CN105372938A - Photosensitive resin composition and carbon black - Google Patents

Photosensitive resin composition and carbon black Download PDF

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Publication number
CN105372938A
CN105372938A CN201510505614.XA CN201510505614A CN105372938A CN 105372938 A CN105372938 A CN 105372938A CN 201510505614 A CN201510505614 A CN 201510505614A CN 105372938 A CN105372938 A CN 105372938A
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group
carbon black
substituent
methyl
carbon number
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CN105372938B (en
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石川达郎
山口尚人
黑子麻祐美
盐田大
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Tokyo Ohka Kogyo Co Ltd
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Tokyo Ohka Kogyo Co Ltd
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  • Materials For Photolithography (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

The invention provides a photosensitive resin composition. The photosensitive resin composition can be well adhered on a substrate, the hermetical property and insulation property of the photosensitive resin composition are excellent, and the insulation property does not degrade when the photosensitive resin composition is heated. The invention also provides a method using the photosensitive resin composition to form a patterned solid substance, a patterned solid substance prepared from the photosensitive resin composition, a display device comprising black matrix or black column shaped partition member, and carbon block used in the photosensitive resin composition. The photosensitive resin composition comprises (A) alkali-soluble resin, (B) light polymerization monomer, (C) photopolymerization initiator, and (D) light screening agent, which is composed of carbon black, which is processed by silane coupling agent having a specific structure.

Description

Photosensitive polymer combination and carbon black
Technical field
The present invention relates to and comprise (A) alkali soluble resin, (B) photopolymerization monomer, (C) photosensitive polymer combination of Photoepolymerizationinitiater initiater and (D) opacifier, use the formation method of the solidfied material of the patterning of this photosensitive polymer combination, the solidfied material of the patterning using this photosensitive polymer combination to be formed, possesses the display device of black matrix (Block ラ ッ Network マ ト リ Network ス) or the black column spacer (Block ラ ッ Network カ ラ system ス ペ ー サ) using this photosensitive polymer combination to be formed, with be adapted at the carbon black being used as (D) opacifier component in this photosensitive polymer combination.
Background technology
When forming the panel of the display device as liquid crystal indicator, the substrate of panel forms the various patterns with various function.As an example of such pattern, the pattern of the shading between can enumerating for pixel and the black matrix that arranges, the pattern etc. of black column spacer formed to make the interval between two plate bases (cel-gap) keep constant.
As the method for the pattern of this black matrix of formation, black column spacer, from the pattern easily forming dimensional accuracy, positional precision excellence, propose to use and comprise carbon black lithographically forms pattern method (with reference to patent documentation 1 and 2) as the photosensitive polymer combination of opacifier.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2000-199967 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2011-170075 publication
Summary of the invention
Invent problem to be solved
But, in the method recorded in patent documentation 1 and 2, there are the following problems: because of the kind of carbon black, not easily formed and easily reduce because of heating the fine pattern of the excellent adhesion of substrate or the pattern not easily forming insulativity excellence or the insulativity of pattern that formed.
The present invention completes in view of above-mentioned problem, its object is to provide can be formed the black pattern that the adaptation of substrate and the excellent and insulativity of insulativity not easily reduce because of heating photosensitive polymer combination, use the formation method of the solidfied material of the patterning of this photosensitive polymer combination, the solidfied material of the patterning that uses this photosensitive polymer combination to be formed, possess the carbon black using the black matrix of this photosensitive polymer combination formation or the display device of black column spacer and be engaged in this photosensitive polymer combination.
For solving the method for problem
The present inventor finds by coordinating the opacifier comprising the carbon black after utilizing the silane coupling agent of ad hoc structure to process can solve the problem as (D) opacifier in the photosensitive polymer combination comprising (A) alkali soluble resin, (B) photopolymerization monomer, (C) Photoepolymerizationinitiater initiater and (D) opacifier, thus completes the present invention.
The 1st aspect of the present invention is a kind of photosensitive polymer combination, it comprises (A) alkali soluble resin, (B) photopolymerization monomer, (C) Photoepolymerizationinitiater initiater and (D) opacifier,
(D) opacifier is for comprising the photosensitive polymer combination of the carbon black after utilizing the silane coupling agent represented by following formula (1) to process.
R 1 pR 2 (3-p)Si-R 3-NH-C(O)-Y-R 4-X…(1)
(in formula (1), R 1for alkoxy, R 2for alkyl, p is the integer of 1 ~ 3, R 3for alkylidene, Y is-NH-,-O-or-S-, R 4for singly-bound or alkylidene, X is the nitrogen-containing hetero aryl can with substituent, monocycle or many rings, in X with-Y-R 4the ring of-bonding is nitrogenous hexa-atomic aromatic rings ,-Y-R 4-with the carbon atom bonding in above-mentioned nitrogenous hexa-atomic aromatic rings.)
The 2nd aspect of the present invention is the formation method of the solidfied material of patterning, and it comprises:
Photosensitive polymer combination involved by first method is coated on operation substrate being formed coated film;
Operation coated film exposed regioselectivity; With
By the operation of the coated film development after exposure.
The 3rd aspect of the present invention is the solidfied material of patterning, and it uses the photosensitive polymer combination involved by first method to be formed.
The 4th aspect of the present invention is display device, and it possesses and uses photosensitive polymer combination involved by first method and the black matrix that formed or black column spacer.
The 5th aspect of the present invention is carbon black, and it is the carbon black after utilizing the silane coupling agent represented by following formula (1) to process.
R 1 pR 2 (3-p)Si-R 3-NH-C(O)-Y-R 4-X…(1)
(in formula (1), R 1for alkoxy, R 2for alkyl, p is the integer of 1 ~ 3, R 3for alkylidene, Y is-NH-,-O-or-S-, R 4for singly-bound or alkylidene, X is the nitrogen-containing hetero aryl can with substituent, monocycle or many rings, in X with-Y-R 4the ring of-bonding is nitrogenous hexa-atomic aromatic rings ,-Y-R 4-with the carbon atom bonding in above-mentioned nitrogenous hexa-atomic aromatic rings.)
Invention effect
According to the present invention, can provide can be formed the black pattern that the adaptation of substrate and the excellent and insulativity of insulativity not easily reduce because of heating photosensitive polymer combination, use the formation method of the solidfied material of the patterning of this photosensitive polymer combination, the solidfied material of the patterning that uses this photosensitive polymer combination to be formed, possess the carbon black using the black matrix of this photosensitive polymer combination formation or the display device of black column spacer and be engaged in this photosensitive polymer combination.
Embodiment
" photosensitive polymer combination "
Photosensitive polymer combination comprises (A) alkali soluble resin, (B) photopolymerization monomer, (C) Photoepolymerizationinitiater initiater and (D) opacifier.(D) opacifier comprises the carbon black after utilizing the silane coupling agent of regulation structure described later to process.Below, to photosensitive polymer combination comprise must or arbitrary composition be described.
< (A) alkali soluble resin >
Alkali soluble resin refers to, utilize the resin solution of resin concentration 20 quality % (solvent: propylene glycol methyl ether acetate) formed on substrate thickness 1 μm resin molding, when it being flooded in the KOH aqueous solution of concentration 0.05 quality % 1 minute again, thickness dissolves the resin of more than 0.01 μm.
(A) as long as the resin that alkali soluble resin demonstrates above-mentioned alkali-soluble is just not particularly limited, can from known resin suitable choice for use.As the resin being suitable as (A) alkali soluble resin, the resin with (A1) Cardo structure (カ Le De Agencies makes) can be enumerated.
There is as (A1) resin of Cardo structure, be not particularly limited, known resin can be used.Wherein, the resin represented by preferred following formula (a-1).
[changing 1]
In above-mentioned formula (a-1), X arepresent the group represented by following formula (a-2).
[changing 2]
In above-mentioned formula (a-2), R a1represent alkyl or the halogen atom of hydrogen atom, carbon number 1 ~ 6 independently of one another, R a2represent hydrogen atom or methyl independently of one another, W arepresent singly-bound or the group represented by following formula (a-3).
[changing 3]
In addition, in above-mentioned formula (a-1), Y arepresent the residue remove anhydride group (-CO-O-CO-) from dicarboxylic anhydride after.As the example of dicarboxylic anhydride, can enumerate: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic (エ Application De メ チ レ Application) tetrabydrophthalic anhydride, chlorendic anhydride, methyl tetrahydrophthalic anhydride, glutaric anhydride etc.
In addition, in above-mentioned formula (a-1), Z arepresent the residue after removing 2 anhydride group from tetracarboxylic dianhydride.As the example of tetracarboxylic dianhydride, can enumerate: pyromellitic acid anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, Biphenyl Ether tetracarboxylic dianhydride etc.
In addition, in above-mentioned formula (a-1), m represents the integer of 0 ~ 20.
(A1) there is the matter average molecular weight (Mw: the measured value based on polystyrene conversion of gel permeation chromatography (GPC) of the resin of Cardo structure.Identical in this manual.) be preferably 1000 ~ 40000, be more preferably 2000 ~ 30000.By being set as above-mentioned scope, good developability can be obtained, and sufficient thermotolerance, film strength can be obtained.
In addition, from the view point of easily forming breakdown strength, solidfied material to the excellent adhesion of substrate, (A2) is at least polymerized has the multipolymer of (a1) unsaturated carboxylic acid also can be suitable as (A) alkali soluble resin.
As (a1) unsaturated carboxylic acid, can enumerate: monocarboxylic acid such as (methyl) acrylic acid, crotonic acid etc.; The dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid; The acid anhydrides of these dicarboxylic acids; Deng.Wherein, from copolyreaction, the viewpoint such as alkali-solubility, the easiness of starting with of resin that obtains, preferably (methyl) acrylic acid and maleic anhydride.These (a1) unsaturated carboxylic acids may be used singly or in combin two or more.
(A2) multipolymer can be the multipolymer of (a1) unsaturated carboxylic acid and (a2) unsaturated compound containing ester ring type epoxy radicals.As (a2) unsaturated compound containing ester ring type epoxy radicals, as long as the unsaturated compound with ester ring type epoxy radicals is just not particularly limited.The ester ring type group of formation ester ring type epoxy radicals can be monocycle also can be many rings.As the ester ring type group of monocycle, can enumerate: cyclopentyl, cyclohexyl etc.In addition, as the ester ring type group of many rings, can enumerate: norborny, isobornyl, three ring nonyls, three ring decyls, tetracyclododecyl group etc.These (a2) unsaturated compounds containing ester ring type epoxy radicals may be used singly or in combin two or more.
Specifically, as (a2) unsaturated compound containing ester ring type epoxy radicals, such as, can enumerate the compound represented by following formula (a2-1) ~ (a2-16).Wherein, in order to realize the developability of appropriateness, the compound represented by preferred following formula (a2-1) ~ (a2-6), the compound more preferably represented by following formula (a2-1) ~ (a2-4).
[changing 4]
[changing 5]
[changing 6]
In above-mentioned formula, R 11represent hydrogen atom or methyl, R 12represent the bivalent aliphatic saturated hydrocarbyl of carbon number 1 ~ 6, R 13represent the bivalent hydrocanbon radical of carbon number 1 ~ 10, n represents the integer of 0 ~ 10.As R 12, the alkylidene of preferred straight-chain or branched, such as methylene, ethylidene, propylidene, tetramethylene, ethylethylene residue, pentamethylene, hexa-methylene.As R 13, such as preferred methylene, ethylidene, propylidene, tetramethylene, ethylethylene residue, pentamethylene, hexa-methylene, phenylene, cyclohexylidene ,-CH 2-Ph-CH 2-(Ph represents phenylene).
(A2), in multipolymer, (a3) unsaturated compound containing ester ring type group without epoxy radicals can also be had with the copolymerization together with (a2) above-mentioned unsaturated compound containing ester ring type epoxy radicals of above-mentioned (a1) unsaturated carboxylic acid.
As (a3) unsaturated compound containing ester ring type group, as long as the unsaturated compound with ester ring type group is just not particularly limited.Ester ring type group can be monocycle also can be many rings.As the ester ring type group of monocycle, can enumerate: cyclopentyl, cyclohexyl etc.In addition, as the ester ring type group of many rings, can enumerate: adamantyl, norborny, isobornyl, three ring nonyls, three ring decyls, tetracyclododecyl group etc.These (a3) unsaturated compounds containing ester ring type group may be used singly or in combin two or more.
Specifically, as (a3) unsaturated compound containing ester ring type group, such as, can enumerate the compound represented by following formula (a3-1) ~ (a3-7).Wherein, in order to realize the developability of appropriateness, the compound represented by preferred following formula (a3-3) ~ (a3-8), more preferably following formula (a3-3), compound represented by (a3-4).
[changing 7]
[changing 8]
In above-mentioned formula, R 21represent hydrogen atom or methyl, R 22represent the bivalent aliphatic saturated hydrocarbyl of singly-bound or carbon number 1 ~ 6, R 23represent the alkyl of hydrogen atom or carbon number 1 ~ 5.As R 22, the alkylidene of preferred singly-bound, straight-chain or branched, such as methylene, ethylidene, propylidene, tetramethylene, ethylethylene residue, pentamethylene, hexa-methylene.As R 23, preference is as methyl, ethyl.
In addition, (A2), in multipolymer, copolymerization (a4) unsaturated compound containing epoxy radicals without ester ring type group can also be had together with above-mentioned (a1) unsaturated carboxylic acid and above-mentioned (a2) unsaturated compound containing ester ring type epoxy radicals and above-mentioned (a3) unsaturated compound containing ester ring type group.
