can difference also can be identical.)
[3] according to above-mentioned [2], refuse ink composition, wherein, aforementioned mixture also comprises the second hydrolysable silanes compound shown in following formula (cx-2).
SiX 2 4···(cx-2)
(X 2represent hydrolization group, 4 X 2each other can difference also can be identical.)
[4] according to any one of above-mentioned [1] ~ [3], refuse ink composition, wherein, aforementioned mixture also comprises the 3rd hydrolysable silanes compound shown in following formula (cx-3).
(Y-Q 3) g-Si(R H3) hX 3 (4-g-h)···(cx-3)
(Y is the group with olefinic double bond.
Q 3for the divalent organic group of the not contain fluorine atoms of carbonatoms 1 ~ 6.
R h3for the alkyl of carbonatoms 1 ~ 6.
X 3for hydrolization group.X 3when existing multiple, they each other can difference also can be identical.
G is 1 or 2, h is 0 or 1, g+h is 1 or 2.
Y-Q 3when existing multiple, they each other can difference also can be identical.)
[5] according to any one of above-mentioned [1] ~ [4], refuse ink composition, wherein, aforementioned second compound is polymkeric substance, and described polymkeric substance comprises the fluoroalkyl optionally containing etheric oxygen atom and/or has the side chain of the optional fluoroalkyl containing etheric oxygen atom.
[6] according to above-mentioned [5], refuse ink composition, wherein, aforementioned second compound is the polymkeric substance comprising the side chain with acidic-group.
[7] according to above-mentioned [5] or [6], refuse ink composition, wherein, aforementioned second compound is the polymkeric substance comprising the side chain with olefinic double bond.
[8] according to any one of above-mentioned [5] ~ [7], refuse ink composition, wherein, aforementioned second compound is the polymkeric substance comprising the side chain with oxyalkylene.
[9] according to any one of above-mentioned [1] ~ [8], refuse ink composition, wherein, aforementioned second Compound Phase is 0.01 ~ 10 for the mass ratio of aforementioned first compound.
[10] according to any one of above-mentioned [1] ~ [9], refuse ink composition, wherein, the containing ratio of fluorine atom is 5 ~ 40 quality %.
[11] negative light-sensitive resin combination, it comprises alkali soluble resin or base soluble monomer (A), Photoepolymerizationinitiater initiater (B) and the solvent (D) refusing ink composition and have light solidified according to any one of above-mentioned [1] ~ [10].
[12] negative light-sensitive resin combination according to above-mentioned [11], it is also included in 1 molecule has more than 2 olefinic double bonds and the linking agent (E) without acidic-group.
[13] negative light-sensitive resin combination according to above-mentioned [11] or [12], wherein, the first compound in all solids composition containing ratio be 0.05 ~ 10 quality %, the second compound containing ratio be 0.01 ~ 5 quality %.
[14] negative light-sensitive resin combination according to any one of above-mentioned [11] ~ [13], wherein, what aforementioned in all solids composition refused ink composition is 0.06 ~ 15 quality % containing ratio.
[15] cured film, is characterized in that, its be the negative light-sensitive resin combination according to any one of above-mentioned [11] ~ [14] is coated substrate surface, remove solvent (D) and exposure.
[16] partition wall, is characterized in that, it comprises the cured film described in above-mentioned [15].
[17] optical element, is characterized in that, it possesses multiple point and the partition wall described in above-mentioned [16].
the effect of invention
Of the present invention refuse ink composition can prepare can form upper surface refuse ink and resistance to UV/O thereof 3the negative light-sensitive resin combination of the partition wall that property is good, have and use this negative light-sensitive resin combination and the optical element of partition wall that obtains possesses to have at the upper surface of partition wall and good refuses ink and not easily residual characteristic of refusing black composition in point, therefore, it is possible in some even spread black, easily form pattern film.
Accompanying drawing explanation
Figure 1A is the process picture sheet of the manufacture method schematically showing the partition wall formed by cured film of the present invention.
Figure 1B is the process picture sheet of the manufacture method schematically showing the partition wall formed by cured film of the present invention.
Fig. 1 C is the process picture sheet of the manufacture method schematically showing the partition wall formed by cured film of the present invention.
Fig. 1 D is the process picture sheet of the manufacture method schematically showing the partition wall formed by cured film of the present invention.
Fig. 1 E is the process picture sheet of the manufacture method schematically showing the partition wall formed by cured film of the present invention.
Fig. 2 A is the process picture sheet of the manufacture method schematically showing the pattern film employing the partition wall formed by cured film of the present invention.
Fig. 2 B is the process picture sheet of the manufacture method schematically showing the pattern film employing the partition wall formed by cured film of the present invention.
Embodiment
In this specification sheets, " (methyl) acryl " is the general designation of " methacryloyl " and " acryl ".(methyl) acrylate, (methyl) acrylamide and (methyl) acrylic resin are also according to this regulation.
In this specification sheets, sometimes the group shown in formula (x) is abbreviated as group (x).
In this specification sheets, sometimes the compound shown in formula (y) is abbreviated as compound (y).
Herein, formula (x), formula (y) represent any formula.
" side chain " in this specification sheets refers to: form in the polymkeric substance of main chain at repeating unit, with the group except hydrogen atom or halogen atom of the carbon atom bonding of formation main chain.
" all solids composition of photosensitive polymer combination " in this specification sheets refers to the composition for the formation of aftermentioned cured film among the composition contained by photosensitive polymer combination, is obtained by residue photosensitive polymer combination being eliminated solvent with 140 DEG C of heating 24 hours.It should be noted that, all solids component amount also can be calculated by charging capacity.
In this specification sheets, the film of photosensitive resin coating composition being called " film ", dried coating film being made and the film that obtains is called " desciccator diaphragm " and then the film that obtains making desciccator diaphragm solidify is called " cured film ".
Cured film can be pattern film, also can be the film not forming pattern.
In this specification sheets, " upper surface " of partition wall does not comprise the side of partition wall.
It is all that " ink " in this specification sheets comprises the liquid possessing optical function and/or electric function.
It is all that " ink " in this specification sheets comprises the ink used in the pattern printing based on ink-jet (IJ) method.
For the optical element such as colour filter and organic tft (Thin Film Transistor, thin film transistor) array of organic EL, liquid crystal cell, IJ method can be utilized to carry out pattern and to print various integrant." ink " in this specification sheets is included in the ink used in such use.
" refusing ink " in this specification sheets refers to the character repelling above-mentioned ink, comprises both water repellency and oil repellent.Refuse ink such as to be evaluated by contact angle when dripping ink.
" resistance to UV/O in this specification sheets 3property " carry out UV/O even if refer to 3also the characteristic of refusing ink is kept well after radiation treatment.
" point " in this specification sheets represents the Minimum Area of the optical modulation carried out in optical element.For the optical element such as colour filter and organic tft array of organic EL, liquid crystal cell, 1 point=1 pixel when showing black and white, such as 3 points (R (red), G (green), B (indigo plant) etc.)=1 pixel when display color.
Below embodiments of the present invention are described.It should be noted that, in this specification sheets, in case of no particular description, % represents quality %.
[refusing ink composition]
Ink composition of refusing of the present invention is (below sometimes also referred to as refusing ink composition (C).) in, comprise the first following compound and the second compound as refusing ink compound.It should be noted that, the raw material of unreacted first compound and the second compound regards as and is included in this and refuses in ink composition (C).
Ink composition (C) of refusing of the present invention is preferably only made up of the first compound and the second compound.
Ink composition of refusing of the present invention can be applied in negative light-sensitive resin combination or positive type photosensitive organic compound etc. and contained to refuse black agent.Particularly preferably be applied to negative light-sensitive resin combination.Partition wall formation composition during the pattern based on IJ method that said composition is suitable as the various integrants of optical element is formed.
In the forming process of partition wall, refuse ink composition and move to upper surface and form thin layer of ink of refusing at partition wall upper surface, partition wall upper surface is given and refuses ink.It should be noted that, ink composition of refusing of the present invention also can be used in other purposes.
Specify that according to the research of the present inventor: the first compound and the second compound is all independent refuses ink in the performance of partition wall upper surface, but under the condition that fluorine atom containing ratio is identical, when combinationally using the first compound and the second compound, that more can improve partition wall upper surface compared with when individually using refuses ink.Its reason is considered as follows.
Even if be used alone the first compound, also can there is crosslinking reaction to a certain degree and be formed at partition wall upper surface thin to refuse layer of ink.But the molecular weight of the first compound is as being about 1000 ~ 2000, and the expansion of each molecule is little, therefore intermolecular easy generation gap.Can think by second this gap of compound landfill, thus refuse Mo Xinghui raising.
According to the research of the present inventor, can think following some be also the effect combinationally using the first compound and the second compound.
(1) be used alone the second Compound Phase ratio, during alkali development, the removal refusing layer of ink of partition wall upper surface is suppressed, refuses ink and improve.
(2) be used alone the first Compound Phase ratio, the storage stability of negative light-sensitive resin combination improves.
(3) be used alone the first Compound Phase ratio, not easily there is the protuberance of the end of partition wall upper surface.
The reason that can show effect (1) is considered as follows.
When being used alone the second compound, if the matter average molecular weight (Mw) of the second compound is more than 100,000, then can refuses ink to the imparting of partition wall upper surface is high, but there is the tendency reduced to the solvability in alkaline developer.Can think: during alkali development, a part for partition wall upper surface is refused layer of ink and is removed, refuses ink and reduce.Can think: by combinationally using first compound that can not produce this tendency, during alkali development, the removal refusing layer of ink of partition wall upper surface is suppressed, refuses ink raising.
The reason that can show effect (2) is considered as follows.
When being used alone the first compound, because silanol group reactivity is each other high, thus exist and comprise the insufficient tendency of the storage stability of the photosensitive polymer combination of the first compound.Can think: by combinationally using the second reactive low compound, silanol group reaction is each other suppressed, the storage stability of photosensitive polymer combination improves.
The reason that can show effect (3) is considered as follows.
When being used alone the first compound, form the tump of the level that scanning electron microscope (SEM) etc. can be utilized to observe sometimes in the end of partition wall upper surface.This protuberance can not cause obstruction especially as partition wall etc., but when supposing that this protuberance comes off because of certain reason, can give refuse ink to the sidewall of partition wall etc., therefore not preferred.
Can think: the first compound due to silanol group reactivity each other high, even if therefore also crosslinking reaction to a certain degree can be there is in non-exposed portion and form above-mentioned protuberance.Can think: by combinationally using the second reactive low compound, the silanol group reaction each other in non-exposed portion is subject to the generation hindering, suppress above-mentioned protuberance.
It should be noted that, the present inventor confirms: in this protuberance compared with other parts, and the content of F and/or Si is more.
(the first compound)
First compound be comprise the first hydrolysable silanes compound mixture (hereinafter also referred to hydrolysable silanes compound.) partial hydrolysis condensate.Comprise the first hydrolysable silanes compound in this hydrolysable silanes compound as essential component, optionally comprise the second hydrolysable silanes compound described later ~ the 5th hydrolysable silanes compound.The hydrolysable silanes compound except the second hydrolysable silanes compound ~ the 5th hydrolysable silanes compound can also be comprised.
First compound is the composition with molecular weight distribution.
< first hydrolysable silanes compound >
The first hydrolysable silanes compound in the present invention is the compound with fluorine alkylidene group and/or fluoroalkyl and hydrolization group.
As hydrolization group, the group etc. that at least one hydrogen in alkoxyl group, halogen atom, acyl group, isocyanate group, amino, amino is replaced by alkyl can be listed.Easily carry out smoothly from the view point of the reaction being formed hydroxyl (silanol group) by hydrolysis reaction and then form Si-O-Si key in intermolecular generation condensation reaction, be preferably the alkoxy or halogen atom of carbonatoms 1 ~ 4, be more preferably methoxyl group, oxyethyl group or chlorine atom, be particularly preferably methoxy or ethoxy.
First hydrolysable silanes compound can be used singly or in combination of two or more.