As (a4) unsaturated compound containing epoxy radicals, can enumerate: (methyl) glycidyl acrylate, (methyl) acrylic acid 2-methylglycidyl esters, (methyl) acrylic acid 3, (methyl) acrylic acid epoxy alkyl esters such as 4-epoxy butyl ester, (methyl) acrylic acid 6,7-epoxy heptyl ester; The alpha-alkyl acrylic acid epoxy alkyl esters such as α-ethylacrylate ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-n-butyl acryloyloxy ethyl acid glycidyl ester, α-ethylacrylate 6,7-epoxy heptyl ester; Deng.Wherein, from the viewpoint such as intensity of the resin after copolyreaction, solidification, preferably (methyl) glycidyl acrylate, (methyl) acrylic acid 2-methylglycidyl esters and (methyl) acrylic acid 6,7-epoxy heptyl ester.These (a4) unsaturated compounds containing epoxy radicals may be used singly or in combin two or more.
In addition, in (A2) multipolymer, copolymerization can also there be other compounds other than the above further.As other such compounds, can enumerate: (methyl) esters of acrylic acid, (methyl) acrylic amide, allyl compound, vinyl ethers, vinyl ester, phenylethylene etc.These compounds may be used singly or in combin two or more.
As (methyl) esters of acrylic acid, can enumerate: (methyl) alkyl acrylate of the straight-chain such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) amyl acrylate, the tertiary monooctyl ester of (methyl) acrylic acid or branched; (methyl) acrylic acid chloroethene ester, (methyl) acrylic acid 2,2-dimethyl hydroxyl propyl ester, (methyl) acrylic acid 2-hydroxy methacrylate, trimethylolpropane list (methyl) acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid chaff ester; Deng.
As (methyl) acrylic amide, can enumerate: (methyl) acrylamide, N-alkyl (methyl) acrylamide, N-aryl (methyl) acrylamide, N, N-dialkyl group (methyl) acrylamide, N, N-aryl (methyl) acrylamide, N-Methyl-N-phenyl (methyl) acrylamide, N-hydroxyethyl-N-methyl (methyl) acrylamide etc.
As allyl compound, can enumerate: the allyl ester classes such as allyl acetate, allyl hexanoate, allyl octanoate, lauric acid allyl ester, palmitic acid allyl ester, stearic acid allyl ester, allyl benzoate, acetoacetic acid allyl ester, allyl lactate; Allyl ethoxy-ethanol; Deng.
As vinyl ethers, can enumerate: the alkyl vinyl ethers such as hexyl vinyl ether, octyl vinyl ether, decave, ethylhexyl vinyl ether, methoxy-ethylvinyl ether, ethoxy ethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethyl aminoethyl vinyl base ether, diethylamino ethyl vinyl ether, Butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; The ethenyl aromatic yl ethers such as vinyl phenyl ether, vinyltoluene base ether, vinyl chloride phenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthryl ether; Deng.
As vinyl ester, can enumerate: vinyl butyrate, vinyl isobutyrate ester, vinyl pivalate, diethacetic acid vinyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate ester, vinyl methoxyacetate ester, butoxy acetic acid vinyl acetate, vinyl phenylacetate ester, acetoacetate vinyl acetate, lactate, beta-phenyl vinyl butyrate, vinyl benzoate, vinyl salicylate, chlorobenzoic acid vinyl acetate, tetrachloro-benzoic acid vinyl acetate, naphthoic acid vinyl acetate etc.
As phenylethylene, can enumerate: styrene; The ring-alkylated styrenes such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl, isopropyl styrene, butylstyrene, hexyl benzene ethene, cyclohexylstyrenes, decyl styrene, benzylstyrene, 1-chloro-4-methyl-benzene, trifluoromethyl styrene, ethoxyl methyl styrene, acetoxymethylstyrene; The alkoxystyrene such as methoxy styrene, 4-methoxyl-3-methyl styrene, dimethoxy styrene; The halogenated styrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorobenzene ethene, pentachlorobenzene ethene, bromstyrol, Dowspray 9, iodobenzene ethene, fluorobenzene ethene, trifluorostyrene, 2-bromo-4-trifluoromethyl styrene, the fluoro-3-trifluoromethyl styrene of 4-; Deng.
The ratio of Component units shared by (A2) multipolymer deriving from above-mentioned (a1) unsaturated carboxylic acid is preferably 1 ~ 50 quality %, is more preferably 5 ~ 45 quality %.
In addition, (A2) multipolymer contains the Component units deriving from above-mentioned (a2) unsaturated compound containing ester ring type epoxy radicals, with when deriving from the Component units of above-mentioned (a4) unsaturated compound containing epoxy radicals, derive from the ratio that the Component units of (a2) unsaturated compound containing ester ring type epoxy radicals is shared in (A2) multipolymer, the total of the ratio shared in (A2) multipolymer with the Component units deriving from above-mentioned (a4) unsaturated compound containing epoxy radicals, be preferably more than 71 quality %, be more preferably 71 ~ 95 quality %, more preferably 75 ~ 90 quality %.Particularly, the ratio of Component units shared by (A2) multipolymer deriving from above-mentioned (a2) unsaturated compound containing ester ring type epoxy radicals is preferably more than 71 quality % separately, is more preferably 71 ~ 80 quality %.By making the ratio of the Component units deriving from above-mentioned (a2) unsaturated compound containing ester ring type epoxy radicals be above-mentioned scope, the ageing stability of photosensitive polymer combination can be improved.
In addition, (A2) when multipolymer contains the Component units deriving from (a3) unsaturated compound containing ester ring type group, the ratio of Component units shared by (A2) multipolymer deriving from above-mentioned (a3) unsaturated compound containing ester ring type group is preferably 1 ~ 30 quality %, is more preferably 5 ~ 20 quality %.
(A2) the matter average molecular weight of multipolymer is preferably 2000 ~ 200000, is more preferably 3000 ~ 30000.By being set as above-mentioned scope, have be easy to obtain photosensitive polymer combination film Forming ability, developability after exposure the tendency of balance.
In addition, as (A) alkali soluble resin, also the resin comprising (A3) multipolymer or (A4) multipolymer can preferably be used, should at least have the Component units deriving from above-mentioned (a1) unsaturated carboxylic acid by (A3) multipolymer, with the Component units with the position can be polymerized with (B) described later photopolymerization monomer, should at least have the Component units deriving from above-mentioned (a1) unsaturated carboxylic acid by (A4) multipolymer, derive from above-mentioned (a2) unsaturated compound containing ester ring type epoxy radicals and/or the Component units of (a4) unsaturated compound containing epoxy radicals, with the Component units with the position can be polymerized with photopolymerization monomer described later (B).(A), when alkali soluble resin comprises (A3) multipolymer or (A4) multipolymer, photosensitive polymer combination can be improved to the breakdown strength after the solidification of the adaptation of substrate, photosensitive polymer combination.
(A3) multipolymer and (A4) multipolymer also can be: also copolymerization have about (A2) multipolymer as described in other compounds, (methyl) esters of acrylic acid, (methyl) acrylic amide, allyl compound, vinyl ethers, vinyl ester, phenylethylene etc.
As the Component units with the position can be polymerized with (B) photopolymerization monomer, preferably there is the Component units of ethylenically unsaturated group as the position can be polymerized with (B) photopolymerization monomer.For there is the multipolymer of such Component units, for (A3) multipolymer, can by make the carboxyl contained by the polymkeric substance containing the Component units deriving from above-mentioned (a1) unsaturated carboxylic acid react to prepare at least partially, with above-mentioned (a2) unsaturated compound containing ester ring type epoxy radicals and/or (a4) unsaturated compound containing epoxy radicals.In addition, (A4) multipolymer can by make to have the Component units that derives from above-mentioned (a1) unsaturated carboxylic acid and derive from (a2) unsaturated compound containing ester ring type epoxy radicals and/or (a4) unsaturated compound containing epoxy radicals Component units multipolymer in epoxy radicals react to prepare at least partially, with (a1) unsaturated carboxylic acid.
(A3) ratio shared by the Component units deriving from (a1) unsaturated carboxylic acid in multipolymer is preferably 1 ~ 50 quality %, is more preferably 5 ~ 45 quality %.(A3) ratio shared by Component units in multipolymer, that have the position can be polymerized with (B) photopolymerization monomer is preferably 1 ~ 45 quality %, is more preferably 5 ~ 40 quality %.(A3), when multipolymer comprises each Component units with such ratio, easily obtain being formed the photosensitive polymer combination with the solidfied material of the excellent adhesion of substrate.
(A4) ratio shared by Component units in multipolymer, that derive from (a1) unsaturated carboxylic acid is preferably 1 ~ 50 quality %, is more preferably 5 ~ 45 quality %.(A4) ratio shared by Component units in multipolymer, that derive from (a2) unsaturated compound containing ester ring type epoxy radicals and/or (a4) unsaturated compound containing epoxy radicals is preferably more than 55 quality %, be more preferably more than 71 quality %, be particularly preferably 71 ~ 80 quality %.
(A4) ratio shared by Component units in multipolymer, that have the position can be polymerized with (B) photopolymerization monomer is preferably 1 ~ 45 quality %, is more preferably 5 ~ 40 quality %.(A4), when multipolymer comprises each Component units with such ratio, easily obtain being formed the photosensitive polymer combination with the black column spacer of the excellent adhesion of substrate.
(A3) the matter average molecular weight of multipolymer and (A4) multipolymer is preferably 2000 ~ 50000, is more preferably 5000 ~ 30000.By being set as above-mentioned scope, have be easy to obtain photosensitive polymer combination film Forming ability, developability after exposure the tendency of balance.
(A) content of alkali soluble resin is preferably 10 ~ 60 quality % relative to the solid constituent of photosensitive polymer combination, is more preferably 15 ~ 50 quality %.When using (A) alkali soluble resin of above-mentioned scope amount, easily obtain the photosensitive polymer combination of developability excellence.
< (B) photopolymerization monomer >
Photopolymerization monomer has monofunctional monomer and polyfunctional monomer.
As monofunctional monomer, can enumerate: (methyl) acrylamide, methylol (methyl) acrylamide, methoxy (methyl) acrylamide, ethoxyl methyl (methyl) acrylamide, propoxy methyl (methyl) acrylamide, butoxymethoxy methyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxymethyl (methyl) acrylamide, (methyl) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methyl propane sulfonic acid, tert-butyl acrylamide sulfonate, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxybutyl, (methyl) acrylic acid 2-phenoxy group-2-hydroxy propyl ester, 2-(methyl) acryloxy-2-hydroxypropyl phthalate, glycerine list (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylate ester, (methyl) glycidyl acrylate, (methyl) acrylic acid 2,2,2-trifluoro ethyl ester, (methyl) acrylic acid 2,2,3,3-tetrafluoro propyl ester, (methyl) acrylate half ester etc. of phthalic acid derivatives.These monofunctional monomers may be used singly or in combin two or more.
On the other hand, as polyfunctional monomer, can enumerate: ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, glycerine two (methyl) acrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, two (4-(methyl) the acryloxy diethoxy phenyl) propane of 2,2-, two (4-(methyl) acryloxypolyethoxyphenyl) propane of 2,2-, 2-hydroxyl-3-(methyl) acryloxypropyl (methyl) acrylate, ethylene glycol diglycidylether two (methyl) acrylate, diethylene glycol diglycidyl glycerin ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) acrylate, glycerol triacrylate, glycerine polyglycidyl ether gathers (methyl) acrylate, carbamate (methyl) acrylate (that is, toluene diisocyanate), the reaction product of trimethyl hexamethylene diisocyanate and hexamethylene diisocyanate and (methyl) acrylic acid 2-hydroxy methacrylate, di-2-ethylhexylphosphine oxide (methyl) acrylamide, (methyl) acrylamide methylene ether, the polyfunctional monomers such as the condensation product of polyvalent alcohol and N-methylol (methyl) acrylamide, 1,3,5-triacryl, six hydrogen-1,3,5-triazines etc.These polyfunctional monomers may be used singly or in combin two or more.
(B) content of photopolymerization monomer is preferably 3 ~ 30 quality % relative to the solid constituent of photosensitive polymer combination, is more preferably 5 ~ 20 quality %.By being set as above-mentioned scope, thus there is the tendency of balance being easy to obtain sensitivity, developability, resolution.
< (C) Photoepolymerizationinitiater initiater >
As (C) Photoepolymerizationinitiater initiater, be not particularly limited, known Photoepolymerizationinitiater initiater can be used.