By using the first hydrolysable silanes compound comprising fluorine alkylidene group and/or fluoroalkyl, the first compound has fluorine alkylidene group and/or fluoroalkyl.Use when comprising the negative light-sensitive resin combination of the first compound, can give the upper surface of partition wall and good refuse ink.And then, even if through UV/O 3radiation treatment also can keep good and refuse ink.
It should be noted that, in order to show the above-mentioned effect of the first hydrolysable silanes compound further, the first hydrolysable silanes compound more preferably has fluoroalkyl, perfluorinated alkylidene or perfluoroalkyl, particularly preferably has perfluoroalkyl.In addition, the perfluoroalkyl of etheric oxygen atom is also preferably comprised.That is, as the first hydrolysable silanes compound, most preferred compound is the compound of the perfluoroalkyl having perfluoroalkyl and/or comprise etheric oxygen atom.
As the first hydrolysable silanes compound, be preferably the compound shown in following formula (cx-1).
(A-R F11) a-Si(R H11) bX 11 (4-a-b)···(cx-1)
In formula (cx-1), R f11for comprise at least 1 fluorine alkylidene group, the divalent organic group of carbonatoms 1 ~ 16 or comprise the divalent organic group of carbonatoms 2 ~ 16 of etheric oxygen atom.
R h11for the alkyl of carbonatoms 1 ~ 6.
X 11for hydrolization group.X 11when existing multiple, they each other can difference also can be identical.
A is 1 or 2, b is 0 or 1, a+b is 1 or 2.
A is the group shown in fluorine atom or following formula (I).
-Si(R H12) cX 12 (3-c)···(I)
In formula (I), R h12for the alkyl of carbonatoms 1 ~ 6.
C is 0 or 1.
X 12for hydrolization group.X 12when existing multiple, they each other can difference also can be identical.
In addition, A-R f11when existing multiple, they each other can difference also can be identical.
Compound (cx-1) is the fluorine-containing water-disintegrable silane compound with 1 or 22 functionalities or 3 functionality hydrolyzable silyl group.
R h11and R h12be preferably the alkyl of carbonatoms 1 ~ 3, be particularly preferably methyl.
In formula (cx-1), particularly preferably be, a is 1, b is 0 or 1.
As the X of hydrolization group 11and X 12concrete example and optimal way described above.
As the first hydrolysable silanes compound, be particularly preferably the compound shown in following formula (cx-1a).
D-R F12-Q 11-SiX 11 3···(cx-1a)
In formula (cx-1a), R f12for the perfluorinated alkylidene optionally comprising etheric oxygen atom of carbonatoms 2 ~ 15.
Q 11for the divalent organic group of the not contain fluorine atoms of carbonatoms 1 ~ 10.
X 11for hydrolization group.3 X 11each other can difference also can be identical.
D is the group shown in fluorine atom or following formula (Ia).
-Q 12-SiX 12 3···(Ia)
In formula (Ia), X 12for hydrolization group.3 X 12each other can difference also can be identical.
Q 12for the divalent organic group of the not contain fluorine atoms of carbonatoms 1 ~ 10.
In formula (cx-1a), when D is fluorine atom, R f12be preferably the perfluorinated alkylidene of carbonatoms 4 ~ 8 or the perfluorinated alkylidene comprising etheric oxygen atom of carbonatoms 4 ~ 10, be more preferably the perfluorinated alkylidene of carbonatoms 4 ~ 8, be particularly preferably the perfluorinated alkylidene of carbonatoms 6.
In addition, in formula (cx-1a), when D is group (Ia), R f12be preferably the perfluorinated alkylidene of carbonatoms 3 ~ 15 or the perfluorinated alkylidene comprising etheric oxygen atom of carbonatoms 3 ~ 15, be particularly preferably the perfluorinated alkylidene of carbonatoms 4 ~ 6.
R f12during for above-mentioned group, refuse ink composition by of the present invention, can obtain can form upper surface refuse ink and resistance to UV/O thereof 3property good partition wall negative light-sensitive resin combination, and compound (cx-1a) is excellent to the solvability in solvent.
As R f12structure, linear chain structure can be listed, branched structure, ring structure, part have the structure etc. of ring, be preferably linear chain structure.
As R f12concrete example, following group can be listed.
-(CF 2) 4-、-(CF 2) 6-、-(CF 2) 8-、-CF 2CF 2OCF 2CF 2OCF 2-、-CF 2CF 2OCF 2CF 2OCF 2CF 2-、-CF 2CF 2OCF 2CF 2OCF 2CF 2OCF 2CF 2OCF 2-、-CF 2CF 2OCF 2CF 2OCF 2CF 2OCF 2CF 2OCF 2CF 2-。-CF 2CF 2CF 2OCF 2-、-CF 2CF 2CF 2OCF 2CF 2-、-CF 2CF 2CF 2OCF(CF 3)-、-CF 2CF 2CF 2OCF(CF 3)CF 2-、-CF 2CF 2CF 2OCF(CF 3)CF 2OCF 2CF 2-、-CF 2CF 2CF 2OCF(CF 3)CF 2OCF(CF 3)-、-CF 2CF 2CF 2OCF(CF 3)CF 2OCF(CF 3)CF 2-、-CF 2OCF(CF 3)CF 2OCF(CF 3)-、-CF 2CF 2OCF(CF 3)CF 2OCF(CF 3)-。
Q 11and Q 12in, with respectively on the atomic bond on right side bonding Si and on the atomic bond in left side bonding R f12form when representing, specifically, preferably :-(CH 2) i1-(i1 is the integer of 1 ~ 5.) ,-CH 2o (CH 2) i2-(i2 is the integer of 1 ~ 4.) ,-SO 2nR 1-(CH 2) i3-(R 1for hydrogen atom, methyl or ethyl, i3 is the integer of 1 ~ 4, R 1with (CH 2) i3carbonatoms add up to less than 4 integer.) or-(C=O)-NR 1-(CH 2) i4-(R 1same as described above, i4 is the integer of 1 ~ 4, R 1with (CH 2) i4carbonatoms add up to less than 4 integer.) shown in group.As Q 11and Q 12, be more preferably integer-(CH that i1 is 2 ~ 4 2) i1-, be particularly preferably-(CH 2) 2-.
It should be noted that, R f12during for perfluorinated alkylidene, as Q 11and Q 12, be preferably-(CH 2) i1-shown group.Integer, i1 that i1 is more preferably 2 ~ 4 are particularly preferably 2.
R f12during for comprising the perfluorinated alkylidene of etheric oxygen atom, as Q 11and Q 12, be preferably-(CH 2) i1-,-CH 2o (CH 2) i2-,-SO 2nR 1-(CH 2) i3-or-(C=O)-NR 1-(CH 2) i4-shown group.Wherein ,-(CH is more preferably 2) i1-, i1 more preferably 2 ~ 4 integer, i1 is particularly preferably 2.
When D is fluorine atom, as the concrete example of compound (cx-1a), following compound can be listed.F(CF 2) 4CH 2CH 2Si(OCH 3) 3、F(CF 2) 6CH 2CH 2Si(OCH 3) 3、F(CF 2) 6CH 2CH 2CH 2Si(OCH 3) 3、F(CF 2) 8CH 2CH 2Si(OCH 3) 3、F(CF 2) 3OCF(CF 3)CF 2O(CF 2) 2CH 2CH 2Si(OCH 3) 3、F(CF 2) 2O(CF 2) 2O(CF 2) 2CH 2CH 2Si(OCH 3) 3。
When D is group (Ia), as the concrete example of compound (cx-1a), following compound can be listed.(CH 3O) 3SiCH 2CH 2(CF 2) 4CH 2CH 2Si(OCH 3) 3、(CH 3O) 3SiCH 2CH 2(CF 2) 6CH 2CH 2Si(OCH 3) 3、(CH 3O) 3SiCH 2CH 2(CF 2) 6CH 2CH 2CH 2Si(OCH 3) 3、(CH 3O) 3SiCH 2CH 2(CF 2) 2OCF 2CF(CF 3)O(CF 2) 2OCF(CF 3)CF 2O(CF 2) 2CH 2CH 2Si(OCH 3) 3。
Wherein, F (CF is particularly preferably 2) 6cH 2cH 2si (OCH 3) 3or F (CF 2) 3oCF (CF 3) CF 2o (CF 2) 2cH 2cH 2si (OCH 3) 3.
In the present invention, as compound (cx-1a), wherein, be particularly preferably F (CF 2) 6cH 2cH 2si (OCH 3) 3, or F (CF 2) 3oCF (CF 3) CF 2o (CF 2) 2cH 2cH 2si (OCH 3) 3.
The ratio that fluorine atom containing ratio in the partial hydrolysis condensate preferably obtained by this mixture containing ratio of the first hydrolysable silanes compound in hydrolysable silanes compound reaches 5 ~ 55 quality %, more preferably reaches 10 ~ 40 quality %, particularly preferably reaches 15 ~ 30 quality %.First hydrolysable silanes compound be more than the lower value of above-mentioned scope containing ratio time, can give the upper surface of cured film and good refuse ink, for below higher limit time, become good with the consistency of other hydrolysable silanes compound in this mixture.
< second hydrolysable silanes compound >
The second hydrolysable silanes compound in the present invention is the compound shown in following formula (cx-2).
SiX 2 4···(cx-2)
In formula (cx-2), X 2represent hydrolization group, 4 X 2each other can difference also can be identical.As X 2, can use and aforementioned X 11and X 12identical group.
Compound (cx-2) can be used singly or in combination of two or more.
As the concrete example of compound (cx-2), following compound can be listed.In addition, as compound (cx-2), as required, the partial hydrolysis condensate these compounds multiple partial hydrolysis condensation in advance obtained can also be used.
As concrete example, be Si (OCH 3) 4, Si (OCH 2cH 3) 4, Si (OCH 3) 4partial hydrolysis condensate (such as COLCOAT CO., Ltd manufacture Methyl Silicate 51 (trade(brand)name)), Si (OCH 2cH 3) 4partial hydrolysis condensate (such as, COLCOAT CO., Ltd manufacture Ethyl Silicate 40, Ethyl Silicate 48 (being trade(brand)name)) etc.
By making inclusion compound (cx-2) in hydrolysable silanes compound, for by comprise the first compound negative light-sensitive resin combination solidification cured film for, can improve refuse ink composition (C) move to upper surface after film-forming properties.Can think: the quantity of the hydrolization group in compound (cx-2) is many, therefore move to the condensation well each other of upper surface rear section hydrolytic condensate, thin film (film-forming properties is excellent) can be formed in upper surface entirety.
In addition, by making inclusion compound (cx-2) in hydrolysable silanes compound, the first compound is soluble in hydrocarbon system solvent.
The ratio that contains of the second hydrolysable silanes compound in hydrolysable silanes compound is preferably 0.01 ~ 5 mole relative to 1 mole of the first hydrolysable silanes compound, is particularly preferably 0.05 ~ 3 mole.When being more than the lower value of above-mentioned scope containing ratio, the film-forming properties refusing ink composition (C) is good, for below higher limit time, can give the upper surface of cured film and good refuse ink.
< the 3rd hydrolysable silanes compound >
The 3rd hydrolysable silanes compound in the present invention is the hydrolysable silanes compound shown in following formula (cx-3).
(Y-Q 3) g-Si(R H3) hX 3 (4-g-h)···(cx-3)
In formula (cx-3), Y is the group with olefinic double bond.
Q 3for the divalent organic group of the not contain fluorine atoms of carbonatoms 1 ~ 6.
R h3for the alkyl of carbonatoms 1 ~ 6.
X 3for hydrolization group.X 3when existing multiple, they each other can difference also can be identical.
G is 1 or 2, h is 0 or 1, g+h is 1 or 2.
Y-Q 3when existing multiple, they each other can difference also can be identical.
As R h3, can use and aforementioned R h11and R h12identical group.
As X 3, can use and aforementioned X 11and X 12identical group.
As Y, be preferably (methyl) acryloxy or ethenylphenyl, be particularly preferably (methyl) acryloxy.
As Q 3concrete example, the alkylidene group of carbonatoms 2 ~ 6, phenylene etc. can be listed.Wherein ,-(CH is preferably 2) 3-.
Preferably, g is 1, h is 0 or 1.
Compound (cx-3) can be used singly or in combination of two or more.
As the concrete example of compound (cx-3), following compound can be listed.
CH 2＝C(CH 3)COO(CH 2) 3Si(OCH 3) 3、
CH 2＝C(CH 3)COO(CH 2) 3Si(OC 2H 5) 3、
CH 2＝CHCOO(CH 2) 3Si(OCH 3) 3、
CH 2＝CHCOO(CH 2) 3Si(OC 2H 5) 3、
[CH 2＝C(CH 3)COO(CH 2) 3]SiCH 3(OCH 3) 2、
[CH 2＝C(CH 3)COO(CH 2) 3]SiCH 3(OC 2H 5) 2。
By making the compound (cx-3) of the group Y comprised in hydrolysable silanes compound containing band olefinic double bond, in the manufacture of the partition wall that negative light-sensitive resin combination is solidified, can improve and refuse the fixation performance of ink composition (C) at partition wall upper surface.
Compound (cx-3) has the group Y of band olefinic double bond, therefore when the exposure of negative light-sensitive resin combination, refuse ink compound each other or other composition with olefinic double bond refused in ink compound and negative light-sensitive resin combination can carry out copolymerization via this group.Can think: by these action effects, refuse ink composition (C) after exposure and be chemically bound in cured film upper surface, thus fixation performance improves.
The ratio that contains of the 3rd hydrolysable silanes compound in hydrolysable silanes compound is preferably 0.1 ~ 5 mole relative to 1 mole of the first hydrolysable silanes compound, is particularly preferably 0.5 ~ 4 mole.When being more than the lower value of above-mentioned scope containing ratio, upper surface movability and the fixation performance of refusing ink composition (C) are good, and in addition, the storage stability refusing ink composition is good.For below higher limit time, refuse ink composition (C) to refuse ink good.
< the 4th hydrolysable silanes compound >
The 4th hydrolysable silanes compound in the present invention is the compound shown in following formula (cx-4).
(R H4) j-SiX 4 (4-j)···(cx-4)
In formula (cx-4), R h4for the alkyl of carbonatoms 1 ~ 6.R h4when existing multiple, they each other can difference also can be identical.
X 4for hydrolization group.X 4when existing multiple, they each other can difference also can be identical.
J is 2 or 3.
As R h4, can use and aforementioned R h11and R h12identical group.
As X 4, can use and aforementioned X 11and X 12identical group.
Compound (cx-4) can be used singly or in combination of two or more.
As the concrete example of compound (cx-4), following compound can be listed.
(CH 3) 3-Si-OCH 3、(CH 3CH 2) 3-Si-OCH 2CH 3、(CH 3) 3-Si-OCH 2CH 3、(CH 3CH 2) 3-Si-OCH 3、(CH 3) 2-Si-(OCH 3) 2、(CH 3) 2-Si-(OCH 2CH 3) 2、(CH 3CH 2) 2-Si-(OCH 2CH 3) 2、(CH 3CH 2) 2-Si-(OCH 3) 2。
When using compound (cx-2) in hydrolysable silanes compound, for the partition wall solidified by negative light-sensitive resin combination, the end on surface forms protuberance thereon sometimes.It is the tump of the level that scanning electron microscope (SEM) etc. can be utilized to observe.The present inventor confirms: in this protuberance, compared with other parts, and the content of F and/or Si is more.
Above-mentioned protuberance can not cause obstruction especially as partition wall etc., and the present inventor finds: by a part for compound (cx-2) is replaced into the few compound of hydrolysising group number (cx-4), can suppress the generation of above-mentioned protuberance.
By the silanol group reaction each other that the compound (cx-2) many by hydrolysising group number generates, the film-forming properties refusing ink composition (C) increases.But can think: produce above-mentioned protuberance because it is reactive high.
On the other hand, can think: by a part for compound (cx-2) is replaced into the few compound of hydrolysising group number (cx-4), silanol group reaction is each other suppressed, being suppressed of above-mentioned protuberance.
The ratio that contains of the 4th hydrolysable silanes compound in hydrolysable silanes compound is preferably 0.05 ~ 5 mole relative to 1 mole of the first hydrolysable silanes compound, is particularly preferably 0.3 ~ 3 mole.When being more than the lower value of above-mentioned scope containing ratio, the protuberance of the end of partition wall upper surface can be suppressed.For below higher limit time, refuse ink composition (C) to refuse ink good.
< the 5th hydrolysable silanes compound >
The 5th hydrolysable silanes compound in the present invention is the compound having sulfydryl and hydrolization group but do not have fluorine alkylidene group and fluoroalkyl.
As hydrolization group, the group identical with the hydrolization group of the first hydrolysable silanes compound can be used.
5th hydrolysable silanes compound can be used singly or in combination of two or more.
By using the 5th hydrolysable silanes compound comprising sulfydryl, negative light-sensitive resin combination can expose with lower exposure.Can think because: links such as the sulfydryl in the 5th hydrolysable silanes compound has chain tra nsfer, the olefinic double bond easily had with aftermentioned alkali soluble resin or base soluble monomer (A), thus promote photocuring.
In addition, the pKa comprising the 5th hydrolysable silanes compound of sulfydryl is about 10, easily takes off proton, namely easily dissociates in alkaline solution.
Herein, by pKa=-log 10ka represents, in formula, Ka represents acid ionization constant.Therefore, alkali-soluble when can think that sulfydryl can improve the development of negative light-sensitive resin combination.
As the 5th hydrolysable silanes compound, be preferably the compound shown in following formula (cx-5).
(HS-Q 5) p-Si(R H5) qX 5 (4-p-q)···(cx-5)
In formula (cx-5), Q 5for the divalent organic group of the not contain fluorine atoms of carbonatoms 1 ~ 10.
R h5for the alkyl of carbonatoms 1 ~ 6.
X 5for hydrolization group.X 5when existing multiple, they each other can difference also can be identical.
P is 1 or 2, q is 0 or 1, p+q is 1 or 2.
HS-Q 5when existing multiple, they each other can difference also can be identical.
As X 5, can use and aforementioned X 1and X 2identical group.
As Q 5, be preferably the alkylidene group of carbonatoms 1 ~ 10, be more preferably the alkylidene group of carbonatoms 1 ~ 5, be particularly preferably the alkylidene group of carbonatoms 1 ~ 3.
As R h5, can use and aforementioned R h11and R h12identical group.
As the concrete example of compound (cx-5), HS-(CH can be listed 2) 3-Si (OCH 3) 3, HS-(CH 2) 3-Si (CH 3) (OCH 3) 2deng.
The ratio that contains of the 5th hydrolysable silanes compound in hydrolysable silanes compound is preferably 0.125 ~ 18 mole relative to 1 mole of the first hydrolysable silanes compound, is particularly preferably 0.125 ~ 8 mole.When being more than the lower value of above-mentioned scope containing ratio, negative light-sensitive resin combination can expose with lower exposure.For below higher limit time, refuse ink composition (C) to refuse ink good.
Other hydrolysable silanes compound of < >
Hydrolysable silanes compound can comprise the one kind or two or more any hydrolysable silanes compound except the first hydrolysable silanes compound ~ the 5th hydrolysable silanes compound.
As other hydrolysable silanes compound, can list and there is oxyalkylene and hydrolization group but the hydrolysable silanes compound without fluorine alkylidene group and fluoroalkyl.Specifically, include, for example out CH 3o (C 2h 4o) ksi (OCH 3) 3(Trimethoxy silane containing polyoxyethylene) (herein, k is such as about 10.) etc.
The combination > of the preferred hydrolysable silanes compound of <
First compound be inclusion compound (cx-1a), arbitrarily inclusion compound (cx-2) ~ (cx-5) and group D in compound (cx-1a) is the partial hydrolysis condensate of the mixture of fluorine atom time, its average group accepted way of doing sth is shown in following formula (II).
[D-R F12-Q 11-SiO 3/2] n1·[SiO 2] n2·[(Y-Q 3) g-Si(R H3) hSiO (4-g-h)/2] n3[(R H4) j-SiO (4-j)/2] n4·[(HS-Q 5) p-Si(R H5) qO (4-p-q)/2] n5···(II)
In formula (II), n1 ~ n5 is the molar percentage of each structural unit of integral molar quantity relative to structural unit.n1>0、n2≥0、n3≥0、n4≥0、n5≥0、n1+n2+n3+n4+n5＝1。Other each symbol is described above.It should be noted that, D is fluorine atom.
Because reality is for remaining the product (partial hydrolysis condensate) of hydrolization group or silanol group, therefore this product is difficult to represent with chemical formula.An average group accepted way of doing sth shown in formula (II) is hydrolization group in hypothesis first compound or silanol group chemical formula when all forming siloxane bond.In addition, in formula (II), can infer that the unit deriving from compound (cx-1a) and (cx-2) ~ (cx-5) respectively arranges randomly.
The feeding intake of n1:n2:n3:n4:n5 in an average group accepted way of doing sth shown in formula (II) and the compound (cx-1a) in hydrolysable silanes compound and (cx-2) ~ (cx-5) forms consistent.
The mol ratio of each composition is designed by the balance of the effect of each composition.
N1 is preferably 0.05 ~ 0.4.
N2 is preferably 0 ~ 0.8, is particularly preferably 0.05 ~ 0.6.
N3 is preferably 0 ~ 0.8, is particularly preferably 0.2 ~ 0.5.
N4 is preferably 0 ~ 0.5, is particularly preferably 0.05 ~ 0.3.
N5 is preferably 0.05 ~ 0.9, is particularly preferably 0.05 ~ 0.4.
It should be noted that, be also same the D of preferred molar ratio in compound (cx-1a) of above-mentioned each composition is group (Ia).
The matter average molecular weight (Mw) of the first compound is preferably more than 500, is more preferably more than 1000.In addition, preferred less than 1,000,000, more preferably less than 10000.Be particularly preferably less than 6000.
Matter average molecular weight (Mw) for more than lower value time, not easily move to upper surface as the first compound refusing black agent.During not enough higher limit, the first compound becomes good to the solvability in solvent.And then during not enough higher limit, the first compound becomes good to the solvability in solvent.
The matter average molecular weight (Mw) of the first compound can utilize manufacturing condition to regulate.
The manufacture > of < partial hydrolysis condensate
First compound known method can be utilized to be hydrolyzed by making said hydrolyzed silane compound mixture and condensation reaction manufactures.
Preferably the organic acids such as the mineral acids such as normally used hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or acetic acid, oxalic acid, toxilic acid are used as catalyzer in this reaction.In addition, also preferred metal complexs such as the organic bases such as mineral alkali, Tetramethylammonium hydroxide, dibutyl tin laurate such as sodium hydroxide etc. are used as catalyzer.
Above-mentioned reaction can use known solvent.
(the second compound)
Second compound is that main chain is hydrocarbon chain and comprises the compound that side chain, the matter average molecular weight (Mw) with fluorine atom are 100 ~ 1,000,000.Matter average molecular weight (Mw) is preferably more than 3000, is more preferably more than 5000.In addition, be preferably less than 300,000, be more preferably less than 200,000.
Second compound preferably comprises the fluoroalkyl optionally containing etheric oxygen atom and/or has the optional polymkeric substance containing the side chain of the fluoroalkyl of etheric oxygen atom.
Second compound preferably has the polymkeric substance of the polymerized unit containing fluoroalkyl.The polymerized unit with fluoroalkyl imports in polymkeric substance preferably by polymerization occurs the polymerizable monomer making to have fluoroalkyl.
In addition, by the various method of modifying making optimization compound react with the polymkeric substance with reactive site, also fluoroalkyl can be imported in polymkeric substance.
Fluoroalkyl can be straight-chain, also can be branched.
As the concrete example of fluoroalkyl, following structure can be listed.