As Photoepolymerizationinitiater initiater, specifically, can enumerate: 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone, two (4-dimethylaminophenyl) ketone, TMDPO, 4-benzoyl-4 '-methyl dimethoxy base thioether, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl esters, EDMAB, 4-dimethylaminobenzoic acid butyl ester, 4-dimethylamino-2-ethylhexyl Benzoic acid, 4-dimethylamino-2-isoamyl benzene formic acid, benzil-'beta '-methoxy ethyl acetal, benzil dimethyl ketal, 1-phenyl-1,2-pentanedione-2-(adjacent ethoxy carbonyl) oxime, o-benzoyl yl benzoic acid methyl esters, 2,4-diethyl thioxanthone, CTX, 2,4-dimethyl thioxanthone, the chloro-4-propoxythioxanthone of 1-, thioxanthene, 2-diuril ton, 2,4-diethyl thioxanthene, 2-methyl thioxanthene, 2-isopropylthioxanthones, 2-EAQ, prestox anthraquinone, 1,2-benzo anthraquinone, 2,3-diphenyl anthraquinone, azoisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer, 2-(Chloro-O-Phenyl)-4,5-bis-(methoxyphenyl) imidazole dimer, 2-(adjacent fluorophenyl)-4,5-diphenyl-imidazole dipolymer, 2-(o-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer, 2,4,5-triarylimidazoles dipolymer, benzophenone, 2-chlorobenzophenone, 4,4 '-bis-dimethylamino benzophenone (that is, michler's ketone), 4,4 '-bis-(diethylamino) benzophenone (that is, ethyl michler's ketone), 4,4 '-dichloro benzophenone, 3,3-dimethyl-4-methoxy benzophenone, benzil, benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin n-butylether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxy acetophenone, to dimethyl acetophenone, to dimethylamino propiophenone, dichloroacetophenone, trichloroacetophenone, p-tert.-butyl acetophenone, to dimethylamino benzoylformaldoxime, to tert-butyl group trichloroacetophenone, to tert-butyl group dichloroacetophenone, α, α,α-dichloro-4-phenoxy acetophenone, thioxanthones, 2-methyl thioxanthones, ITX, Dibenzosuberone, amyl group-4-dimethylaminobenzoic acid ester, 9-phenylacridine, two (9-acridinyl) heptane of 1,7-, two (9-acridinyl) pentane of 1,5-, two (9-acridinyl) propane of 1,3-, to methoxyl triazine, 2,4,6-tri-(trichloromethyl) s-triazine, two (trichloromethyl) s-triazine of 2-methyl-4,6-, two (trichloromethyl) s-triazine of 2-[2-(5-methylfuran-2-base) vinyl]-4,6-, two (trichloromethyl) s-triazine of 2-[2-(furans-2-base) vinyl]-4,6-, two (trichloromethyl) s-triazine of 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4,6-, two (trichloromethyl) s-triazine of 2-[2-(3,4-Dimethoxyphenyl) vinyl]-4,6-, two (trichloromethyl) s-triazine of 2-(4-methoxyphenyl)-4,6-, two (trichloromethyl) s-triazine of 2-(4-ethoxystyrene base)-4,6-, two (trichloromethyl) s-triazine of 2-(4-n-butoxyphenyl)-4,6-, 2,4-pair-trichloromethyl-6-(the bromo-4-methoxyl of 3-) phenyl s-triazine, 2,4-pair-trichloromethyl-6-(the bromo-4-methoxyl of 2-) phenyl s-triazine, 2,4-pair-trichloromethyl-6-(the bromo-4-methoxyl of 3-) styryl phenyl s-triazine, 2,4-pair-trichloromethyl-6-(the bromo-4-methoxyl of 2-) styryl phenyl s-triazine, " IRGACUREOXE02 ", " IRGACUREOXE01 ", " IRGACURE369 ", " IRGACURE651 ", " IRGACURE907 " (trade name: BASF manufactures), " NCI-831 " (trade name: ADEKA manufactures) etc.These Photoepolymerizationinitiater initiaters may be used singly or in combin two or more.
Photosensitive polymer combination preferably contains oxime ester compound as (C) Photoepolymerizationinitiater initiater in compound described above.Oxime ester compound is two organic groups by the compound of the oxime ester bond bonding represented with=N-O-CO-.When being combined with oxime ester compound in photosensitive polymer combination as (C) Photoepolymerizationinitiater initiater, easily obtain the photosensitive polymer combination of exposure sensitivity excellence.
The oxime ester compound being used as (C) Photoepolymerizationinitiater initiater is not particularly limited.Known oxime ester compound can be used as (C) Photoepolymerizationinitiater initiater.Among oxime ester compound, the compound represented by preferred following formula (c1).
[changing 9]
In above-mentioned formula (c1), R c1expression can have substituent carbon number 1 ~ 10 alkyl, substituent phenyl can be had or substituent carbazyl can be had.A is 0 or 1.R c2expression can have substituent carbon number 1 ~ 10 alkyl, substituent phenyl can be had or substituent carbazyl can be had.R c3represent the alkyl of hydrogen atom, carbon number 1 ~ 6 or substituent phenyl can be had.
R c1when for having the alkyl of substituent carbon number 1 ~ 10, the substituent kind that alkyl has is not particularly limited in the scope not hindering object of the present invention.
The substituent example be applicable to that alkyl as carbon number 1 ~ 10 can have, can enumerate: the alkoxy of carbon number 1 ~ 20, the naphthenic base of carbon number 3 ~ 10, the cycloalkyloxy of carbon number 3 ~ 10, the representative examples of saturated aliphatic acyl group of carbon number 2 ~ 20, the alkoxy carbonyl of carbon number 2 ~ 20, the representative examples of saturated aliphatic acyloxy of carbon number 2 ~ 20, substituent phenyl can be had, substituent phenoxy group can be had, substituent thiophenyl can be had, substituent benzoyl can be had, substituent phenyloxycarbonyl can be had, substituent benzoyl oxygen base can be had, the phenylalkyl of substituent carbon number 7 ~ 20 can be had, substituent naphthyl can be had, substituent naphthoxy can be had, substituent naphthoyl can be had, substituent naphthoxycarbonyl can be had, substituent Naphthoyloxy can be had, the naphthylalkyl of substituent carbon number 11 ~ 20 can be had, substituent heterocyclic radical can be had, substituent Heterocyclylcarbonyl can be had, amino, amino after being replaced by 1 or 2 organic groups, morpholine-1-base and piperazine-1-base, halogen, nitro and cyano group etc.
The alkyl of carbon number 1 ~ 10 can be able to be side chain for straight-chain.In this case, the carbon number of alkyl is preferably 1 ~ 8, is more preferably 1 ~ 5.
R c1when for having substituent phenyl, substituent kind is not particularly limited in the scope not hindering object of the present invention.As the substituent applicable example that phenyl can have, can enumerate: alkyl, alkoxy, naphthenic base, cycloalkyloxy, representative examples of saturated aliphatic acyl group, alkoxy carbonyl, representative examples of saturated aliphatic acyloxy, substituent phenyl can be had, substituent phenoxy group can be had, substituent benzoyl can be had, substituent phenyloxycarbonyl can be had, substituent benzoyloxy can be had, substituent phenylalkyl can be had, substituent naphthyl can be had, substituent naphthoxy can be had, substituent naphthoyl can be had, substituent naphthoxycarbonyl can be had, substituent Naphthoyloxy can be had, substituent naphthylalkyl can be had, substituent heterocyclic radical can be had, amino, amino after being replaced by 1 or 2 organic groups, morpholine-1-base and piperazine-1-base, halogen, nitro and cyano group etc.R c1for substituent phenyl can be had and under phenyl has multiple substituent situation, multiple substituting group can be the same or different.
When the substituting group that phenyl has is alkyl, its carbon number is preferably 1 ~ 20, is more preferably 1 ~ 10, and more preferably 1 ~ 6, be particularly preferably 1 ~ 3, most preferably be 1.In addition, alkyl can be straight-chain also can be branched.The concrete example when substituting group had as phenyl is alkyl, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, secondary octyl, tertiary octyl group, n-nonyl, different nonyl, positive decyl and isodecyl etc.In addition, alkyl can contain ehter bond (-O-) in carbochain.In this case, as the substituting group that phenyl has, such as, alkoxyalkyl, alkoxy alkoxy alkyl can be enumerated.When the substituting group that phenyl has is alkoxyalkyl, be preferably-R c4-O-R c5represented group.R c4for the alkylidene of the straight or branched of carbon number 1 ~ 10.R c5for the alkyl of the straight or branched of carbon number 1 ~ 10.R c4carbon number be preferably 1 ~ 8, be more preferably 1 ~ 5, be particularly preferably 1 ~ 3.R c5carbon number be preferably 1 ~ 8, be more preferably 1 ~ 5, be particularly preferably 1 ~ 3, most preferably be 1.As the example of alkyl in carbochain with ehter bond, can enumerate: methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyl group ethoxyethyl group and methoxy-propyl etc.
When the substituting group that phenyl has is alkoxy, its carbon number is preferably 1 ~ 20, is more preferably 1 ~ 6.In addition, alkoxy can be straight chain also can be side chain.The concrete example when substituting group had as phenyl is alkoxy, can enumerate: methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, secondary amoxy, tertiary amoxy, just own oxygen base, positive heptan oxygen base, n-octyloxy, different octyloxy, secondary octyloxy, tertiary octyloxy, positive ninth of the ten Heavenly Stems oxygen base, different ninth of the ten Heavenly Stems oxygen base, n-decyloxy and isodecyl oxygen base etc.In addition, alkoxy can contain ehter bond (-O-) in carbochain.As the example of alkoxy in carbochain with ehter bond, can enumerate: methoxy ethoxy, ethoxy ethoxy, 2-methoxyl-1-methyl ethoxy, methoxyethoxyethoxy, ethoxy ethoxy ethoxy, propoxy ethoxyethoxy and methoxy propoxy etc.
The substituting group that phenyl has be naphthenic base or cycloalkyloxy when, its carbon number is preferably 3 ~ 10, is more preferably 3 ~ 6.The concrete example when substituting group had as phenyl is naphthenic base, can enumerate: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group etc.The concrete example when substituting group had as phenyl is cycloalkyloxy, can enumerate: ring propoxyl group, cyclobutoxy group, cyclopentyloxy, cyclohexyloxy, ring oxygen in heptan base and ring octyloxy etc.
The substituting group that phenyl has be representative examples of saturated aliphatic acyl group or representative examples of saturated aliphatic acyloxy when, its carbon number is preferably 2 ~ 20, is more preferably 2 ~ 7.The concrete example when substituting group had as phenyl is representative examples of saturated aliphatic acyl group; can enumerate: acetyl group, propiono, positive bytyry, 2-methylpropionyl, positive valeryl, 2,2-Dimethylpropanoyl, positive caproyl, positive heptanoyl group, positive caprylyl, positive pelargonyl group, positive capryl, n-undecane acyl group, n-dodecane acyl group, n-tridecane acyl group, n-tetradecane acyl group, n-pentadecane acyl group and n-hexadecane acyl group etc.The concrete example when substituting group had as phenyl is representative examples of saturated aliphatic acyloxy, can enumerate: acetoxyl group, propionyloxy, positive butyryl acyloxy, 2-methylpropionyloxy, positive penta acyloxy, 2,2-dimethylpropanoyloxy, positive hexylyloxy, positive heptan acyloxy, just pungent acyloxy, positive ninth of the ten Heavenly Stems acyloxy, positive last of the ten Heavenly stems acyloxy, n-undecane acyloxy, n-dodecane acyloxy, n-tridecane acyloxy, n-tetradecane acyloxy, n-pentadecane acyloxy and n-hexadecane acyloxy etc.
When the substituting group that phenyl has is alkoxy carbonyl, its carbon number is preferably 2 ~ 20, is more preferably 2 ~ 7.The concrete example when substituting group had as phenyl is alkoxy carbonyl, can enumerate: methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, n-butoxycarbonyl, isobutoxy carbonyl, s-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, isoamoxy carbonyl, secondary pentyloxy carbonyl, tert-pentyloxy carbonyl, positive hexyloxy carbonyl, positive heptan oxygen base carbonyl, n-octyloxy carbonyl, different carbonyl octyloxy, secondary carbonyl octyloxy, tertiary carbonyl octyloxy, positive ninth of the ten Heavenly Stems oxygen base carbonyl, different ninth of the ten Heavenly Stems oxygen base carbonyl, n-decyloxy carbonyl and isodecyl oxygen base carbonyl etc.
When the substituting group that phenyl has is phenylalkyl, its carbon number is preferably 7 ~ 20, is more preferably 7 ~ 10.In addition, when the substituting group that phenyl has is naphthylalkyl, its carbon number is preferably 11 ~ 20, is more preferably 11 ~ 14.The concrete example when substituting group had as phenyl is phenylalkyl, can enumerate: benzyl, 2-phenylethyl, 3-phenyl propyl and 4-phenyl butyl.The concrete example when substituting group had as phenyl is naphthylalkyl, can enumerate: Alpha-Naphthyl methyl, betanaphthyl methyl, 2-(Alpha-Naphthyl) ethyl and 2-(betanaphthyl) ethyl.The substituting group that phenyl has be phenylalkyl or naphthylalkyl when, substituting group can have substituting group further on phenyl or naphthyl.
When the substituting group that phenyl has is heterocyclic radical, heterocyclic radical is five yuan of monocycles or the single six-membered rings of N, S, the O comprising more than 1, or described monocycle to each other or the heterocyclic radical that condenses of described monocycle and phenyl ring.When heterocyclic radical is condensed ring, the quantity set of the ring condensed is for 3.As the heterocycle forming described heterocyclic radical, can enumerate: furans, thiophene, pyrroles, oxazole, isoxazole, thiazole, thiadiazoles, isothiazole, imidazoles, pyrazoles, triazole, pyridine, pyrazine, pyrimidine, pyridazine, coumarone, benzothiophene, indoles, iso-indoles, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazines, cinnolines and quinoxaline etc.When the substituting group that phenyl has is heterocyclic radical, heterocyclic radical can have substituting group further.