-CF 3、-CF 2CF 3、-CF 2CHF 2、-(CF 2) 2CF 3、-(CF 2) 3CF 3、-(CF 2) 4CF 3、-(CF 2) 5CF 3、-(CF 2) 6CF 3、-(CF 2) 7CF 3、-(CF 2) 8CF 3、-(CF 2) 9CF 3、-(CF 2) 11CF 3、-(CF 2) 15CF 3。
Fluoroalkyl optionally comprises etheric oxygen atom.
Concrete example when comprising etheric oxygen atom as fluoroalkyl, can list following structure.
-CF(CF 3)O(CF 2) 5CF 3、
-CF 2O(CF 2CF 2O) r1CF 3、
-CF(CF 3)O(CF 2CF(CF 3)O) r2C 6F 13、
-CF(CF 3)O(CF 2CF(CF 3)O) r3C 3F 7。
In above-mentioned formula, the integer that the integer that r1 is 1 ~ 8, r2 are 1 ~ 4, r3 are the integer of 1 ~ 5.
Fluoroalkyl becomes good viewpoint be preferably perfluoroalkyl from refusing ink.
The carbonatoms of fluoroalkyl is preferably 4 ~ 15.Refuse ink excellent, in addition, when manufacturing the second compound, the consistency with the monomer outside the monomer of fluoroalkyl and this monomer aftermentioned becomes good.
As the monomer with fluoroalkyl, CH can be listed 2=CR 4cOOR 5r f, CH 2=CR 4cOOR 6nR 4sO 2r f, CH 2=CR 4cOOR 6nR 4cOR f, CH 2=CR 4cOOCH 2cH (OH) R 5r f, CH 2=CR 4cR 4=CFR fdeng.
In above-mentioned formula, be respectively: R ffor fluoroalkyl, R 4for hydrogen atom or methyl, R 5for the divalent organic group of singly-bound or carbon number 1 ~ 6, R 6for the divalent organic group of carbon number 1 ~ 6.
As R 5and R 6concrete example, can-CH be listed 2-,-CH 2cH 2-,-CH (CH 3)-,-CH 2cH 2cH 2-,-C (CH 3) 2-,-CH (CH 2cH 3)-,-CH 2cH 2cH 2cH 2-,-CH (CH 2cH 2cH 3)-,-CH 2(CH 2) 3cH 2-and-CH (CH 2cH (CH 3) 2)-.
Above-mentioned polymerizable monomer may be used singly or in combination of two or more.
Second compound becomes good from the view point of the alkali-soluble of the second compound, preferably comprises the polymkeric substance of the side chain with acidic-group.
It should be noted that, the side chain with fluoroalkyl optionally comprises acidic-group.In addition, also can exist different from the side chain with fluoroalkyl, there is acidic-group but not there is the side chain of fluoroalkyl.
As acidic-group, at least a kind of acidic-group in the group preferably selecting free carboxyl group, phenolic hydroxyl group and sulfonic group to form or its salt.
From having photocrosslinking reaction, solidifying partition wall forming process on upper strata, refusing the lasting viewpoint of Mo Xinghui, the second compound preferably comprises the polymkeric substance of the side chain with olefinic double bond.
Be particularly preferably the polymkeric substance comprising more than 2 olefinic double bonds in 1 side chain.
It should be noted that, the side chain with fluoroalkyl optionally comprises olefinic double bond.
In addition, can also exist different from the side chain with fluoroalkyl, there is olefinic double bond and not there is the side chain of fluoroalkyl.
Second compound can be the polymkeric substance comprising the side chain with oxyalkylene.The form of the polyoxy alkylidene chain (POA chain) that oxyalkylene can link with multiple oxyalkylene and involved.As oxyalkylene, oxygen ethylidene, oxygen propylidene can be listed, be preferably oxygen ethylidene.
Oxyalkylene self does not have photocrosslinking reaction, but second compound with oxyalkylene is identical with the situation with olefinic double bond, solidifies in partition wall forming process on upper strata, it is lasting to refuse Mo Xinghui.Oxyalkylene has wetting ability, therefore also has the effect improved for the wettability of developing solution.
It should be noted that, the side chain with fluoroalkyl optionally comprises oxyalkylene.In addition, also can exist different from the side chain with fluoroalkyl, there is oxyalkylene and not there is the side chain of fluoroalkyl.
Second compound can comprise the side chain with acidic-group, the side chain with olefinic double bond and have more than a kind side chain among the side chain of oxyalkylene.Also two or more among acidic-group, olefinic double bond and oxyalkylene can be comprised in 1 side chain.
The side chain with any group except the side chain that second compound can comprise side chain except having acidic-group, have the side chain of olefinic double bond and have an oxyalkylene.
As there is acidic-group and not there is the introduction method of the side chain of fluoroalkyl, the monomer preferably making to have fluoroalkyl with there is acidic-group and not there is the method for the monomer generation copolymerization of fluoroalkyl.In addition, by the various method of modifying making optimization compound react with the polymkeric substance with reactive site, also acidic-group can be imported in polymkeric substance.
As the monomer with carboxyl, (methyl) vinylformic acid, vinylacetic acid, β-crotonic acid, methylene-succinic acid, toxilic acid, fumaric acid, styracin and their salt can be listed.They may be used singly or in combination of two or more.
As the monomer with phenolic hydroxyl group, o-hydroxystyrene, hydroxy styrenes, 4-Vinyl phenol etc. can be listed.In addition, the compound that more than 1 hydrogen atom on their phenyl ring is replaced by haloalkyl, nitro, cyano group or amide group that more than 1 hydrogen atom of the alkoxyl groups such as the alkyl such as methyl, ethyl, normal-butyl, methoxyl group, oxyethyl group, n-butoxy, halogen atom, alkyl is replaced by halogen atom can be listed.
As having sulfonic monomer, vinyl sulfonic acid, styrene sulfonic acid, (methyl) allyl sulphonic acid, 2-hydroxyl-3-(methyl) allyloxy propanesulfonic acid, (methyl) vinylformic acid-2-Sulfoethyl esters, (methyl) vinylformic acid-2-sulphopropyl, 2-hydroxyl-3-(methyl) acryloxy propanesulfonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic and their salt can be listed.
As by making the various method of modifying that optimization compound and the polymkeric substance with reactive site react and the method imported to by carboxyl in polymkeric substance, include, for example out the monomer generation copolymerization that (1) makes to have hydroxyl in advance, then make the method that itself and acid anhydrides react; (2) make the acid anhydrides generation copolymerization with olefinic double bond in advance, then make the method that it reacts with the compound with hydroxyl.
As the concrete example of monomer with hydroxyl, (methyl) vinylformic acid 2-hydroxy methacrylate can be listed, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 5-hydroxyl pentyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxycyclohexyl, neopentyl glycol single (methyl) acrylate, 3-chlorine-2-hydroxyl propyl group (methyl) acrylate, glycerine list (methyl) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol mono vinyl ether, 2-hydroxyethyl allyl ethers, N-hydroxymethyl (methyl) acrylamide, N, two (hydroxymethyl) (methyl) acrylamides of N-etc.They may be used singly or in combination of two or more.
The monomer with hydroxyl can for having the monomer of the polyoxy alkylidene chain (POA chain) that end is hydroxyl.
Include, for example out CH 2=CHOCH 2c 6h 10cH 2o (C 2h 4o) k1h, CH 2=CHOC 4h 8o (C 2h 4o) k1h, CH 2=CHCOOC 2h 4o (C 2h 4o) k1h, CH 2=C (CH 3) COOC 2h 4o (C 2h 4o) k1h, CH 2=CHCOOC 2h 4o (C 2h 4o) k2(C 3h 6o) k3h, CH 2=C (CH 3) COOC 2h 4o (C 2h 4o) k2(C 3h 6o) k3h etc.They may be used singly or in combination of two or more.
In above-mentioned formula, the integer that the integer that k1 is 1 ~ 100, k2 are 0 ~ 100, k3 be 1 ~ 100 integer, k2+k3 be 1 ~ 100.
As acid anhydrides, the acid anhydrides of the compound in 1 molecule with more than 2 carboxyls can be listed.Trimethylacetic acid acid anhydride and trimellitic acid 1,2-anhydride can be listed.In addition, maleic anhydride, itaconic anhydride, citraconic anhydride, Tetra hydro Phthalic anhydride, 3-methyl nadic anhydride, methyl-5-norbornylene-2 can be listed, 3-dicarboxylic anhydride, 3,4,5,6-Tetra Hydro Phthalic Anhydride, cis-1,2,3,6-Tetra Hydro Phthalic Anhydride, 2-butylene-1-base succinyl oxide etc. have the acid anhydrides of olefinic double bond.They may be used singly or in combination of two or more.
As the compound with hydroxyl, as long as have the compound of more than 1 hydroxyl, the Trivalin SF classes such as cellosolve class, 2-(2-methoxy ethoxy) ethanol, 2-(2-ethoxy ethoxy) ethanol, 2-(2-Butoxyethoxy) ethanol such as aforementioned shown alcohols, 2-methyl cellosolve, cellosolvo, the butoxy ethanol such as the concrete example with the monomer of hydroxyl, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, ethylene glycol can be listed.Wherein, the compound in molecule with 1 hydroxyl is preferably.They may be used singly or in combination of two or more.
According to aforesaid method, the side chain comprising acidic-group, the side chain comprising acidic-group and olefinic double bond can be imported or comprise the side chain of acidic-group and oxyalkylene.
Also can use not hydroxyl and acidic-group but there is monomer, such as following formula (POA-1), the monomer shown in (POA-2) of polyoxy alkylidene chain (POA chain).
CH 2＝CR 71-COO-W-(R 72-O) k4-R 73···(POA-1)、
CH 2＝CR 71-O-W-(R 72-O) k4-R 73···(POA-2)
(R 71for the cycloalkyl of the alkyl of hydrogen atom, chlorine atom, bromine atoms, atomic iodine, cyano group, carbon number 1 ~ 20, the alkyl replaced by aryl of carbon number 7 ~ 20, the aryl of carbon number 6 ~ 20 or carbon number 3 ~ 20.
R 72for the alkylidene group of carbonatoms 1 ~ 5.
R 73for the alkyl of carbonatoms 1 ~ 4.
W is the divalent organic group without fluorine atom of singly-bound or carbon number 1 ~ 10.
K4 is the integer of 6 ~ 30.)
In addition, suitably select known monomer and reaction by composition desirably, the second compound of the one kind or two or more side chain among the side chain that comprises the side chain with acidic-group, the side chain with olefinic double bond and there is oxyalkylene can be obtained.
Refuse the second Compound Phase in ink composition (C) mass ratio (quality of quality/the first compound of the second compound) of the first compound is preferably to 0.01 ~ 10, is more preferably 0.02 ~ 5, is particularly preferably 0.05 ~ 2.
In addition, the containing ratio refusing the fluorine atom in ink composition (C) is preferably 5 ~ 40 quality %, is more preferably 10 ~ 35 quality %, more preferably 13 ~ 32 quality %.During for this scope, refuse refusing ink and becoming good with characteristics such as the consistencies of other composition in negative light-sensitive resin combination of ink composition (C).
[negative light-sensitive resin combination]
Negative light-sensitive resin combination of the present invention contains the alkali soluble resin with light solidified or base soluble monomer (A), Photoepolymerizationinitiater initiater (B), above-mentionedly refuses ink composition (C) and solvent (D).Also linking agent (E), tinting material (F) etc. can be contained as required.
(alkali soluble resin or base soluble monomer (A))
Alkali soluble resin is given to symbol (AP), given symbol (AM) to base soluble monomer, is described respectively.
As alkali soluble resin (AP), be preferably the photoresist in 1 molecule with acidic-group and olefinic double bond.By having olefinic double bond in the molecule of alkali soluble resin (AP), there is polymerization because of the free radical produced from Photoepolymerizationinitiater initiater (B) thus solidification in the exposure portion of negative light-sensitive resin combination.The exposure portion of solidifying in this wise can not be removed by alkaline developer.
In addition, in the molecule there is acidic-group by alkali soluble resin (AP), thus optionally can remove the non-exposed portion of uncured negative light-sensitive resin combination with alkaline developer.Its result, can form the cured film of desired pattern, i.e. partition wall.
As acidic-group, can list carboxyl, phenolic hydroxyl group, sulfo group, phosphate etc., they can be used singly or in combination of two or more.
As olefinic double bond, the double bond that (methyl) acryl, allyl group, vinyl, vinyl oxygen base, vinyl oxygen base alkyl etc. have polyaddition can be listed.They can be used singly or in combination of two or more.
It should be noted that, one of the hydrogen atom that olefinic double bond has or all optionally replaced by alkyl such as methyl.
As alkali soluble resin (AP), can list containing have acidic-group side chain and have olefinic double bond side chain resin (A-1), in epoxy resin, be imported with the resin (A-2) etc. of acidic-group and olefinic double bond.They can be used singly or in combination of two or more.
Resin (A-1) such as can utilize the method for following (i) or (ii) to synthesize.
(i) side chain is had monomer generation copolymerization that reactive group outside acidic-group, such as hydroxyl, the monomer of epoxy group(ing) isoreactivity group and side chain have acidic-group, thus obtain containing there is the side chain of reactive group and there is the multipolymer of side chain of acidic-group.Then, this multipolymer is made to react with the compound with the functional group and olefinic double bond that can be bonded to above-mentioned reactive group.Or, after making side chain have the monomer copolymerization of the acidic-groups such as carboxyl, make to have and can be bonded to the functional group of acidic-group and the compound of olefinic double bond reacts with the amount that acidic-group can remain after the reaction.
(ii) monomer making side chain have the reactive group outside the acidic-group identical with above-mentioned (i) reacts with the compound with the functional group that can be bonded to this reactive group and the olefinic double bond protected.Then, after making this monomer and side chain have the monomer copolymerization of acidic-group, the protection of removal olefinic double bond.Or, side chain is had after the monomer of acidic-group and side chain have the monomer copolymerization of the olefinic double bond protected, the protection of removal olefinic double bond.
It should be noted that, (i) and (ii) preferably implements in a solvent.
Among aforesaid method, preferably use the method for (i).Below, the method for (i) is specifically described.
About having the monomer of hydroxyl as reactive group, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, neopentyl glycol single (methyl) acrylate, glycerine list (methyl) acrylate, 2-hydroxyethyl vinyl ether, 2-hydroxyethyl allyl ethers, N-hydroxymethyl (methyl) acrylamide, two (hydroxymethyl) (methyl) acrylamides of N, N-etc. can be listed.
There is use while the monomer of hydroxyl as reactive group, want the monomer with acidic-group of copolymerization except the aftermentioned monomer with carboxyl, as the monomer with phosphate, 2-(methyl) acryloyl-oxyethyl phosphoric acid ester etc. also can be listed.There is hydroxyl to carry out according to existing known method as the monomer of reactive group and the copolymerization of the monomer with acidic-group.
As to react with gained multipolymer, have and can be bonded to the functional group of hydroxyl and the compound of olefinic double bond, the acid anhydrides with olefinic double bond, the compound with isocyanate group and olefinic double bond can be listed, there is the compound etc. of acid chloride group and olefinic double bond.
As the acid anhydrides with olefinic double bond, toxilic acid acid, itaconic anhydride, citraconic anhydride, methyl-5-norbornylene-2,3-dicarboxylic anhydride, 3 can be listed, 4,5,6-Tetra Hydro Phthalic Anhydride, cis-1,2,3,6-Tetra Hydro Phthalic Anhydride, 2-butylene-1-base succinyl oxide etc.
As the compound with isocyanate group and olefinic double bond, 2-(methyl) acryloyloxyethyl isocyanate, 1,1-two ((methyl) acryloyloxymethyl) ethyl isocyanates etc. can be listed.
As the compound with acid chloride group and olefinic double bond, (methyl) acrylate chloride etc. can be listed.
About having the monomer of epoxy group(ing) as reactive group, (methyl) glycidyl acrylate, vinylformic acid 3,4-epoxycyclohexanecarboxylate etc. can be listed.
As will with there is the monomer with acidic-group of epoxy group(ing) as the monomer copolymerization of reactive group, can use with above-mentioned have hydroxyl as the monomer of reactive group in the identical monomer of the monomer that illustrates, for there is epoxy group(ing) as the monomer of reactive group and the copolymerization of monomer with acidic-group, also can carry out according to existing known method.
As to react with gained multipolymer, have and can be bonded to the functional group of epoxy group(ing) and the compound of olefinic double bond, the compound etc. with carboxyl and olefinic double bond can be listed.As the concrete example of described compound, vinylformic acid, methacrylic acid, vinylacetic acid, β-crotonic acid, methylene-succinic acid, toxilic acid, fumaric acid, styracin and their salt can be listed, its monoesters etc. can be listed when diprotic acid.It should be noted that, the acid anhydrides making the dehydrating condensation part of hydroxyl and the carboxylic acid generated form a part for ring texture herein reacts, and also can import carboxyl in resin (A-1).
About having the monomer of carboxyl as reactive group, vinylformic acid, methacrylic acid, vinylacetic acid, β-crotonic acid, methylene-succinic acid, toxilic acid, fumaric acid, styracin and their salt can be listed, its monoesters etc. can be listed when diprotic acid.It should be noted that, these monomers also can be used as the above-mentioned monomer with acidic-group.
Use when there is the monomer of carboxyl as reactive group, as mentioned above, this monomer is polymerized.As to react with resulting polymers, have and can be bonded to the functional group of carboxyl and the compound of olefinic double bond, the compound with epoxy group(ing) and olefinic double bond can be listed.As described compound, (methyl) glycidyl acrylate, vinylformic acid 3,4-epoxycyclohexanecarboxylate etc. can be listed.It should be noted that, now, to react with the polymkeric substance with carboxyl, have the amount that can be bonded to the functional group of carboxyl and the compound of olefinic double bond be set to reaction after in the polymer carboxyl residue in the amount of side chain with the form of acidic-group.
Resin (A-2) reacts with polycarboxylic acid or its acid anhydride and synthesizes after can reacting by making epoxy resin and the compound with carboxyl and olefinic double bond described later.
Specifically, by making epoxy resin react with the compound with carboxyl and olefinic double bond, thus olefinic double bond is imported in epoxy resin.Then, by making polycarboxylic acid or its acid anhydride react with the epoxy resin being imported with olefinic double bond, carboxyl can be imported.
As epoxy resin, be not particularly limited, bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, tris-phenol type epoxy resin, the epoxy resin with naphthalene skeleton, the epoxy resin with biphenyl backbone shown in following formula (A-2a), fluorenes replacement bisphenol A type epoxy resin, the epoxy resin etc. with biphenyl backbone shown in following formula (A-2c) shown in following formula (A-2b) can be listed.
(v is the integer of 1 ~ 50, is preferably the integer of 2 ~ 10.In addition, the phenyl that is optionally optionally substituted with a substituent by the alkyl of carbonatoms 1 ~ 12, halogen atom or a part of hydrogen atom independently of one another of the hydrogen atom of phenyl ring replace.)
(R 31, R 32, R 33and R 34be the alkyl of hydrogen atom, chlorine atom or carbonatoms 1 ~ 5 independently of one another, w is the integer of 0 or 1 ~ 10.)
(phenyl that the hydrogen atom of phenyl ring is optionally optionally substituted with a substituent by the alkyl of carbonatoms 1 ~ 12, halogen atom or a part of hydrogen atom independently of one another replace.Z is the integer of 0 or 1 ~ 10.)
It should be noted that, time after epoxy resin shown in formula (A-2a) ~ (A-2c) and the compound with carboxyl and olefinic double bond are reacted again with polycarboxylic acid anhydride reactant, as polybasic acid anhydride, preferably use the mixture of dicarboxylic anhydride and tetracarboxylic dianhydride.
As the compound with carboxyl and olefinic double bond, vinylformic acid, methacrylic acid, vinylacetic acid, β-crotonic acid, methylene-succinic acid, toxilic acid, fumaric acid, styracin and their salt can be listed.This compound is preferably monoesters when diprotic acid, is particularly preferably (methyl) vinylformic acid.
As alkali soluble resin (AP), from the stripping of cured film during development be suppressed, can obtain the viewpoint of high-resolution pattern, line pattern the good viewpoint of rectilinearity, easily obtain the viewpoint on level and smooth cured film surface, preferably use resin (A-2).
As resin (A-2), be particularly preferably and imported the resin of acidic-group and olefinic double bond in bisphenol A type epoxy resin, the resin of acidic-group and olefinic double bond has been imported in bisphenol f type epoxy resin, the resin of acidic-group and olefinic double bond has been imported in phenol novolak type epoxy resin, the resin of acidic-group and olefinic double bond has been imported in cresol novolak type epoxy resin, the resin of acidic-group and olefinic double bond has been imported in tris-phenol type epoxy resin, or in the epoxy resin shown in formula (A-2a) ~ (A-2c), imported the resin of acidic-group and olefinic double bond.
As base soluble monomer (AM), such as, preferably use the monomer (A-3) of the side chain comprising and there is acidic-group and the side chain with olefinic double bond.Acidic groups is identical with alkali soluble resin (AP) with olefinic double bond.
As monomer (A-3), 2,2,2-tri-acryloyloxymethyl ethyl phthalic acid etc. can be listed.
The alkali soluble resin (AP) comprised in negative light-sensitive resin combination or base soluble monomer (AM) can be used singly or in combination of two or more.
The ratio that contains of the alkali soluble resin in all solids composition in negative light-sensitive resin combination or base soluble monomer (A) is preferably 5 ~ 80 quality %, is particularly preferably 10 ~ 60 quality %.When being above-mentioned scope containing ratio, light solidified and the developability of negative light-sensitive resin combination are good.
(Photoepolymerizationinitiater initiater (B))
Photoepolymerizationinitiater initiater (B) in the present invention, as long as have the compound of the function as Photoepolymerizationinitiater initiater, is just not particularly limited, and preferably utilizes light and produces the compound of free radical.
As Photoepolymerizationinitiater initiater (B), the α-diones such as methyl phenyl glyoxylate ester, 9,10-phenanthrenequione can be listed; The acyloin classes such as bitter almond oil camphor; The acyloin ethers such as benzoin methylether, ethoxybenzoin, benzoin iso-propylether; The thioxanthene ketones such as thioxanthone, CTX, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone; Benzophenone, 4, the benzophenones such as 4 '-bis-(dimethylamino) benzophenone, 4,4 '-bis-(diethylin) benzophenone; Methyl phenyl ketone, 2-(4-tosyloxy)-2-phenyl acetophenone, to dimethylamino methyl phenyl ketone, 2, the acetophenones such as 2 '-dimethoxy-2-phenyl acetophenone, p-methoxy-acetophenone, 2-methyl-[4-(methylthio group) phenyl]-2-morpholinyl-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone; The quinones such as anthraquinone, 2-ethyl-anthraquinone, camphorquinone, 1,4-naphthoquinone; The aminobenzoic acids such as 2-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester; The halogen compounds such as phenacyl chloride (phenacyl chloride), trihalomethyl group phenylsulfone; Acylphosphine oxide class; The superoxide such as ditertiary butyl peroxide; { 1-[4-(thiophenyl)-2-(O-benzoyl oxime)] } oxime ester class such as 1,2-acetyl caproyl, acetyl oxime; The aliphatics amines such as trolamine, methyldiethanolamine, tri-isopropanolamine, n-Butyl Amine 99, N methyldiethanol amine, diethylaminoethyl methacrylate; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, Isosorbide-5-Nitrae-butanols two (3-mercaptobutylate), three (2-mercaptopropionyl oxygen base ethyl) mercaptan compound etc. such as isocyanuric acid ester, tetramethylolmethane four (3-mercaptobutylate).
Among Photoepolymerizationinitiater initiater (B), when benzophenone, aminobenzoic acids, aliphatics amine, mercaptan compound etc. use jointly with other radical initiator, showing sensitization effect sometimes, is preferred.