When the substituting group that phenyl has is the amino after being replaced by 1 or 2 organic groups, the example be applicable to of organic group can be enumerated: the alkyl of carbon number 1 ~ 20, the naphthenic base of carbon number 3 ~ 10, the representative examples of saturated aliphatic acyl group of carbon number 2 ~ 20, the representative examples of saturated aliphatic acyloxy of carbon number 2 ~ 20, substituent phenyl can be had, substituent benzoyl can be had, the phenylalkyl of substituent carbon number 7 ~ 20 can be had, substituent naphthyl can be had, substituent naphthoyl can be had, the naphthylalkyl and heterocyclic radical etc. of substituent carbon number 11 ~ 20 can be had.As the concrete example of the organic group that these are applicable to, for the substituting group that phenyl has, the group same with above-mentioned group can be enumerated.As the concrete example of the amino after being replaced by 1 or 2 organic groups, can enumerate: methylamino, ethylamino, diethylamino, n-pro-pyl is amino, diη-propyl is amino, isopropylamino, n-butylamino, di-n-butyl is amino, n-pentyl is amino, n-hexyl is amino, n-heptyl is amino, n-octyl is amino, n-nonyl is amino, positive Decylamino, phenyl amino, naphthyl-amino, acetyl-amino, propanoylamino, positive bytyry is amino, positive pentanoylamino, positive caproyl is amino, positive heptanoyl group is amino, positive octanoylamino, positive decanoylamino, benzoyl-amido, α-naphthoylamino, β-naphthoylamino and N-acetyl group-N-acetoxyl group amino etc.
There is as the phenyl, naphthyl and the heterocyclic radical that contain in the substituting group that phenyl has substituting group in substituent situation further, can enumerate: the representative examples of saturated aliphatic acyl group of the alkyl of carbon number 1 ~ 6, the alkoxy of carbon number 1 ~ 6, carbon number 2 ~ 7, the alkoxy carbonyl of carbon number 2 ~ 7, the representative examples of saturated aliphatic acyloxy of carbon number 2 ~ 7, the alkyl monosubstituted amino with the alkyl of carbon number 1 ~ 6, the dialkyl amido with the alkyl of carbon number 1 ~ 6, morpholine-1-base, piperazine-1-base, halogen, nitro and cyano group etc.Under the phenyl, naphthyl and the heterocyclic radical that contain in the substituting group that phenyl has have substituent situation further, its substituent number does not limit in the scope not hindering object of the present invention, is preferably 1 ~ 4.Under the phenyl, naphthyl and the heterocyclic radical that contain in the substituting group that phenyl has have multiple substituent situation, multiple substituting group can be the same or different.
Above, illustrated R c1in substituting group when for substituent phenyl can be had, preferred alkyl or alkoxyalkyl.
R c1when for having substituent phenyl, substituent number and substituent bonding position are not particularly limited in the scope not hindering object of the present invention.R c1when for substituent phenyl can be had, from the viewpoint of the generation efficiency excellence of alkali, substituent phenyl can be had and preferably can have substituent o-tolyl.
R c1when for having substituent carbazyl, substituent kind is not particularly limited in the scope not hindering object of the present invention.As the substituent example be applicable to that carbazyl can have on carbon atom, can enumerate: the alkyl of carbon number 1 ~ 20, the alkoxy of carbon number 1 ~ 20, the naphthenic base of carbon number 3 ~ 10, the cycloalkyloxy of carbon number 3 ~ 10, the representative examples of saturated aliphatic acyl group of carbon number 2 ~ 20, the alkoxy carbonyl of carbon number 2 ~ 20, the representative examples of saturated aliphatic acyloxy of carbon number 2 ~ 20, substituent phenyl can be had, substituent phenoxy group can be had, substituent thiophenyl can be had, substituent phenylcarbonyl group can be had, substituent benzoyl can be had, substituent phenyloxycarbonyl can be had, substituent benzoyloxy can be had, the phenylalkyl of substituent carbon number 7 ~ 20 can be had, substituent naphthyl can be had, substituent naphthoxy can be had, substituent naphthyl carbonyl can be had, substituent naphthoyl can be had, substituent naphthoxycarbonyl can be had, substituent Naphthoyloxy can be had, the naphthylalkyl of substituent carbon number 11 ~ 20 can be had, substituent heterocyclic radical can be had, substituent Heterocyclylcarbonyl can be had, amino, amino after being replaced by 1 or 2 organic groups, morpholine-1-base and piperazine-1-base, halogen, nitro and cyano group etc.
R c1when for substituent carbazyl can be had, as the substituent example be applicable to that carbazyl can have on nitrogen-atoms, can enumerate: the alkyl of carbon number 1 ~ 20, the naphthenic base of carbon number 3 ~ 10, the representative examples of saturated aliphatic acyl group of carbon number 2 ~ 20, the alkoxy carbonyl of carbon number 2 ~ 20, substituent phenyl can be had, substituent benzoyl can be had, substituent phenyloxycarbonyl can be had, the phenylalkyl of substituent carbon number 7 ~ 20 can be had, substituent naphthyl can be had, substituent naphthoyl can be had, substituent naphthoxycarbonyl can be had, the naphthylalkyl of substituent carbon number 11 ~ 20 can be had, substituent heterocyclic radical can be had and can substituent Heterocyclylcarbonyl etc. be had.In these substituting groups, the alkyl of preferred carbon number 1 ~ 20, the more preferably alkyl of carbon number 1 ~ 6, particularly preferably ethyl.
For the substituent concrete example that carbazyl can have; about alkyl, alkoxy, naphthenic base, cycloalkyloxy, representative examples of saturated aliphatic acyl group, alkoxy carbonyl, representative examples of saturated aliphatic acyloxy, substituent phenylalkyl can be had, substituent naphthylalkyl can be had, substituent heterocyclic radical and the amino after being replaced by 1 or 2 organic groups can be had, with R c1the substituent example had for phenyl when can have substituent phenyl is identical.
R c1in, there is as the phenyl, naphthyl and the heterocyclic radical that contain in the substituting group that carbazyl has substituent example in substituent situation further, can enumerate: the alkyl of carbon number 1 ~ 6; The alkoxy of carbon number 1 ~ 6; The representative examples of saturated aliphatic acyl group of carbon number 2 ~ 7; The alkoxy carbonyl of carbon number 2 ~ 7; The representative examples of saturated aliphatic acyloxy of carbon number 2 ~ 7; Phenyl; Naphthyl; Benzoyl; Naphthoyl; Benzoyl after the group be selected from the alkyl of carbon number 1 ~ 6, morpholine-1-base, piperazine-1-base and phenyl replaces; There is the alkyl monosubstituted amino of the alkyl of carbon number 1 ~ 6; There is the dialkyl amido of the alkyl of carbon number 1 ~ 6; Morpholine-1-base; Piperazine-1-base; Halogen; Nitro; Cyano group.Under the phenyl, naphthyl and the heterocyclic radical that contain in the substituting group that carbazyl has have substituent situation further, its substituent number does not limit in the scope not hindering object of the present invention.In this case, substituent number is preferably 1 ~ 4.Under phenyl, naphthyl and heterocyclic radical have multiple substituent situation, multiple substituting group can be the same or different.
R c2for the alkyl of substituent carbon number 1 ~ 10 can be had or can have substituent phenyl or can have substituent carbazyl.
R c2when for having the alkyl of substituent carbon number 1 ~ 10, alkyl can be straight chain also can be side chain.In this case, the carbon number of alkyl is preferably 1 ~ 8, is more preferably 1 ~ 5.
R c2in, the substituting group that alkyl or phenyl has is not particularly limited in the scope not hindering object of the present invention.
As the substituent example be applicable to that alkyl can have on carbon atom, can enumerate: the alkoxy of carbon number 1 ~ 20, the naphthenic base of carbon number 3 ~ 10, the cycloalkyloxy of carbon number 3 ~ 10, the representative examples of saturated aliphatic acyl group of carbon number 2 ~ 20, the alkoxy carbonyl of carbon number 2 ~ 20, the representative examples of saturated aliphatic acyloxy of carbon number 2 ~ 20, substituent phenyl can be had, substituent phenoxy group can be had, substituent thiophenyl can be had, substituent benzoyl can be had, substituent phenyloxycarbonyl can be had, substituent benzoyl oxygen base can be had, the phenylalkyl of substituent carbon number 7 ~ 20 can be had, substituent naphthyl can be had, substituent naphthoxy can be had, substituent naphthoyl can be had, substituent naphthoxycarbonyl can be had, substituent naphthoyl oxygen base can be had, the naphthylalkyl of substituent carbon number 11 ~ 20 can be had, substituent heterocyclic radical can be had, substituent Heterocyclylcarbonyl can be had, amino, amino after being replaced by 1 or 2 organic groups, morpholine-1-base and piperazine-1-base, halogen, nitro and cyano group etc.
As the substituent example be applicable to that phenyl can have on carbon atom, except the above-mentioned group exemplified, the alkyl of carbon number 1 ~ 20 can also be enumerated except applicable substituting group can be had as alkyl on carbon atom.
For the substituent concrete example that alkyl or phenyl can have; about alkyl, alkoxy, naphthenic base, cycloalkyloxy, representative examples of saturated aliphatic acyl group, alkoxy carbonyl, representative examples of saturated aliphatic acyloxy, substituent phenylalkyl can be had, substituent naphthylalkyl can be had, substituent heterocyclic radical and the amino after being replaced by 1 or 2 organic groups can be had, with R c1the substituent example had for phenyl when can have substituent phenyl is identical.
R c2in, there is as the phenyl, naphthyl and the heterocyclic radical that contain in the substituting group that alkyl or phenyl has substituent example in substituent situation further, can enumerate: the alkyl of carbon number 1 ~ 6; The alkoxy of carbon number 1 ~ 6; The representative examples of saturated aliphatic acyl group of carbon number 2 ~ 7; The alkoxy carbonyl of carbon number 2 ~ 7; The representative examples of saturated aliphatic acyloxy of carbon number 2 ~ 7; Phenyl; Naphthyl; Benzoyl; Naphthoyl; Benzoyl after the group be selected from the alkyl of carbon number 1 ~ 6, morpholine-1-base, piperazine-1-base and phenyl replaces; There is the alkyl monosubstituted amino of the alkyl of carbon number 1 ~ 6; There is the dialkyl amido of the alkyl of carbon number 1 ~ 6; Morpholine-1-base; Piperazine-1-base; Halogen; Nitro; Cyano group.Under the phenyl, naphthyl and the heterocyclic radical that contain in the substituting group that alkyl or phenyl has have substituent situation further, its substituent number does not limit in the scope not hindering object of the present invention, is preferably 1 ~ 4.Under phenyl, naphthyl and heterocyclic radical have multiple substituent situation, multiple substituting group can be the same or different.
R c2when for having substituent carbazyl, the substituent kind that carbazyl has is not particularly limited in the scope not hindering object of the present invention.As the substituent applicable example that carbazyl can have, with R c1for substituent example when can have substituent carbazyl is identical.
From the reactive view of the compound represented by formula (c1), as R c2, the group represented by preferred following formula (c2) or the group represented by following formula (c3).
[changing 10]
In formula (c2), R c6and R c7be respectively monovalent organic group, b is 0 or 1.In formula (c3), R c8for being selected from the group in monovalent organic group, amino, halogen, nitro and cyano group, A to be S or O, c be 0 ~ 4 integer.
R in formula (c2) c6do not hindering within the scope of the object of the invention and can select from various organic group.As R c6be applicable to example, can enumerate: hydrogen atom, the alkyl of carbon number 1 ~ 20, the naphthenic base of carbon number 3 ~ 10, the representative examples of saturated aliphatic acyl group of carbon number 2 ~ 20, the alkoxy carbonyl of carbon number 2 ~ 20, substituent phenyl can be had, substituent benzoyl can be had, substituent phenyloxycarbonyl can be had, the phenylalkyl of substituent carbon number 7 ~ 20 can be had, substituent naphthyl can be had, substituent naphthoyl can be had, substituent naphthoxycarbonyl can be had, the naphthylalkyl of substituent carbon number 11 ~ 20 can be had, substituent heterocyclic radical can be had and can substituent Heterocyclylcarbonyl etc. be had.
R c6in, the alkyl of preferred carbon number 1 ~ 20, the more preferably alkyl of carbon number 1 ~ 6, particularly preferably ethyl.
R in formula (c2) c7be not particularly limited in the scope not hindering object of the present invention, can select from various organic group.As being suitable as R c7the concrete example of group, can enumerate: the alkyl of hydrogen atom, carbon number 1 ~ 20, substituent phenyl can be had, substituent naphthyl can be had and substituent heterocyclic radical can be had.As R c7, more preferably can have substituent phenyl in these groups and substituent naphthyl can be had, particularly preferably 2-aminomethyl phenyl and naphthyl.
As R c6or R c7in the phenyl, naphthyl and the heterocyclic radical that contain there is substituting group in substituent situation further, can enumerate: the representative examples of saturated aliphatic acyl group of the alkyl of carbon number 1 ~ 6, the alkoxy of carbon number 1 ~ 6, carbon number 2 ~ 7, the alkoxy carbonyl of carbon number 2 ~ 7, the representative examples of saturated aliphatic acyloxy of carbon number 2 ~ 7, the alkyl monosubstituted amino with the alkyl of carbon number 1 ~ 6, the dialkyl amido with the alkyl of carbon number 1 ~ 6, morpholine-1-base, piperazine-1-base, halogen, nitro and cyano group etc.R c6or R c7in under the phenyl, naphthyl and the heterocyclic radical that contain have substituent situation further, its substituent number does not limit in the scope not hindering object of the present invention, is preferably 1 ~ 4.R c6or R c7in under the phenyl, naphthyl and the heterocyclic radical that contain have multiple substituent situation, multiple substituting group can be the same or different.