As Photoepolymerizationinitiater initiater (B); be preferably 2-methyl-[4-(methylthio group) phenyl]-2-morpholinyl-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, { 1-[4-(thiophenyl)-2-(O-benzoyl oxime)] } 1; 2-acetyl caproyl, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime) ethyl ketone or 2,4-diethyl thioxanthone.And then, be particularly preferably they and benzophenone, such as 4, the combination of 4 '-bis-(diethylin) benzophenone.
Photoepolymerizationinitiater initiater (B) can be used singly or in combination of two or more.
The ratio that contains of the Photoepolymerizationinitiater initiater (B) in all solids composition in negative light-sensitive resin combination is preferably 0.1 ~ 50 quality %, is more preferably 0.5 ~ 30 quality %, is particularly preferably 5 ~ 15 quality %.When being above-mentioned scope containing ratio, light solidified and the developability of negative light-sensitive resin combination are good.
(refusing ink composition (C))
The ratio that contains of the first compound in all solids composition in negative light-sensitive resin combination is preferably 0.05 ~ 10 quality %, is more preferably 0.1 ~ 3 quality %, is particularly preferably 0.2 ~ 1 quality %.
The ratio that contains of the second compound in all solids composition in negative light-sensitive resin combination is preferably 0.01 ~ 5 quality %, is more preferably 0.03 ~ 2 quality %, is particularly preferably 0.05 ~ 0.5 quality %.
The ratio that contains refusing ink composition (C) in all solids composition in negative light-sensitive resin combination is preferably 0.06 ~ 15 quality %, is more preferably 0.13 ~ 5 quality %, is particularly preferably 0.25 ~ 1.5 quality %.
In negative light-sensitive resin combination, the second Compound Phase is preferably 0.01 ~ 10 for the mass ratio (quality of quality/the first compound of the second compound) of the first compound, is more preferably 0.02 ~ 5, is particularly preferably 0.05 ~ 2.During scope for aforementioned mass ratio, the storage stability of negative light-sensitive resin combination, refuse ink, its resistance to UV/O 3property, light solidified and developability are good.
(solvent (D))
Negative light-sensitive resin combination in the present invention is by containing solvent (D), viscosity is minimized, negative light-sensitive resin combination becomes easy to the coating on substrate surface.Its result, can form the film of the negative light-sensitive resin combination of homogeneous film thickness.
As solvent (D), known solvent can be used.
The ratio that contains of the solvent (D) in negative light-sensitive resin combination is preferably 50 ~ 99 quality %, is more preferably 60 ~ 95 quality %, is particularly preferably 65 ~ 90 quality %.
(linking agent (E))
As the linking agent (E) in the present invention, be preferably in 1 molecule and there are more than 2 olefinic double bonds but the compound without acidic-group.Contain linking agent (E) by negative light-sensitive resin combination, even if thus exposure time negative light-sensitive resin combination solidified nature improve utilize low exposure also can form partition wall.
As linking agent (E), Diethylene Glycol two (methyl) acrylate can be listed, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, ditrimethylolpropane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, ethoxylation tricarbimide triacrylate, 6-caprolactone modification three-(2-acryloyl-oxyethyl) isocyanuric acid ester, 9, two [4-(2-acryloyloxyethoxy) phenyl] fluorenes of 9-, urethane acrylate etc.
From photoreactive viewpoint, preferably there is multiple olefinic double bond.Such as, tetramethylolmethane four (methyl) acrylate, ditrimethylolpropane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, ethoxylation tricarbimide triacrylate, urethane acrylate etc. are preferably.
Linking agent (E) can be used singly or in combination of two or more.
The ratio that contains of the linking agent (E) in all solids composition in negative light-sensitive resin combination is preferably 10 ~ 60 quality %, is particularly preferably 20 ~ 55 quality %.
(tinting material (F))
As the tinting material (F) in the present invention, carbon black, nigrosine, black pigment, perylene system of anthraquinone system black pigment, specifically C.I. Pigment black 1,6,7,12,20,31 etc. can be listed.Also the mixture of the pigment dyestuffs such as red pigment, blue pigments and veridian and/or mineral dye can be used.
The ratio that contains of the tinting material (F) in all solids composition in negative light-sensitive resin combination of the present invention is preferably 15 ~ 65 quality %, is particularly preferably 20 ~ 50 quality %.During for above-mentioned scope, the sensitivity of gained negative light-sensitive resin combination is good, and in addition, the opacifying property of the partition wall formed is excellent.
(other composition)
It is one kind or two or more that negative light-sensitive resin combination of the present invention can also contain in other additives such as thermal cross-linking agent, macromolecule dispersing agent, dispersing auxiliary, silane coupling agent, particulate, phosphate cpd, curing catalyst, thickening material, softening agent, defoamer, flow agent, antishrinking agent, UV light absorber as required.
[partition wall]
Partition wall of the present invention is by the coating of above-mentioned negative light-sensitive resin combination on substrate surface and carry out the figuratum cured film of tool that exposes and develop.
Below, use Figure 1A ~ Fig. 1 E that one example of the manufacture method of partition wall is described, but the manufacture method of partition wall is not limited to following explanation.
As shown in Figure 1A, to the surface integral coating negative light-sensitive resin combination and form film 21 of base material 10.Now, in film 21, there is the first compound of refusing ink and the second compound integrally dissolves and disperses equably.It should be noted that, in figure, refuse ink composition (C) and schematically show, in fact do not exist with this particle shape.
Then, as shown in Figure 1B, make film 21 dry and make desciccator diaphragm 22.As drying means, heat drying, drying under reduced pressure and heating under reduced pressure drying etc. can be listed.
Although also depend on the kind of solvent (D), when heat drying, Heating temperature is preferably 50 ~ 120 DEG C, is more preferably 70 ~ 120 DEG C, more preferably 80 ~ 120 DEG C.
In this drying process, refuse ink composition (C) to the upper surface of desciccator diaphragm and neighbouring movement thereof.
Then, as shown in Figure 1 C, across having the photomask 30 of opening portion 31 of predetermined pattern, irradiate light L to expose to desciccator diaphragm 22.Film after exposing desciccator diaphragm 22 is called exposed film 23.In exposed film 23,23A is exposure portion, 23B is non-exposed portion.In this operation, exposure portion 23A carries out photocuring.
As the light L irradiated, visible ray can be listed; Ultraviolet; Far ultraviolet rays yue; KrF excimer laser, ArF excimer laser, F 2excimer laser, Kr 2excimer laser, KrAr excimer laser, Ar 2the excimer laser such as excimer laser; X-ray; Electron beam etc.
As the light L irradiated, be preferably the light of wavelength 100 ~ 600nm, be more preferably the light of 300 ~ 500nm, be particularly preferably the light comprising i ray (365nm), h ray (405nm) or g ray (436nm).
As Exposure mode, can list that whole face exposes in the lump, scan exposure etc.Also can expose several times same position.Now, the condition of multiple-exposure is identical or different.
Exposure in above-mentioned any Exposure mode, such as, is all preferably 5 ~ 1000mJ/cm 2, be more preferably 5 ~ 500mJ/cm 2, more preferably 5 ~ 300mJ/cm 2, be particularly preferably 5 ~ 200mJ/cm 2, most preferably be 5 ~ 50mJ/cm 2.It should be noted that, exposure is suitably optimized according to the wavelength, the composition of negative light-sensitive resin combination, the thickness of film etc. of the light irradiated.
The time shutter of per unit area is not particularly limited, and is designed by the exposure power of the exposure apparatus used and the exposure etc. of necessity.It should be noted that, during scan exposure, obtain the time shutter by the sweep velocity of light.
The time shutter of per unit area is generally about 1 ~ 60 second.
Then, as shown in figure ip, use alkaline developer to develop, form the cured film 24 with desired pattern.In cured film 24, the exposure portion 23A in previous exposure becomes protuberance 24A, non-exposed portion 23B becomes pattern openings portion 24B.
It should be noted that, in this operation, the ink composition (C) of refusing of non-exposed portion 23B is dissolved in alkaline developer well, can not residue in pattern openings portion 24B.
The figuratum cured film 24 of tool can heat as referring to figure 1e further.Heating temperature is preferably 130 ~ 250 DEG C, is more preferably 180 ~ 250 DEG C, more preferably 200 ~ 230 DEG C.By heating, refuse ink composition (C) and be firmly bonded in cured film, form thin layer more nearby on distance surface.
After above-mentioned heating, for for utilizing IJ method pattern to print for the purposes such as the partition wall of the organic layer such as luminescent layer of organic EL, generally for the development residue removing negative light-sensitive resin combination residual in pattern openings portion 24B, and UV/O is carried out to base material 10 3radiation treatment.
According to negative light-sensitive resin combination of the present invention, the partition wall with following characteristic can be formed: even if upper surface has and good refuses ink and through UV/O 3radiation treatment its refuse Mo Xingye and be able to can not remain and refuse black agent in good maintenance, point.
Partition wall of the present invention, when utilizing IJ method to carry out pattern printing, can be used as the partition wall of delimiting black injection zone.
The upper surface of partition wall of the present invention has good refuses ink, when therefore utilizing IJ method to carry out pattern printing, can be coated with ink equably in the region surrounded by partition wall.In addition, can suppress to cross partition wall inject in undesirably region ink, can with desired pattern printing ink well.
As shown in Figure 2 A, after formation cured film 24, (Fig. 1 E) drips ink 51 by ink gun 40, and the pattern openings portion 24B to cured film 24 injects ink 51.Then, carry out drying and/or heating etc. and remove solvent, as shown in Figure 2 B, the pattern film 52 of expectation can be obtained.
[optical element]
Optical element of the present invention possesses the partition wall of multiple point and the invention described above.
As optical element, the colour filter, organic tft array element etc. of organic EL, liquid crystal cell can be listed.
Organic tft array element refers to following element: multiple point is configured to overlook rectangular, is provided with pixel electrode and the TFT as the switching element for driving it in each point, uses organic semiconductor layer as the semiconductor layer of channel layer comprising TFT.
Organic tft array element is equipped with as tft array substrate in organic EL or liquid crystal cell etc.
Organic EL such as can operate to manufacture as follows.
By optically transparent electrodes such as film forming tin-doped indium oxide (ITO) such as sputtering methods on the light-transmitting substrates such as glass.This optically transparent electrode carries out patterning as required.
Then, use negative light-sensitive resin combination of the present invention, by comprising coating, partition wall is formed as overlooking reticulation along the profile of each point by the photolithography of exposure and development.
Then, known method is utilized to implement ink-receptiveization process to the point surrounded by partition wall as required.
Then, in point, utilize IJ method to be coated with the material also drying of hole injection layer, hole transmission layer, luminescent layer, hole blocking layer and electron injecting layer respectively, stack gradually these layers.Kind and the quantity of the organic layer formed in point can suitably design.
Finally, vapour deposition method etc. is utilized to form the reflecting electrodes such as aluminium.
Embodiment
Based on embodiment, the present invention will be described, and the present invention is not by their limited explanation.Example 1 ~ 10, example 14 and example 15 is embodiment, and example 11 ~ 13 is comparative example.
Each mensuration utilizes following methods to carry out.
[number-average molecular weight (Mn) and matter average molecular weight (Mw)]
Utilize gel permeation chromatography, using polystyrene as reference material, measure number-average molecular weight (Mn) and matter average molecular weight (Mw).As gel permeation chromatograph, use HPLC-8220GPC (TOSOH Co., Ltd's system).As post, use the post be formed by connecting by 3 shodex LF-604.As detector, use RI (Refractive Index, specific refractory power) detector.As reference material, use EasiCal PS1 (Polymer Laboratories Inc.).And then, when measuring number-average molecular weight and matter average molecular weight, post being kept with 37 DEG C, as elutriant, using tetrahydrofuran (THF), flow velocity is set to 0.2mL/ minute, injecting 0.5 quality % tetrahydrofuran solution 40 μ L of working sample.
[fluorine atom containing ratio]
The containing ratio (quality %) of the fluorine atom in the first compound and the second compound, using Isosorbide-5-Nitrae-dual-trifluoromethyl benzene as reference material, utilizes 19f NMR measures and calculates.In addition, the fluorine atom containing ratio refusing ink composition (C) is calculated by the first compound and the content of the second compound and the fluorine atom containing ratio of the first compound and the second compound.
[content of olefinic double bond (C=C)]
The content of the olefinic double bond (C=C) in the first compound and the second compound is calculated by the compounding ratio of raw material with carrying out theoretical property.
[acid number]
Acid number in second compound is calculated by the compounding ratio of raw material with carrying out theoretical property.
The abbreviation of the compound used in each example is below shown.
(raw material of the first compound)
Be equivalent to the compound (cx-11) of compound (cx-1): CF 3(CF 2) 5cH 2cH 2si (OC H 3) 3(Asahi Glass Co., Ltd's system), compound (cx-12): CF 3(CF 2) 5cH 2cH 2si (C H 3) (OCH 3) 2,
Be equivalent to the compound (cx-21) of compound (cx-2): Si (OC 2h 5) 4(COLCOAT CO., Ltd system), compound (cx-22): Si (OC 2h 5) 4partial hydrolysis condensate (COLC OAT CO., Ltd system, trade(brand)name: Ethyl Silicate 48),
Be equivalent to the compound (cx-31) of compound (cx-3): CH 2=CHCOO (CH 2) 3si (O CH 3) 3(Tokyo HuaCheng Industry Co., Ltd's system),
Be equivalent to the compound (cx-41) of compound (cx-4): (CH 3) 3siOCH 3(Tokyo HuaCheng Industry Co., Ltd's system),
Be equivalent to the compound (cx-51) of compound (cx-5): SH (CH 2) 3si (OCH 3) 3(Shin-Etsu Chemial Co., Ltd's system, trade(brand)name: KBM-803),
Other hydrolysable silanes compound (cx-61): CH 3o (C 2h 4o) ksi (OCH 3) 3(containing the Trimethoxy silane of polyoxyethylene, in formula, k is about 10.)。
DBTDL: dibutyl tin laurate
(raw material of the second compound)
C6FMA：CH 2＝C(CH 3)COOCH 2CH 2(CF 2) 6F。
MAA: methacrylic acid.
2-HEMA: 2-hydroxyethyl methacrylate.
PME-400:CH 2=C (CH 3) COO (CH 2cH 2o) kcH 3(Alpha-Methyl-ω-methacryloxy gathers (oxygen ethene), and the k in formula represents intermolecular mean value, and k is about 9.NOF Corp's system, trade(brand)name: BLEMMER PME-400).
IBMA: isobornyl methacrylate.
V-65:2,2 '-azo two (2,4-methyl pentane nitrile) (with Guang Chun medicine Co., Ltd. system).
N-DM: n-dodecyl mercaptan.
BEI:1,1-(two acryloyloxymethyl) ethyl isocyanate (Showa Denko K. K's system, trade(brand)name: Karenz BEI).
AOI:2-acryloyloxyethyl isocyanate (Showa Denko K. K's system, trade(brand)name: Karenz AOI).
DBTDL: dibutyl tin laurate.
TBQ: tertiary butyl para benzoquinone.
MEK:2-butanone.
(alkali soluble resin (AP))
A-11: cresol novolak type epoxy resin and vinylformic acid are reacted, then reacts to import acryl and carboxyl with 1,2,3,6-Tetra Hydro Phthalic Anhydride, thereafter, the resin of purifying with hexane, solids component 70 quality %, acid number 60mgKOH/g.
A-12: the resin (Nippon Kayaku K. K's system, trade(brand)name: KAYARAD ZAR-2002H, solids component 70 quality %, acid number 60mgKOH/g) importing carboxyl and olefinic double bond in bisphenol A type epoxy resin.
A-13: having shown in upper quadrant (A-2a) imports olefinic double bond and acidic-group resin (Nippon Kayaku K. K's system, trade(brand)name: ZCR-1642H, matter average molecular weight (Mw): 5800, acid number: 100mgKOH/g, solids component: 70 quality %) in the epoxy resin of biphenyl backbone.
A-14: the resin (solids component: 70 quality %, PGMEA:30 quality % importing olefinic double bond and acidic-group in the epoxy resin of biphenyl backbone to having shown in formula (A-2b).Acid number 70mgKOH/g.)。
(Photoepolymerizationinitiater initiater (B))
IR907:2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinopropane-1-ketone (BASF AG's system, trade(brand)name: IRGACURE907).
OXE02:1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime) (BASF AG's system, trade(brand)name: OXE02 ETHANON).
OXE01:{1-[4-(thiophenyl)-2-(O-benzoyl oxime)] } 1,2-acetyl caproyl (BASF AG's system, trade(brand)name: OXE01).
(sensitizing agent)
EAB:4,4 '-bis-(diethylin) benzophenone (Tokyo HuaCheng Industry Co., Ltd's system).
NR1: three (2-mercaptopropionyl oxygen base ethyl) isocyanuric acid ester (Showa Denko K. K's system, trade(brand)name: Karenz MT NR1).
PE1: tetramethylolmethane four (3-mercaptobutylate) (Showa Denko K. K's system, trade(brand)name: Karenz MT PE1).
BTT:2-mercaptobenzothiazole
(solvent (D))
PGMEA: propylene glycol methyl ether acetate.
PGME: propylene glycol monomethyl ether.
EDM: diethylene glycol ethylmethyl ether.
EDGAC: diethylene glycol monoethyl ether acetic ester.
(linking agent (E))
A9550W: the melange (chemical industry Co., Ltd. of Xin Zhong village system, trade(brand)name: NK ESTER A-9550W) of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate.
UX5002D: polyfunctional carbamate origoester acrylate (Nippon Kayaku K. K's system, trade(brand)name: KAYARAD UX-5002D-P20).
ADPH: dipentaerythritol acrylate (chemical industry Co., Ltd. of Xin Zhong village system, trade(brand)name: NK ESTER A-DPH).
Two [4-(2-acryloyloxyethoxy) phenyl] fluorenes (chemical industry Co., Ltd. of Xin Zhong village system, trade(brand)name: NK ESTER A-BPEF) of ABPEF:9,9-.
(tinting material (F))
Mixing pigment dyestuff: C.I. pigment Blue 15: 6, the mixture (solids component: 25 quality %, PGMEA:75 quality % of the 10:5:5:5 of C.I. Pigment red 254, C.I. pigment yellow 13 9 and macromolecule dispersing agent.)。
(other)
BHT: stopper (2,6 ditertiary butyl p cresol).
XD1000: polyfunctional epoxy resin (Nippon Kayaku K. K's system, trade(brand)name: XD1000).
[synthesis example 1: the synthesis of compound (CX-1)]
Possessing the 1000cm of stirrer 3there-necked flask in drop into compound (cx-11) 14.5g, compound (cx-21) 32.9g, compound (cx-31) 21.9g, compound (cx-41) 21.9g and compound (cx-51) 8.8g, obtain hydrolysable silanes compound.Then, in this mixture, drop into PGMEA 320.2g, make material solution.
1 quality % aqueous nitric acid 98.7g is dripped in gained material solution.After dropping terminates, stir 5 hours with 40 DEG C, obtain the solution (compound concentration: 10 quality %, hereinafter also referred to (CX-1) solution of compound (CX-1).)。
It should be noted that, after reaction terminates, use gas chromatograph to measure reaction solution, confirm each compound as raw material below detection limit.
Raw material composition and evaluation result (content of number-average molecular weight (Mn), matter average molecular weight (Mw), fluorine atom containing ratio and olefinic double bond) are shown in table 1.
[synthesis example 2 ~ 6: compound (CX-2) ~ (CX-6)]
Except by raw material composition be set to table 1 shownschematically except, to operate equally with synthesis example 1, the solution obtaining compound (CX-2) ~ (CX-6) (is compound concentration: 10 quality %, also each solution is called (CX-2) ~ (CX-6) liquid below.)。
Evaluation result (content of number-average molecular weight (Mn), matter average molecular weight (Mw), fluorine atom containing ratio and olefinic double bond) is shown in table 1.
[table 1]
[synthesis example 7: the synthesis of compound (CY-1)]
Possessing the internal volume 1000cm of stirrer 3autoclave in drop into MEK 420.0g, C6FMA 81.0g, MAA 18.0g, 2-HEMA 81.0g, polymerization starter V-65 5.0g and n-DM 4.7g, limit is stirred in a nitrogen atmosphere, while with 50 DEG C polymerization 24 hours.And then, make polymerization starter inactivation with 70 DEG C of heating 5 hours, obtain the solution of copolymer 1.The number-average molecular weight (Mn) of copolymer 1 is 5540, matter average molecular weight (Mw) is 13200.
Then, to the internal volume 300cm possessing stirrer 3autoclave in drop into solution 130.0g, BEI 30.5g, DBTDL 0.12g and TBQ 1.5g of above-mentioned copolymer 1, while stirring with 40 DEG C of reactions 24 hours, synthesis crude polymer.Add after hexane carries out redeposition purifying in the solution of gained crude polymer, carry out vacuum-drying, obtain 65.6g compound (CY-1).
The evaluation result (content of number-average molecular weight (Mn), matter average molecular weight (Mw), fluorine atom containing ratio, olefinic double bond and acid number) of raw material composition, output and gained compound is shown in table 2.
[synthesis example 8: the synthesis of compound (CY-2)]
Except using except the solution of above-mentioned copolymer 1, AOI, DBTDL and TBQ with composition table 2 Suo Shi, to operate equally with synthesis example 7, obtaining compound (CY-2).
[synthesis example 9: the synthesis of compound (CY-3)]
Possessing the internal volume 1000cm of stirrer 3autoclave in drop into MEK, C6FMA, MAA, 2-HEMA, PME-400 and polymerization starter V-65 with the composition shown in table 2, limit is stirred in a nitrogen atmosphere, while with 50 DEG C of polymerizations 24 hours.And then, with 70 DEG C of heating 5 hours, make polymerization starter inactivation, obtain the solution of compound (CY-3).Remove solvent with Rotary Evaporators with the temperature of 50 DEG C distillation, thereafter, carry out vacuum-drying, obtain compound (CY-3).
[synthesis example 10 ~ 11: the synthesis of compound (CY-4) ~ (CY-5)]
Except raw material composition is set to table 2 shownschematically except, to operate equally with synthesis example 9, obtain compound (CY-4) ~ (CY-4).
[synthesis example 12: compound (CY-6)]
As compound (CY-6), prepare the trade(brand)name that Liao great Japanese ink Co., Ltd. manufactures: Megafac RS10 2.
This compound is the polymkeric substance with following repeating unit.It should be noted that, m2/m1=3 ~ 4.
[synthesis example 13: the synthesis of compound (CY-7)]
Except using except MEK, C6FMA, MAA, 2-HEMA and polymerization starter V-65 with the raw material composition shown in table 2, the method identical with the copolymer 1 of synthesis example 7 is utilized to obtain the solution of multipolymer 2.The number-average molecular weight (Mn) of multipolymer 2 is 32400, matter average molecular weight (Mw) is 69320.
Except with except the solution of the above-mentioned multipolymer 2 of raw material composition use shown in table 2, AOI, DBTDL and TBQ, the method same with example 5 is utilized to obtain compound (CY-7).
The raw material of compound (CY-2) ~ compound (CY-7) composition, output and evaluation result (content of number-average molecular weight (Mn), matter average molecular weight (Mw), fluorine atom containing ratio, olefinic double bond and acid number) are shown in table 2.
[table 2]
[example 1: the manufacture of negative light-sensitive resin combination and partition wall]
(manufacture of negative light-sensitive resin combination)
Compound (CY-1) 0.015g, A-11 16.07g obtained in the compound obtained in synthesis example 1 (CX-1) 1.5g (containing the compound (CX-1) of 0.15g with solid component meter, remaining as solvent PGMEA), synthesis example 7 (solids component be 11.25g, remaining as solvent PGMEA), IR907 1.21g, EAB 1.125g, A9550W 11.25g, PGMEA 55.0g and EDM 20.0g are fed into 200cm 3stirring container in, stir and manufacture negative light-sensitive resin combination in 5 hours.Raw material composition is shown in table 3.