R in formula (c3) c8when for organic group, R c8do not hindering within the scope of the object of the invention and can select from various organic group.As R in formula (c3) c8for the example be applicable to when organic group, can enumerate: the alkyl of carbon number 1 ~ 6; The alkoxy of carbon number 1 ~ 6; The representative examples of saturated aliphatic acyl group of carbon number 2 ~ 7; The alkoxy carbonyl of carbon number 2 ~ 7; The representative examples of saturated aliphatic acyloxy of carbon number 2 ~ 7; Phenyl; Naphthyl; Benzoyl; Naphthoyl; Benzoyl after the group be selected from the alkyl of carbon number 1 ~ 6, morpholine-1-base, piperazine-1-base and phenyl replaces; There is the alkyl monosubstituted amino of the alkyl of carbon number 1 ~ 6; There is the dialkyl amido of the alkyl of carbon number 1 ~ 6; Morpholine-1-base; Piperazine-1-base; Halogen; Nitro; Cyano group; 2-aminomethyl phenyl carbonyl; 4-(piperazine-1-base) phenylcarbonyl group; 4-(phenyl) phenylcarbonyl group.
R c8in, preferred benzoyl; Naphthoyl; Benzoyl after the group be selected from the alkyl of carbon number 1 ~ 6, morpholine-1-base, piperazine-1-base and phenyl replaces; Nitro, more preferably benzoyl; Naphthoyl; 2-aminomethyl phenyl carbonyl; 4-(piperazine-1-base) phenylcarbonyl group; 4-(phenyl) phenylcarbonyl group.
In addition, in formula (c3), c is preferably the integer of 0 ~ 3, is more preferably the integer of 0 ~ 2, is particularly preferably 0 or 1.When c is 1, R c8bonding position preferably relative to R c8the phenyl of institute's bonding and the binding site of-A-bonding are contraposition.
R c3for hydrogen atom, carbon number 1 ~ 6 alkyl or substituent phenyl can be had.R c3when for substituent phenyl can be had, substituting group and the R of phenyl can be had c1for the situation can with substituent phenyl is identical.As R c3, preferable methyl, ethyl or phenyl, more preferably methyl or phenyl.
Oxime ester compound represented by above-mentioned formula (c1) such as can be synthesized by the method for following explanation when a is 0.First, utilize hydramine by R c2-CO-R c1represented ketonic compound oximate, obtains R c2-(C=N-OH)-R c1represented oxime compound.Then, obtained oxime compound is utilized R c3etheride, (R represented by-CO-Hal (Hal represents halogen) c3cO) 2acid anhydrides represented by O carries out acidylate, thus obtains the oxime ester compound represented by above-mentioned formula (c1) that a is 0.
In addition, the oxime ester compound represented by above-mentioned formula (c1) such as can be synthesized by the method for following explanation when a is 1.First, R is made in presence of hydrochloric acid c2-CO-CH 2-R c1represented ketonic compound and nitrites react, and obtain R c2-CO-(C=N-OH)-R c1represented oxime compound.Then, obtained oxime compound is utilized R c3etheride, (R represented by-CO-Hal (Hal represents halogen) c3cO) 2acid anhydrides represented by O carries out acidylate, thus obtains the oxime ester compound represented by above-mentioned formula (c1) that a is 1.
As the compound represented by above-mentioned formula (c1), the compound represented by following formula (c4) can be enumerated.
[changing 12]
In above-mentioned formula (c4), a, R c2, and R c3as mentioned above.R c9for being selected from the group in monovalent organic group, amino, halogen, nitro and cyano group, d is the integer of 0 ~ 4.
In above-mentioned formula (c4), R c9be not particularly limited in the scope not hindering object of the present invention, when for organic group, suitably select from various organic group.As R c9be applicable to example, can enumerate: alkyl, alkoxy, naphthenic base, cycloalkyloxy, representative examples of saturated aliphatic acyl group, alkoxy carbonyl, representative examples of saturated aliphatic acyloxy, substituent phenyl can be had, substituent phenoxy group can be had, substituent benzoyl can be had, substituent phenyloxycarbonyl can be had, substituent benzoyl oxygen base can be had, substituent phenylalkyl can be had, substituent naphthyl can be had, substituent naphthoxy can be had, substituent naphthoyl can be had, substituent naphthoxycarbonyl can be had, substituent naphthoyl oxygen base can be had, substituent naphthylalkyl can be had, substituent heterocyclic radical can be had, amino, amino after being replaced by 1 or 2 organic groups, morpholine-1-base, piperazine-1-base, halogen, nitro and cyano group etc.When d is the integer of 2 ~ 4, R c9can be the same or different.In addition, further the had substituent carbon number of substituting group is not comprised in substituent carbon number.
R c9when for alkyl, carbon number is preferably 1 ~ 20, and carbon number is more preferably 1 ~ 6.In addition, R c9when for alkyl, can be that straight chain also can for side chain.As R c9for concrete example when alkyl, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, secondary octyl, tertiary octyl group, n-nonyl, different nonyl, positive decyl and isodecyl etc.In addition, R c9when for alkyl, alkyl can contain ehter bond (-O-) in carbochain.As the example of alkyl in carbochain with ehter bond, can enumerate: methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyl group ethoxyethyl group and methoxy-propyl etc.
R c9when for alkoxy, carbon number is preferably 1 ~ 20, and carbon number is more preferably 1 ~ 6.In addition, R c9when for alkoxy, it can be straight chain also can be side chain.As R c9for concrete example when alkoxy, can enumerate: methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, secondary amoxy, tertiary amoxy, just own oxygen base, positive heptan oxygen base, n-octyloxy, different octyloxy, secondary octyloxy, tertiary octyloxy, positive ninth of the ten Heavenly Stems oxygen base, different ninth of the ten Heavenly Stems oxygen base, n-decyloxy and isodecyl oxygen base etc.In addition, R c9when for alkoxy, alkoxy can contain ehter bond (-O-) in carbochain.As the example of alkoxy in carbochain with ehter bond, can enumerate: methoxy ethoxy, ethoxy ethoxy, methoxyethoxyethoxy, ethoxy ethoxy ethoxy, propoxy ethoxyethoxy and methoxy propoxy etc.
R c9when for naphthenic base or cycloalkyloxy, carbon number is preferably 3 ~ 10, and carbon number is more preferably 3 ~ 6.As R c9for concrete example when naphthenic base, can enumerate: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group etc.As R c9for concrete example when cycloalkyloxy, can enumerate: ring propoxyl group, cyclobutoxy group, cyclopentyloxy, cyclohexyloxy, ring oxygen in heptan base and ring octyloxy etc.
R c9when for representative examples of saturated aliphatic acyl group or representative examples of saturated aliphatic acyloxy, carbon number is preferably 2 ~ 20, and carbon number is more preferably 2 ~ 7.As R c9for concrete example when representative examples of saturated aliphatic acyl group; can enumerate: acetyl group, propiono, positive bytyry, 2-methylpropionyl, positive valeryl, 2,2-Dimethylpropanoyl, positive caproyl, positive heptanoyl group, positive caprylyl, positive pelargonyl group, positive capryl, n-undecane acyl group, n-dodecane acyl group, n-tridecane acyl group, n-tetradecane acyl group, n-pentadecane acyl group and n-hexadecane acyl group etc.As R c9for concrete example when representative examples of saturated aliphatic acyloxy, can enumerate: acetoxyl group, propionyloxy, positive butyryl acyloxy, 2-methylpropionyloxy, positive penta acyloxy, 2,2-dimethylpropanoyloxy, positive hexylyloxy, positive heptan acyloxy, just pungent acyloxy, positive ninth of the ten Heavenly Stems acyloxy, positive last of the ten Heavenly stems acyloxy, n-undecane acyloxy, n-dodecane acyloxy, n-tridecane acyloxy, n-tetradecane acyloxy, n-pentadecane acyloxy and n-hexadecane acyloxy etc.
R c9when for alkoxy carbonyl, carbon number is preferably 2 ~ 20, and carbon number is more preferably 2 ~ 7.As R c9for concrete example when alkoxy carbonyl, can enumerate: methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, n-butoxycarbonyl, isobutoxy carbonyl, s-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, isoamoxy carbonyl, secondary pentyloxy carbonyl, tert-pentyloxy carbonyl, positive hexyloxy carbonyl, positive heptan oxygen base carbonyl, n-octyloxy carbonyl, different carbonyl octyloxy, secondary carbonyl octyloxy, tertiary carbonyl octyloxy, positive ninth of the ten Heavenly Stems oxygen base carbonyl, different ninth of the ten Heavenly Stems oxygen base carbonyl, n-decyloxy carbonyl and isodecyl oxygen base carbonyl etc.
R c9when for phenylalkyl, carbon number is preferably 7 ~ 20, and carbon number is more preferably 7 ~ 10.In addition, R c9when for naphthylalkyl, carbon number is preferably 11 ~ 20, and carbon number is more preferably 11 ~ 14.As R c9for concrete example when phenylalkyl, can enumerate: benzyl, 2-phenylethyl, 3-phenyl propyl and 4-phenyl butyl.As R c9for concrete example when naphthylalkyl, can enumerate: Alpha-Naphthyl methyl, betanaphthyl methyl, 2-(Alpha-Naphthyl) ethyl and 2-(betanaphthyl) ethyl.R c9when for phenylalkyl or naphthylalkyl, R c9substituting group can be had further on phenyl or naphthyl.
R c9when for heterocyclic radical, heterocyclic radical is five yuan of monocycles or the single six-membered rings of N, S, the O comprising more than 1, or described monocycle to each other or the heterocyclic radical that condenses of described monocycle and phenyl ring.When heterocyclic radical is condensed ring, the quantity set of the ring condensed is for 3.As the heterocycle forming described heterocyclic radical, can enumerate: furans, thiophene, pyrroles, oxazole, isoxazole, thiazole, thiadiazoles, isothiazole, imidazoles, pyrazoles, triazole, pyridine, pyrazine, pyrimidine, pyridazine, coumarone, benzothiophene, indoles, iso-indoles, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazines, cinnolines and quinoxaline etc.R c9when for heterocyclic radical, heterocyclic radical can have substituting group further.
R c9when for amino after being replaced by 1 or 2 organic groups, the example be applicable to of organic group can be enumerated: the representative examples of saturated aliphatic acyl group of the alkyl of carbon number 1 ~ 20, the naphthenic base of carbon number 3 ~ 10, carbon number 2 ~ 20, can have substituent phenyl, can have substituent benzoyl, can have the phenylalkyl of substituent carbon number 7 ~ 20, can have substituent naphthyl, can have substituent naphthoyl, can have the naphthylalkyl of substituent carbon number 11 ~ 20 and heterocyclic radical etc.The concrete example of these organic groups be applicable to and R c9identical.As the concrete example of the amino after being replaced by 1 or 2 organic groups, can enumerate: methylamino, ethylamino, diethylamino, n-pro-pyl is amino, diη-propyl is amino, isopropylamino, n-butylamino, di-n-butyl is amino, n-pentyl is amino, n-hexyl is amino, n-heptyl is amino, n-octyl is amino, n-nonyl is amino, positive Decylamino, phenyl amino, naphthyl-amino, acetyl-amino, propanoylamino, positive bytyry is amino, positive pentanoylamino, positive caproyl is amino, positive heptanoyl group is amino, positive octanoylamino, positive decanoylamino, benzoyl-amido, α-naphthoylamino and β-naphthoylamino etc.
As R c9in the phenyl, naphthyl and the heterocyclic radical that contain there is substituting group in substituent situation further, can enumerate: the representative examples of saturated aliphatic acyl group of the alkyl of carbon number 1 ~ 6, the alkoxy of carbon number 1 ~ 6, carbon number 2 ~ 7, the alkoxy carbonyl of carbon number 2 ~ 7, the representative examples of saturated aliphatic acyloxy of carbon number 2 ~ 7, the alkyl monosubstituted amino with the alkyl of carbon number 1 ~ 6, the dialkyl amido with the alkyl of carbon number 1 ~ 6, morpholine-1-base, piperazine-1-base, halogen, nitro and cyano group etc.R c9in under the phenyl, naphthyl and the heterocyclic radical that contain have substituent situation further, its substituent number does not limit in the scope not hindering object of the present invention, is preferably 1 ~ 4.R c9in under the phenyl, naphthyl and the heterocyclic radical that contain have multiple substituent situation, multiple substituting group can be the same or different.
R c9in; the viewpoints such as stable, steric restriction synthesis that is few, oxime ester compound is easy are chemically set out; be preferably selected from the group in the alkyl of carbon number 1 ~ 6, the alkoxy of carbon number 1 ~ 6 and the representative examples of saturated aliphatic acyl group of carbon number 2 ~ 7; more preferably the alkyl of carbon number 1 ~ 6, particularly preferably methyl.
About R c9with the position of phenyl bonding, for R c9the phenyl of institute's bonding, is set to 1 in the position of the binding site of the main framing by phenyl and oxime ester compound, when the position of methyl is set to 2, preferably 4 or 5, more preferably 5.In addition, d is preferably the integer of 0 ~ 3, is more preferably the integer of 0 ~ 2, is particularly preferably 0 or 1.
R in above-mentioned formula (c4) c3for hydrogen atom, carbon number 1 ~ 6 alkyl or substituent phenyl can be had.R c3concrete example, as described in for formula (c1).As the R in formula (c4) c3, preferable methyl, ethyl and phenyl, more preferably methyl and phenyl.