In table, solids component total amount refers to and desolventizes the amount (quality %) of all solids composition outside (D) relative to negative light-sensitive resin combination total amount.
Solids component composition represents by the amount (quality %) of each solid material relative to all solids component amount.
Solvent (D) composition represents by the amount (quality %) of each solvent (D) relative to total composition.
The quality of quality/the first compound of the second compound is also shown in table 3 in the lump.
(manufacture of partition wall)
Glass substrate EtOH Sonicate ripple square for 10cm is cleaned 30 seconds, then, carries out the UV/O of 5 minutes 3process.UV/O 3process uses PL2001N-58 (SenEngineering Co., Ltd. system) as UV/O 3generating unit.The luminous power that 254nm converts is 10mW/cm 2.It should be noted that, following all UV/O 3this device is all used in process.
Use on the glass baseplate surface of spinner after above-mentioned cleaning and be coated with above-mentioned negative light-sensitive resin combination, then with 100 DEG C on hot plate dry 2 minutes, form the desciccator diaphragm of thickness 2.4 μm.
Across having the photomask of patterns of openings (2.5cm × 5cm), the mode exposed in the lump with whole face is with 100mJ/cm 2exposure to gained desciccator diaphragm irradiate 365nm convert exposure power be 25mW/cm 2the UV light of ultrahigh pressure mercury lamp.During exposure, clip the light of below 330nm.In addition, the spacing distance between desciccator diaphragm and photomask is set to 50 μm.
Then, the glass substrate after above-mentioned exposure-processed is flooded in 2.38 quality % tetramethylammonium hydroxide aqueous solutions and within 40 seconds, develops, rinse non-exposed portion with water and make it dry.Then, it is heated 60 minutes with 230 DEG C on hot plate, thus obtains the partition wall (cured film) with the pattern corresponding to the patterns of openings of photomask.
For gained partition wall, implement following evaluation.Evaluation result is shown in table 3.
The consistency > of < negative light-sensitive resin combination
Use the negative light-sensitive resin combination after just manufacturing, under the formation condition of above-mentioned desciccator diaphragm, obtain desciccator diaphragm.Detect by an unaided eye gained desciccator diaphragm, evaluates according to following benchmark.
Zero (well): film is clear, colorless.△ (can): film generation white opacity, but can't see foreign matter.× (bad): film generation white opacity, visible foreign matters in film.
The storage stability > of < negative light-sensitive resin combination
Use saves the negative light-sensitive resin combination of 30 days with 60 DEG C, under the formation condition of above-mentioned desciccator diaphragm, obtain desciccator diaphragm.Detect by an unaided eye gained desciccator diaphragm, evaluates according to following benchmark.
If there is large foreign matter in negative light-sensitive resin combination, then during spin coating, foreign matter is drawn to periphery, and gained film produces radial striped.
Zero (well): foreign and radial-like streak.△ (can): visible foreign matters but without radial-like streak.× (bad): there is radial-like streak.
The thickness > of < cured film
Laser microscope (Keyemce Inc., device name: VK-8500) is used to measure.
< partition wall upper surface refuse ink and resistance to UV/O thereof 3property >
Following method is utilized to measure the PGMEA contact angle of gained cured film upper surface.
Utilize sessile drop method, according to JIS R3257 " base plate glass wettability of the surface test method ", at 3 place mounting PGMEA drops of cured film upper surface, measure for each PGMEA drop.Drop is that 2 μ L/ drip, and carries out at being determined at 20 DEG C.Contact angle is obtained by the mean value of 3 measured values.It should be noted that, PGMEA is the abbreviation of propylene glycol methyl ether acetate.
(light quantity counts 1800mJ/cm with 254nm conversion to carry out 3 minutes to the whole surface of the glass substrate being formed with cured film 2) UV/O 3after radiation treatment, aforesaid method is again utilized to measure the PGMEA contact angle of cured film upper surface.
The SEM of < partition wall upper surface observes >
The SEM carrying out gained partition wall upper surface observes (5000 times, Keyemce Inc., device name: 3D real surface viewing microscope VE-9800), the end observing partition wall upper surface, with or without protuberance, is evaluated according to following benchmark.
Zero (well): the end of partition wall upper surface does not observe protuberance.
△ (can): protuberance is observed in the end of partition wall upper surface.
[example 2 ~ 15]
Except negative light-sensitive resin combination being changed to composition shown in table 3 in example 1, profit uses the same method and manufactures negative light-sensitive resin combination and partition wall and evaluate.Evaluation result is shown in table 3.
[table 3]
In table 3, " % " is " quality % ".
(summary of result)
Combinationally use the first compound and the second compound, namely use refuse ink composition (C) example 1 ~ 10, example 14 and example 15 in, partition wall upper surface has excellent refuses ink, even if it refuses ink at UV/O 3also be able to well maintained after process.
At UV/O 3in evaluation before radiation treatment, the partition wall upper surface of example 1 ~ 10, example 14 and example 15 to refuse the partition wall upper surface that Mo Xingyu only used the example 13 of second compound of matter average molecular weight (Mw) more than 100,000 be equal.
At UV/O 3in evaluation before radiation treatment, the partition wall upper surface of example 1 ~ 10, example 14 and example 15 refuse ink higher than only used the example 11 of the first compound and only used the example 12 that matter average molecular weight (Mw) is second compound of less than 50,000.
The storage stability combinationally using the negative light-sensitive resin combination of the example 1 ~ 10 of the first compound and the second compound is also good.Improve as seen relative to the example 11 that only used the first compound.
Protuberance is not observed in the end combinationally using the partition wall upper surface of the example 1 ~ 10 of the first compound and the second compound, can form the partition wall of neat shape.Improve as seen relative to the example 11 that only used the first compound.
The negative light-sensitive resin combination of the example 12 and example 13 that only used the second compound is at UV/O 3the ink of refusing of the partition wall upper surface after process significantly reduces.
utilizability in industry
Ink composition of refusing of the present invention can be suitably used as photosensitive polymer combination that partition wall when utilizing ink jet method to carry out pattern printing formed or wherein containedly refuse black agent etc. in the optical elements such as the colour filter of organic EL, liquid crystal cell and organic tft array.
In addition, can be used as the partition wall (projection) for utilizing IJ method pattern to print the organic layer such as luminescent layer in organic EL by the partition wall formed containing the photosensitive polymer combination refusing ink composition of the present invention, or can be used as in liquid crystal cell that (this partition wall can double as black matrix" (BM) for utilizing the partition wall of IJ method pattern printing colour filter.), and then to can be used as in organic tft array for utilizing the partition wall of IJ method pattern printed conductor pattern or semiconductor pattern, can be used as the partition wall for utilizing the printing of IJ method pattern to become the organic semiconductor layer of the channel layer of TFT, gate electrode, source electrode, drain electrode, grating routing and source wiring etc. in addition.
It should be noted that, quote so far by the full content of the specification sheets of No. 2012-209084, the Japanese patent application of application on September 24th, 2012, claims, accompanying drawing and summary, as the open of specification sheets of the present invention, group enters.
description of reference numerals
10: base material, 21: film, 22: desciccator diaphragm, 23: exposed film, 23A: exposure portion, 23B: non-exposed portion, 24: cured film, 24A: protuberance, 24B: pattern openings portion, 30: photomask, 40: ink gun, 51: ink, 52: pattern film, L: light.

Claims (17)

1. refuse ink composition for one kind, it is characterized in that, it comprises the first compound and the second compound, described first compound is the partial hydrolysis condensate of the mixture comprising the first hydrolysable silanes compound with fluorine alkylidene group and/or fluoroalkyl and hydrolization group, and the main chain of described second compound is hydrocarbon chain and comprises side chain, the matter average molecular weight (Mw) with fluorine atom is 100 ~ 1,000,000.
2. according to claim 1ly refuse ink composition, wherein, described first hydrolysable silanes compound is the compound shown in following formula (cx-1),
(A-R F11) a-Si(R H11) bX 11 (4-a-b)···(cx-1)
R f11for comprise at least 1 fluorine alkylidene group, the divalent organic group of carbonatoms 1 ~ 16 or comprise the divalent organic group of carbonatoms 2 ~ 16 of etheric oxygen atom, R h11for the alkyl of carbonatoms 1 ~ 6,
X 11for hydrolization group, X 11when existing multiple, they each other can difference also can be identical;
A is 1 or 2, b is 0 or 1, a+b is 1 or 2,
A is the group shown in fluorine atom or following formula (I),
-Si(R H12) cX 12 (3-c)···(I)
R h12for the alkyl of carbonatoms 1 ~ 6,
C is 0 or 1,
X 12for hydrolization group, X 12when existing multiple, they each other can difference also can be identical,
A-R f11when existing multiple, they each other can difference also can be identical.
3. according to claim 2ly refuse ink composition, wherein, described mixture also comprises the second hydrolysable silanes compound shown in following formula (cx-2),
SiX 2 4···(cx-2)
X 2represent hydrolization group, 4 X 2each other can difference also can be identical.
4. according to any one of claims 1 to 3, refuse ink composition, wherein, described mixture also comprises the 3rd hydrolysable silanes compound shown in following formula (cx-3),
(Y-Q 3) g-Si(R H3) hX 3 (4-g-h)···(cx-3)
Y is the group with olefinic double bond,
Q 3for the divalent organic group of the not contain fluorine atoms of carbonatoms 1 ~ 6,
R h3for the alkyl of carbonatoms 1 ~ 6,
X 3for hydrolization group, X 3when existing multiple, they each other can difference also can be identical,
G is 1 or 2, h is 0 or 1, g+h is 1 or 2,
Y-Q 3when existing multiple, they each other can difference also can be identical.
5. according to any one of Claims 1 to 4, refuse ink composition, wherein, described second compound is polymkeric substance, and described polymkeric substance comprises optional fluoroalkyl containing etheric oxygen atom and/or has the side chain of the optional fluoroalkyl containing etheric oxygen atom.
6. according to claim 5ly refuse ink composition, wherein, described second compound is the polymkeric substance comprising the side chain with acidic-group.
7. according to claim 5 or 6, refuse ink composition, wherein, described second compound is the polymkeric substance comprising the side chain with olefinic double bond.
8. according to any one of claim 5 ~ 7, refuse ink composition, wherein, described second compound is the polymkeric substance comprising the side chain with oxyalkylene.
9. according to any one of claim 1 ~ 8, refuse ink composition, wherein, described second Compound Phase is 0.01 ~ 10 for the mass ratio of described first compound.
10. according to any one of claim 1 ~ 9, refuse ink composition, wherein, the containing ratio of fluorine atom is 5 ~ 40 quality %.
11. 1 kinds of negative light-sensitive resin combinations, it is characterized in that, it comprises alkali soluble resin or base soluble monomer (A), Photoepolymerizationinitiater initiater (B) and the solvent (D) refusing ink composition and have light solidified according to any one of claim 1 ~ 10.
12. negative light-sensitive resin combinations according to claim 11, it is also included in 1 molecule has more than 2 olefinic double bonds and the linking agent (E) without acidic-group.
13. negative light-sensitive resin combinations according to claim 11 or 12, wherein, the first compound in all solids composition be 0.05 ~ 10 quality % containing ratio, the second compound be 0.01 ~ 5 quality % containing ratio.
14. negative light-sensitive resin combinations according to any one of claim 11 ~ 13, wherein, what refuse ink composition described in all solids composition is 0.06 ~ 15 quality % containing ratio.
15. 1 kinds of cured film, is characterized in that, its be the negative light-sensitive resin combination according to any one of claim 11 ~ 14 is coated substrate surface, remove solvent (D) and exposure.
16. 1 kinds of partition walls, is characterized in that, it comprises cured film according to claim 15.
17. 1 kinds of optical elements, is characterized in that, it possesses multiple point and partition wall according to claim 16.
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