In oxime ester compound, as formula (c1) comprise but the suitable examples of compound that do not comprise of formula (c4), following compound can be enumerated.
[changing 13]
In addition, among the oxime ester compound represented by the particularly suitable formula of oxime ester compound (c4), as particularly suitable compound, the compound of following formula can be enumerated.
[changing 14]
[changing 15]
[changing 16]
[changing 17]
[changing 18]
[changing 19]
[changing 20]
When (C) Photoepolymerizationinitiater initiater contains oxime ester compound, (C) Photoepolymerizationinitiater initiater preferably only containing oxime ester compound, but also can contain the compound beyond oxime ester compound.(C) content of the compound beyond the oxime ester compound in Photoepolymerizationinitiater initiater is preferably below 10 quality % relative to the gross mass of (C) Photoepolymerizationinitiater initiater, is more preferably below 5 quality %, is particularly preferably below 3 quality %.
(C) content of Photoepolymerizationinitiater initiater is preferably 1 ~ 15 quality % relative to the quality of the solid constituent in photosensitive polymer combination.By being set as above-mentioned scope, easily preparing and having good coating and the photosensitive polymer combination of curability concurrently.
< (D) opacifier >
Photosensitive polymer combination contains the opacifier comprising the carbon black after utilizing the silane coupling agent represented by following formula (1) to process.When photosensitive polymer combination contains the carbon black after utilizing the silane coupling agent represented by following formula (1) to process as (D) opacifier, use sense photosensitive resin composition, easily formed to the adaptation of substrate and insulativity excellent and inhibit the pattern of the reduction because heating the insulativity caused.(D) carbon black contained by opacifier also can be processed by the silane coupling agent represented by two or more formula of combination (1).
(D) opacifier is do not hinder can containing the colorant beyond carbon black for objects such as the adjustments of tone within the scope of the object of the invention.(D) opacifier, particularly carbon black preferably use spreading agent to disperse.Below, about (D) opacifier, the process of carbon black carried out the colorant utilized beyond silane coupling agent, carbon black, carbon black, silane coupling agent successively and the process for dispersing of carbon black are described.
(silane coupling agent)
(D) opacifier contains the carbon black after utilizing the silane coupling agent represented by following formula (1) to process.
R 1 pR 2 (3-p)Si-R 3-NH-C(O)-Y-R 4-X…(1)
(in formula (1), R 1for alkoxy, R 2for alkyl, p is the integer of 1 ~ 3, R 3for alkylidene, Y is-NH-,-O-or-S-, R 4for singly-bound or alkylidene, X is the nitrogen-containing hetero aryl can with substituent, monocycle or many rings, in X with-Y-R 4the ring of-bonding is nitrogenous hexa-atomic aromatic rings ,-Y-R 4-with the carbon atom bonding in above-mentioned nitrogenous hexa-atomic aromatic rings.)
In formula (1), R 1for alkoxy.For R 1, the carbon number of alkoxy is preferably 1 ~ 6, is more preferably 1 ~ 4, from reactive viewpoint of silane coupling agent, is particularly preferably 1 or 2.As R 1preferred concrete example, can enumerate: methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy and just own oxygen base.In these alkoxys, preferred methoxyl and ethoxy.
By making alkoxy R 1the silanol group generated through hydrolysis, to react containing the functional group of active hydrogen atom with the hydroxyl, carboxyl etc. on the surface being present in carbon black, thus the surface bond of silane coupling agent and carbon black.Therefore, from the view point of the surface making silane coupling agent easily be bonded to carbon black, p is preferably 3.
In formula (1), R 2for alkyl.For R 2, the carbon number of alkyl is preferably 1 ~ 12, is more preferably 1 ~ 6, from reactive viewpoint of silane coupling agent, is particularly preferably 1 or 2.As R 2preferred concrete example, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base and dodecyl.
In formula (1), R 3for alkylidene.For R 3, the carbon number of alkylidene is preferably 1 ~ 12, is more preferably 1 ~ 6, is particularly preferably 2 ~ 4.As R 3preferred concrete example, can enumerate: methylene, 1, 2-ethylidene, 1, 1-ethylidene, propane-1, 3-bis-base, propane-1, 2-bis-base, propane-1, 1-bis-base, propane-2, 2-bis-base, butane-1, 4-bis-base, butane-1, 3-bis-base, butane-1, 2-bis-base, butane-1, 1-bis-base, butane-2, 2-bis-base, butane-2, 3-bis-base, pentane-1, 5-bis-base, pentane-1, 4-bis-base, and hexane-1, 6-bis-base, heptane-1, 7-bis-base, octane-1, 8-bis-base, nonane-1, 9-bis-base, decane-1, 10-bis-base, undecane-1, 11-bis-base and dodecane-1, 12-bis-base.In these alkylidenes, preferably 1,2-ethylidene, propane-1,3-bis-base and butane-Isosorbide-5-Nitrae-two base.
Y is-NH-,-O-or-S-, is preferably-NH-.This is because compared with the key represented by-CO-O-or-CO-S-, the key represented by-CO-NH-is not vulnerable to hydrolysis.Use comprise utilize Y be the photosensitive polymer combination of carbon black after the compound of-NH-processes as silane coupling agent to form pattern when, the structure of silane coupling agent can not change because of the process based on alkaline developer etc., therefore easily obtains the effect desired by obtaining by using silane coupling agent.
R 4for singly-bound or alkylidene, be preferably singly-bound.R 4for preferred example when alkylidene and R 3identical.
X is the nitrogen-containing hetero aryl can with substituent, monocycle or many rings, in X with-Y-R 4the ring of-bonding is nitrogenous hexa-atomic aromatic rings ,-Y-R 4-with the carbon atom bonding in this nitrogenous hexa-atomic aromatic rings.Although reason is not clear, uses when comprising the photosensitive polymer combination of compound as silane coupling agent with such X, the solidfied material of the adaptation to base material, water tolerance and excellent solvent resistance can be formed.
When X is polyheteroaromatic, heteroaryl both can be the group of multiple monocycle condensation, also can for multiple monocycle is by the group of singly bound.When X is polyheteroaromatic, the number of rings contained by polyheteroaromatic is preferably 1 ~ 3.When X is polyheteroaromatic, heteroatoms can be comprised with the ring of the nitrogenous hexa-atomic aromatic rings condensation in X or bonding and also can not comprise heteroatoms, can be that aromatic rings may not be aromatic rings.
As the substituting group that the X for nitrogen-containing hetero aryl can have, can enumerate: the aliphatic acyl radical of the thiazolinyl of the alkyl of carbon number 1 ~ 6, the alkoxy of carbon number 1 ~ 6, carbon number 2 ~ 6, the alkene oxygen base of carbon number 2 ~ 6, carbon number 2 ~ 6, benzoyl, nitro, nitroso-, amino, hydroxyl, sulfydryl, cyano group, sulfonic group, carboxyl and halogen atom etc.The substituent number that X has is not particularly limited in the scope not hindering object of the present invention.The substituent number that X has is preferably less than 5, is more preferably less than 3.Under X has multiple substituent situation, multiple substituting group can be the same or different.
As the preferred example of X, the group of following formula can be enumerated.
[changing 21]
In above-mentioned group, as the group of X more preferably following formula.
[changing 22]
As the concrete example be applicable to of the compound represented by described above, formula (1), following compound 1 ~ 8 can be enumerated.
[changing 23]
(carbon black)
Carbon black is not particularly limited in the scope not hindering object of the present invention, can from known carbon black suitable choice for use.As carbon black, channel black, furnace black, thermal black, the known carbon black such as dim can be used.
In addition, as carbon black, preferably use the carbon black implementing the process introducing acidic-group.Use and comprise when introducing photosensitive polymer combination as (D) opacifier of the carbon black of acidic-group, there is the advantage that the pattern that easily forms insulativity excellence is such, exist but then and be difficult to be formed to such bad of the fine pattern of the excellent adhesion of substrate.But, by utilizing the silane coupling agent represented by above-mentioned formula (1) to process introducing the carbon black of acidic-group, can eliminate above-mentioned about bad to the adaptation of substrate of pattern.
The acidic-group introducing carbon black is the functional group of the display acidity based on bronsted definition.As the concrete example of acidic-group, can enumerate: carboxyl, sulfonic group, phosphate etc.The acidic-group introducing carbon black can form salt.The kation forming salt with acidic-group is not particularly limited in the scope not hindering object of the present invention.As cationic example, can enumerate: the kation, ammonium ion etc. of each metal ion species, nitrogen-containing compound, alkali metal ion, the ammonium ions such as preferred sodion, potassium ion, lithium ion.
Described above implement introduce acidic-group process carbon black in, preferably there is the carbon black of the functional group of more than a kind of being selected from carboxylic acid group, carboxylate group, sulfonic group and sulphonate-base.
The method introducing acidic-group to carbon black is not particularly limited.As the method introducing acidic-group, such as, following methods can be enumerated.
1) by using the direct method of substitution of the concentrated sulphuric acid, oleum, chlorosulfonic acid etc. or using the indirect method of substitution of sulphite, hydrosulfite etc., sulfonic method is introduced to carbon black.
2) the amino and organic compound of acidic-group and the method for carbon black generation diazo coupling is made to have.
3) make to have the organic compound of halogen atom and acidic-group, carried out the method for reacting by Williamson's etherification method with the carbon black with hydroxyl.
4) method making to have the organic compound of the acidic-group of halo carbonyl and the protection of protected base, react with the carbon black with hydroxyl.
5) use the organic compound of the acidic-group with halo carbonyl and the protection of protected base, the reaction of Fu's row Dare Kerafyrm thatch is carried out to carbon black, then carries out the method for deprotection.
In these methods, from the view point of the introducing process of acidic-group easily and safety, method for optimizing 2).As method 2) the middle organic compound with amino and acidic-group used, on aromatic group, be preferably bonded with compound that is amino and acidic-group.As the example of such compound, can enumerate: the aminobenzoic acid that the such aminobenzenesulfonic acid of sulfanilic acid, PABA are such.
The molal quantity of the acidic-group introduced in carbon black is not particularly limited in the scope not hindering object of the present invention.The molal quantity of the acidic-group introduced in carbon black is preferably 1 ~ 200mmol relative to carbon black 100g, is more preferably 5 ~ 100mmol.
Carbon black can implement the coating treatment utilizing resin.Use comprise utilize resin-coated after the photosensitive polymer combination of carbon black time, be easy to be formed light-proofness and insulativity is excellent, surface reflectivity is low pattern.As the example of coating resin that can be used in carbon black, can enumerate: the heat-curing resins such as phenolics, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin, alkyl benzene resin; The thermoplastic resins such as polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, Noryl, polysulfones, polyparaphenylene terephthalamide, polyamidoimide, polyimide, PABM, polyethersulfone, PPSU, polyarylate, polyetheretherketone.When the total amount of carbon black and resin is set to 100 mass parts, resin-phase is preferably 1 ~ 30 mass parts for the amount of coating of carbon black.
(colorant beyond carbon black)
For the object etc. of adjustment tone, (D) opacifier can comprise the pigment of black pigment beyond carbon black, the colour such as red, blue, green, yellow, purple together with carbon black.As the black pigment beyond carbon black, can enumerate that: perylene pigment, silver-colored ashbury metal, titanium are black, the metal oxide of copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver etc., composite oxides, metal sulfide, metal sulfate or metal carbonate etc.When the gross mass of (D) opacifier is set to 100 mass parts, the consumption of the colorant beyond carbon black is preferably below 15 mass parts, is more preferably below 10 mass parts.
(process of the carbon black utilizing silane coupling agent to carry out)
The disposal route based on silane coupling agent of carbon black is not particularly limited in the scope not hindering object of the present invention.Typically, preferably in the solvable organic solvent of silane coupling agent, the method that in presence of water carbon black and silane coupling agent reacted.
As the organic solvent that can be applicable in the process of the carbon black utilizing silane coupling agent to carry out using, can enumerate: the monovalence alkanols such as methyl alcohol, ethanol, n-propanol, isopropyl alcohol and normal butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, TEG, polyglycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, ammediol, Isopropanediol, polypropylene glycol, pentanediol, propylene glycol, butylene glycol, i-butylene glycol, thio-diethylene glycol, 1,2-hexanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 1,2-pentanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 1, ammediol, BDO, 1,7-heptandiol, 1,8-ethohexadiol and 2-butene-1, the polyalcohols such as 4-glycol and glycerine, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, the tertiary butyl ether of ethylene glycol list, ethylene glycol ether, ethyleneglycol monopropylether, ethylene glycol list phenyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list isopropyl ether, diethylene glycol monobutyl ether, the tertiary butyl ether of diethylene glycol list, Triethylene glycol ethyl ether, triethylene glycol butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, propylene glycol t-butyl ether, propylene glycol monopropyl ether, monoisopropyl ether, propylene glycol list phenyl ether, dipropylene glycol monomethyl ether, DPE, Dipropylene glycol mono-n-butyl Ether, the glycol ethers such as dipropylene glycol monopropyl ether and dipropylene glycol list isopropyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol ether acetic acid esters, ethylene glycol monomethyl ether acetate, ethylene glycol list phenyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, Diethylene glycol monopropyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol list phenyl ether acetate, butyl carbitol acetate, diethylene glycol monoethyl ether acetic acid esters, acetic acid 2-methoxybutyl, acetic acid 3-methoxybutyl, acetic acid 4-methoxybutyl, acetic acid 3-methyl-3-methoxybutyl, acetic acid 3-ethyl-3-methoxybutyl, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, acetic acid 2-Ethoxybutyl, acetic acid 4-Ethoxybutyl, acetic acid 4-propoxyl group butyl ester, acetic acid 2-methoxyl pentyl ester, acetic acid 3-methoxyl pentyl ester, acetic acid 4-methoxyl pentyl ester, acetic acid 2-methyl-3-methoxyl pentyl ester, acetic acid 3-methyl-3-methoxyl pentyl ester, the diol alcohol esters such as acetic acid 3-methyl-4-methoxyl pentyl ester and acetic acid 4-methyl-4-methoxyl pentyl ester, the ketones solvents such as acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone.For the consumption of organic solvent, as long as the amount that easily can stir the treating fluid containing carbon black and silane coupling agent is just not particularly limited.The solid component concentration of the treating fluid that the consumption of organic solvent is preferably containing carbon black and silane coupling agent reaches the amount of 5 ~ 60 quality %.
For the consumption of silane coupling agent, be just not particularly limited as long as desired effect can be obtained.The consumption of silane coupling agent is preferably 0.5 ~ 15 mass parts relative to carbon black 100 mass parts, is more preferably 3 ~ 7 mass parts.
The process of the carbon black utilizing silane coupling agent to carry out is carried out in the presence of water.Water can be added in the treating fluid containing carbon black and silane coupling agent, but and not necessarily need water to be added in treating fluid.When the process utilizing silane coupling agent to carry out is carried out under the air atmosphere containing abundant moisture, alkoxy hydrolysis silane coupling agent being had by the moisture in air, generates silanol group.
Temperature when processing carbon black for utilizing silane coupling agent, as long as the reaction of silane coupling agent and carbon black is just not particularly limited well.The process of the carbon black utilizing silane coupling agent to carry out is typically preferred to be carried out at 25 ~ 100 DEG C, more preferably carries out at 40 ~ 60 DEG C.
After utilizing silane coupling agent to process carbon black according to the method described above, the suspending liquid of the carbon black obtained after process can be directly used in the dispersion liquid of (D) opacifier, the preparation of photosensitive polymer combination.In addition, also by after the suspending liquid drying of carbon black that obtains after process, obtained pulverous carbon black can be used for the dispersion liquid of (D) opacifier, the preparation of photosensitive polymer combination.
It should be noted that, when (D) opacifier contains the colorant beyond carbon black, also can carry out the process based on the silane coupling agent represented by formula (1) for the colorant beyond carbon black in the same manner as carbon black.In addition, the process can also carrying out based on silane coupling agent to (D) opacifier of the potpourri as the colorant beyond carbon black and carbon black.
(process for dispersing of carbon black)
As mentioned above, the carbon black contained by (D) opacifier preferably uses spreading agent to disperse.The form of the dispersion liquid utilizing the carbon black after dispersant usually to obtain to utilize spreading agent to carry out dispersion treatment to carbon black in dispersion medium uses.The preparation method of the dispersion liquid of carbon black is not particularly limited, prepared by the preparation method by the dispersion liquid of in the past known various pigment.
As the example be applicable to of the preparation method of dispersion liquid, the method using known diverting device to process the suspending liquid comprising dispersion medium, carbon black and spreading agent can be enumerated.Below, other compositions that the preparation method of carbon black dispersion liquid, spreading agent, dispersion medium and carbon black dispersion liquid can contain are described.
[preparation method of carbon black dispersion liquid]
As the diverting device used in the dispersion treatment of carbon black, the various diverting devices in the past used in the dispersion of pigment can be used.As the concrete example of the diverting device be applicable to, can enumerate: the process of kneader, salt mill kneader, roller mill, planetary-type mixer, paint mixer, bowl mill, sand mill, attitor, ball mill, annular space bowl mill, homomixer, homogenizer, wet shotcrete technology grinding machine, high-pressure homogenizer, ultrasonic homogenizer etc.When diverting device use medium, as this medium, beaded glass, zirconium oxide bead, alumina bead, magnetic beads, styrene pearl etc. can be used.
When utilizing ultrasonic homogenizer to carry out dispersion treatment, preferred use utilize in advance above-mentioned kneader, salt grind process kneader, roller mill, planetary-type mixer, homomixer, homogenizer, wet shotcrete technology grinding machine, high-pressure homogenizer and ball mill etc. carry out pre-dispersed after carbon black.
[spreading agent]
For the kind of spreading agent, as long as carbon black can be made to disperse well to be just not particularly limited.Since can using in the past for pigment dispersion various spreading agents as spreading agent.As the example be applicable to of spreading agent, macromolecule dispersing agent, the pigment derivative etc. such as polyethyleneimine system macromolecule dispersing agent, carbamate resins system macromolecule dispersing agent and acrylic resin macromolecule dispersing agent can be enumerated.Macromolecule dispersing agent, pigment derivative use the amount same with the amount used when the dispersion treatment of pigment in the past.
In addition, also the spreading agent comprising polyamic acid is preferably used to make carbon black dispersion.Use the photosensitive polymer combination containing (D) opacifier comprising carbon black, wherein said carbon black uses the dispersant and the carbon black that obtains that comprise polyamic acid, in this case, the pattern that inhibit because heating the insulativity reduction caused easily is formed.
Think that the strand of polyamic acid is by hydrogen bond, the interaction such with the intermolecular force of carbon blacksurface and on the surface of carbon black primary particle to combine.Therefore think, in the surface of the primary particle of carbon black, the strand of polyamic acid plays the effect of sept, while the dispersion promoting carbon black, makes decentralized stabilization.Therefore, containing comprising in the photosensitive polymer combination of (D) opacifier of the carbon black using polyamic acid to disperse as spreading agent, not easily there is the aggegation of carbon black.
The molecular weight of polyamic acid is preferably 5,000 ~ 30,000 in matter average molecular weight, is more preferably 10,000 ~ 20,000.When the molecular weight of polyamic acid is in above-mentioned scope, carbon black can be made to disperse well.
For the consumption of polyamic acid, as long as make carbon black disperse well to be just not particularly limited.From the view point of the easiness of the dispersion of carbon black, polyamic acid preferably uses 20 ~ 80 mass parts relative to carbon black 100 mass parts, more preferably uses 30 ~ 70 mass parts.
As the polyamic acid be applicable to, such as, can enumerate the polyamic acid of the Component units comprised represented by following formula (D1).
[changing 24]
(in formula (D1), R d1for quadrivalent organic radical group, R d2for divalent organic group, the repeat number of the Component units of n represented by formula (D1).)
In formula (D1), R d1and R d2be respectively quadrivalent organic radical group, its carbon number is preferably 2 ~ 50, is more preferably 2 ~ 30.R d1and R d2respectively can for aliphatic group, aromatic group, combine the group of their structure.R d1and R d2halogen atom, oxygen atom and sulphur atom can also be comprised beyond carbon atom and hydrogen atom.R d1and R d2when comprising oxygen atom, nitrogen-atoms or sulphur atom, oxygen atom, nitrogen-atoms or sulphur atom can be selected from nitrogen heterocycle ,-CONH-,-NH-,-N=N-,-CH=N-,-COO-,-O-,-CO-,-SO-,-SO 2-, the mode of the group of-S-and-S-S-is included in R d1and R d2in, more preferably to be selected from-O-,-CO-,-SO-,-SO 2-, the mode of the group of-S-and-S-S-is included in R d1and R d2in.
Polyamic acid is usually by making tetracarboxylic dianhydride's composition and diamine component react to prepare.Below, the manufacture method for the preparation of tetracarboxylic dianhydride's composition of polyamic acid, diamine component and polyamic acid is described.
Tetracarboxylic dianhydride's composition
For be used as polyamic acid synthesis material tetracarboxylic dianhydride's composition for, as long as the compound that can react with diamine component and form polyamic acid is just not particularly limited.Tetracarboxylic dianhydride's composition can be used as suitably to select the tetracarboxylic dianhydride of the synthesis material of polyamic acid since in the past.Tetracarboxylic dianhydride's composition can be aromatic tetracarboxylic acid's dianhydride, also can be aliphatics tetracarboxylic dianhydride, is preferably aromatic tetracarboxylic acid's dianhydride.Tetracarboxylic dianhydride's composition can combinationally use two or more.
As the concrete example be applicable to of aromatic tetracarboxylic acid's dianhydride, can enumerate: pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4, the two phthalic anhydride and 3 of 4 '-oxygen, 3 ', 4,4 '-diphenylsulfone acid dianhydride etc.Among these, from price, easiness etc. of starting with, preferably 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride and pyromellitic acid anhydride.
Diamine component
For be used as polyamic acid synthesis material diamine component for, as long as the compound that can react with tetracarboxylic dianhydride's composition and form polyamic acid is just not particularly limited.Diamine component can be used as suitably to select the diamines of the synthesis material of polyamic acid since in the past.Diamine component can be aromatic diamine also can be aliphatic diamine, optimization aromatic diamines.Diamine component can combinationally use two or more.
As the concrete example be applicable to of aromatic diamine, can enumerate: p-phenylenediamine (PPD), m-phenylene diamine, 2, 4-diaminotoluene, 4, 4 '-benzidine, 4, 4 '-diamido-2, 2 '-bis-(trifluoromethyl) biphenyl, 3, 3 '-diamino diphenyl sulfone, 4, 4 '-diamino diphenyl sulfone, 4, 4 '-diaminodiphenyl sulfide, 4, 4 '-diaminodiphenyl-methane, 4, 4 '-diamino-diphenyl ether, 3, 4 '-diamino-diphenyl ether, 3, 3 '-diamino-diphenyl ether, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 4, 4 '-bis-(4-amino-benzene oxygen) biphenyl, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two [4-(3-amino-benzene oxygen) phenyl] sulfone, 2, two [4-(4-amino-benzene oxygen) phenyl] propane and 2 of 2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-etc.Among these, from price, easiness etc. of starting with, preferred p-phenylenediamine (PPD), m-phenylene diamine, 2,4-diaminotoluenes and 4,4 '-diamino-diphenyl ether.
The manufacture method of polyamic acid
By making tetracarboxylic dianhydride's composition described above and diamine component react in the solvent that can dissolve both, polyamic acid can be obtained.Tetracarboxylic dianhydride's composition during synthesizing polyamides acid and the consumption of diamine component are not particularly limited.Relative to tetracarboxylic dianhydride's composition 1 mole, preferably use the diamine component of 0.50 ~ 1.50 mole, more preferably use 0.60 ~ 1.30 mole, particularly preferably use 0.70 ~ 1.20 mole.
As the solvent that can use in the synthesis of polyamic acid, such as can enumerate: N, N, N ', N '-tetramethylurea, METHYLPYRROLIDONE, N, the aprotic polar organic solvents such as dinethylformamide, DMA, hexamethyl phosphoramide, DMI and gamma-butyrolacton; The glycol ethers such as diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene-glycol monoalky lether acetic acid esters and propylene-glycol monoalky lether propionic ester.These solvents can combinationally use two or more.Among these, preferably use N, N, N ', N '-tetramethylurea.
For the consumption of solvent during synthesizing polyamides acid, as long as the polyamic acid that can synthesize desired molecular weight is just not particularly limited.Typically, relative to total 100 mass parts of the amount of tetracarboxylic dianhydride's composition and the amount of diamine component, the consumption of solvent is preferably 100 ~ 4000 mass parts, is more preferably 150 ~ 2000 mass parts.
For temperature when reacting for making tetracarboxylic dianhydride's composition and diamine component, as long as reaction is just not particularly limited well.Typically, the temperature of reaction of tetracarboxylic dianhydride's composition and diamine component is preferably-5 ~ 150 DEG C, is more preferably 0 ~ 120 DEG C, is particularly preferably 0 ~ 70 DEG C.In addition, the time that tetracarboxylic dianhydride's composition and diamine component are reacted is different and different because of temperature of reaction, but typically, preferably 1 ~ 50 hour, more preferably 2 ~ 40 hours, particularly preferably 5 ~ 30 hours.
[dispersion medium]
For dispersion medium when making carbon black dispersion, as long as carbon black can be made to disperse well to be just not particularly limited.Dispersion medium can for since in the past as the liquid medium of dispersion medium when making carbon black dispersion, suitably can select from the solvable medium of spreading agent.Typically, preferred polar organic solvent is as dispersion medium.Dispersion medium can contain water in the solvable scope of spreading agent.
As the concrete example be applicable to of dispersion medium, can enumerate: water, ethylene glycol, diethylene glycol, triethylene glycol, TEG, polyglycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, ammediol, Isopropanediol, polypropylene glycol, pentanediol, trimethylene, butylene glycol, i-butylene glycol, thio-diethylene glycol, 1,2-hexanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 1,2-pentanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 1, ammediol, BDO, 1,7-heptandiol, 1,8-ethohexadiol and 2-butene-1, the polyalcohols such as 4-glycol, glycerine, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, the tertiary butyl ether of ethylene glycol list, ethylene glycol ether, ethyleneglycol monopropylether, ethylene glycol list phenyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list isopropyl ether, diethylene glycol monobutyl ether, the tertiary butyl ether of diethylene glycol list, Triethylene glycol ethyl ether, triethylene glycol butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, propylene glycol t-butyl ether, propylene glycol monopropyl ether, monoisopropyl ether, propylene glycol list phenyl ether, dipropylene glycol monomethyl ether, DPE, Dipropylene glycol mono-n-butyl Ether, the polyvalent alcohol ethers such as dipropylene glycol monopropyl ether and dipropylene glycol list isopropyl ether, the ketones such as acetonyl acetone, the ester classes such as gamma-butyrolacton, diacetine, triethyl phosphate, the lower alkoxy such as 2-methyl cellosolve and cellosolvo alcohols, the amines such as monoethanolamine, diethanolamine, triethanolamine, N methyldiethanol amine, N-ethyldiethanolamine, trien, tetren and five methyl diethylentriamine, the amide-types such as formamide, DMF, N-METHYLFORMAMIDE and DMA, N, N, N ', N '-tetramethylurea and N, N, N ', the ureas such as N '-tetraethyl urea, 2-Pyrrolidone, N-ethyl-2-pyrrolidone, METHYLPYRROLIDONE, cyclohexyl pyrrolidone, morpholine, N-ethylmorpholine, 2-oxazolidone, 1, the heterocycles such as 3-dimethyl-2-imidazolinone, imidazoles, methylimidazole, hydroxy imidazole, dimethyl aminopyridine, PS, hydroxyethyl piperazine and piperazine, the sulfoxide types such as dimethyl sulfoxide (DMSO), the sulfone classes such as sulfolane.N, N, N described above ', the solvent beyond N '-tetramethylurea can combine two or more and be included in containing N, N, N ', in the solvent of N '-tetramethylurea.
In dispersion medium described above, preferably containing N, N, N ', the organic solvent of N '-tetramethylurea.Containing N, N, N ', in the organic solvent of N '-tetramethylurea, by making carbon black dispersion using polyamic acid as spreading agent, can make carbon black rapidly and disperseing well.
For containing N, N, N ', the N in the organic solvent of N '-tetramethylurea, N, N ', the content of N '-tetramethylurea, as long as be just not particularly limited in the scope making the disperse state of carbon black keep good.Typically, containing N, N, N ', the N in the organic solvent of N '-tetramethylurea, N, N ', the content of N '-tetramethylurea is preferably more than 50 quality %, is more preferably more than 70 quality %, is particularly preferably more than 90 quality %, most preferably is 100 quality %.
For the content of the dispersion medium in carbon black dispersion liquid, as long as make the disperse state of carbon black keep well just being not particularly limited.Carbon black dispersion liquid usually reaches 5 ~ 60 quality %, the preferably mode of the amount of 20 ~ 40 quality % with the solid component concentration of carbon black dispersion liquid and contains dispersion medium.
[other compositions]
Carbon black dispersion liquid can comprise the various adjuvants be in the past engaged in carbon black dispersion liquid.As such adjuvant, can enumerate: viscosity modifier, surfactant, antioxidant, ultraviolet light absorber, pH adjusting agent and defoamer etc.These adjuvants bring in dysgenic scope in the character not to carbon black dispersion liquid can use the amount same with the amount be engaged in carbon black dispersion liquid in the past.
The content of (D) opacifier in photosensitive polymer combination suitably can be selected in the scope not hindering object of the present invention, typically, relative to the total solid composition of photosensitive polymer combination, be preferably 25 ~ 70 quality %, be more preferably 30 ~ 65 quality %, be particularly preferably 35 ~ 60 quality %.By using the opacifier of the amount of above-mentioned scope, use sense photosensitive resin composition can be made and the light-proofness of the black matrix that formed or black column spacer is good, and easily suppress ill-exposed when photosensitive polymer combination is exposed and solidify bad.
< (E) light absorber >
Photosensitive polymer combination can contain light absorber.As light absorber, be not particularly limited, the compound that can absorb exposure light can be used, particularly preferably absorb the compound of the light of the wavelength region may of 200 ~ 450nm.Such as can enumerate: naphthalene compound, two naphthalene compounds, anthracene compound, phenanthroline compounds, dyestuff etc.
Specifically, can enumerate: the cinnamic acid derivatives such as cinnamic acid 2-Octyl Nitrite, Neo Heliopan AV, methoxycinnamate isopropyl propionate, methoxycinnamate isoamyl valerate; Alpha-Naphthol, betanaphthol, alpha-Naphthol methyl ether, alpha-Naphthol ethylether, 1,2-dihydroxy naphthlene, 1,3-dihydroxy naphthlene, Isosorbide-5-Nitrae-dihydroxy naphthlene, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene, 1,7-dihydroxy naphthlene, 1,8-dihydroxy naphthlene, 2,3-dihydroxy naphthlenes, 2, the naphthalene derivativeses such as 6-dihydroxy naphthlene, 2,7-dihydroxy naphthlenes; Anthracene and the derivants thereof such as anthracene, 9,10-dihydroxy-anthracenes; The dyestuffs such as azo based dye, benzophenone based dye, amino ketones based dye, quinoline based dye, anthraquinone based dye, diphenylcyanoacrylate based dye, triazine based dye, p-aminobenzoic acid based dye; Deng.Wherein, preferably use cinnamic acid derivative, naphthalene derivatives, particularly preferably use cinnamic acid derivative.These light absorbers may be used singly or in combin two or more.
(E) content of light absorber is preferably 0.5 ~ 20 mass parts relative to solid constituent 100 mass parts of photosensitive polymer combination.By being set as above-mentioned scope, while keeping the breakdown strength after solidifying well, the ratio of Thickness Variation when changing exposure can be increased.
< (S) organic solvent >
Photosensitive polymer combination is preferably containing the organic solvent for diluting.As organic solvent, such as can enumerate: glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol positive propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list positive propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol list positive propyl ether, dipropylene glycol mono-n-butyl ether, Tripropylene glycol monomethyl Ether, (gathering) alkylene glycol monoalkyl ethers such as tripropylene glycol list ether, (gathering) alkylene glycol monoalkyl ether acetate classes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, other ethers such as diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, the ketones such as methyl ethyl ketone, cyclohexanone, 2-HEPTANONE, 3-heptanone, the lactic acid alkyl ester classes such as 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl ethyl propionate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, acetic acid 3-methyl-3-methoxybutyl, propionic acid 3-methyl-3-methoxybutyl, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, other ester classes such as 2-Oxobutyric acid ethyl ester, toluene, dimethylbenzene etc. aromatic hydrocarbon based, the amide-types etc. such as 1-METHYLPYRROLIDONE, DMF, DMA.
Wherein, preferred alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetate class, other above-mentioned ethers, lactic acid alkyl ester class, other above-mentioned ester classes, more preferably alkylene glycol monoalkyl ether acetate class, other above-mentioned ethers, other above-mentioned ester classes.These solvents may be used singly or in combin two or more.
(S) content of organic solvent preferably makes the solid component concentration of photosensitive polymer combination reach the amount of 1 ~ 50 quality %, is more preferably the amount making it reach 5 ~ 30 quality %.
Other compositions of < >
Photosensitive polymer combination of the present invention can contain various adjuvant as required.As adjuvant, can enumerate: sensitizer, curing accelerator, filling agent, closely sealed promoter, antioxidant, anticoalescent, thermal polymerization inhibitor, defoamer, surfactant etc.
As closely sealed promoter, preferred silane coupling agent.Independent of the silane coupling agent represented by the formula used in the process of carbon black (1), silane coupling agent is coordinated to photosensitive polymer combination, can obtain thus forming the photosensitive polymer combination to the extremely excellent pattern of the adaptation of substrate.
As closely sealed promoter silane coupling agent can silane coupling agent represented by above-mentioned formula (1) also can silane coupling agent beyond the silane coupling agent represented by formula (1).
As the example be applicable to of the silane coupling agent beyond the silane coupling agent represented by formula (1), can enumerate: N-2-(amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, N-2-(amino-ethyl)-APTES, 3-TSL 8330, APTES and 3-triethoxysilyl-N-(1,3-dimethyl-Ding support group) propyl group amine.
" the formation method of the solidfied material of patterning "
The formation method of the solidfied material of patterning of the present invention comprises: above-mentioned photosensitive polymer combination is coated operation substrate being formed coated film; The contrast shape of pattern and operation that regioselectivity ground exposes formed coated film; With the operation making the coated film after exposure develop.
First, in the operation forming coated film, the substrate of solidfied material that will form patterning uses roll coater, reverses non-contact type apparatus for coating such as the contact such as coating machine, bar coater transfer printing type apparatus for coating or whirler (rotary apparatus for coating), curtain curtain coater etc., photosensitive resin coating composition.After coating, remove desolventizing by dry as required, thus form coated film.
Then, across negative-appearing image type mask, to coated film irradiation ultraviolet radiation, excimer laser isoreactivity energy-ray, with the shape of pattern accordingly to the partial exposure of coated film.In exposure, high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp, carbon arc lamp etc. can be used to send ultraviolet light source.Exposure is different according to the composition of photosensitive polymer combination, and preference is as 10 ~ 600mJ/cm 2left and right.
It should be noted that, TFT substrate etc. on the substrate that its surface possesses element, be formed with black column spacer as solidfied material, sometimes to need on element or the substrate paired with the substrate being formed with element with elements relative to position form black column spacer.In this case, consider the height of element, need the height changing black column spacer at the position and other positions that are formed with element.Therefore, in this case, preferably expose across half-tone mask.
Then, utilize developer solution to develop to the coated film after position optionally exposes, form solidfied material thus.Developing method is not particularly limited, and can use infusion process, gunite etc.As the concrete example of developer solution, can enumerate: the developer solution of the organic systems such as monoethanolamine, diethanolamine, triethanolamine; The aqueous solution of NaOH, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt etc.
Then, cure after as required the insoluble part of the coated film after development being implemented, form the solidfied material of patterning.After cure and preferably at 150 ~ 250 DEG C, carry out 15 ~ 60 minutes.
The adaptation to substrate of the solidfied material of the patterning of formation like this and insulativity are excellent, inhibit the reduction of the insulativity caused because of thermal conductance, are therefore suitable as the black matrix in various display device, black column spacer.
Embodiment
Below, illustrate that embodiment specifically describes the present invention further, but scope of the present invention is not limited to these embodiments.
[embodiment 1 ~ 14 and comparative example 1 ~ 8]
After the carbon black dispersion liquid of the amount recorded in alkali soluble resin (solid component concentration 55 quality %, solvent: acetic acid 3-methoxybutyl) 114 mass parts, photopolymerization monomer 25 mass parts, Photoepolymerizationinitiater initiater 12 mass parts and table 1 is mixed, become solid component concentration to be 15 quality % with organic solvent diluting, thus obtain the photosensitive polymer combination of each embodiment and comparative example.
As the organic solvent of dilution, use the mixed solvent (mixing ratio (mass ratio) is MA/PM/AN=60/20/20) of acetic acid 3-methoxybutyl (MA), propylene glycol methyl ether acetate (PM) and cyclohexanone (AN).
As carbon black dispersion liquid, use and the spreading agent recorded in the carbon black table 1 of the kind recorded in the table 1 after utilizing the silane coupling agent recorded in table 1 to process is carried out dispersion treatment and the dispersion liquid that obtains.
It should be noted that, in the photosensitive polymer combination of embodiment 13 and 14 and comparative example 5 and 6, add closely sealed promoter 3 mass parts of the kind recorded in table 1 further.
Details for the preparation of the material of photosensitive polymer combination will be described hereinafter.
[table 1]
Below, be described for the preparation of the carbon black dispersion liquid of photosensitive polymer combination, alkali soluble resin, photopolymerization monomer and Photoepolymerizationinitiater initiater.
(carbon black dispersion liquid)
In the preparation of carbon black dispersion liquid, use following carbon black CB and CB-A.
CB: carbon black (manufacture of Regal250R, Cabot company)
CB-A: carbon black that prepare by the following method, that implement the process introducing acidic-group.
As the silane coupling agent used in the process of carbon black, use following SC-A, SC-B and SC-C.In following silane coupling agent, SC-A and SC-C is also used as closely sealed promoter.
[changing 25]
When utilizing silane coupling agent to process carbon black, the process based on silane coupling agent is carried out by the following method.
[preparation example of CB-A]
Joining carbon black CB (manufacture of Regal250R, Cabot company) 550g, sulfanilic acid 31.5g and ion exchange water 1000g by jacket temperature set is 60 DEG C possess in the reaction vessel of chuck and stirring apparatus.The solution obtained being dissolved with sodium nitrite 12.6g in deionized water 100g adds after in Bo Lang (Block ラ ウ) stirrer, is stirred 2 hours by the potpourri in stirrer, carry out diazo coupling under the condition of 60 DEG C, 50 revs/min.After stirring, the content of stirrer is cooled to room temperature.Then, the carbon black purifying using deionized water will to be contained in the content of stirrer by diafiltration.From washings, the benzene sulfonic acid class deriving from sulfanilic acid do not detected, knownly in carbon black, introduce benzene sulfonic acid base by diazo coupling.Carbon black after purifying is pulverized after 75 DEG C of drying one nights, obtains the carbon black (CB-A) introducing benzene sulfonic acid base.
[silane coupling agent process]
The aqueous isopropanol 200g of silane coupling agent of the carbon black 50g of the kind recorded in table 1 and the silane coupling agent that contains the kind recorded in table 1 with the concentration of 1 quality % mix, 60 DEG C of stirrings 3 hours.The suspending liquid containing carbon black after stirring is heated to 100 DEG C, makes the methyl alcohol volatilization that isopropyl alcohol and accessory substance generate, thus obtain the powder of the carbon black after utilizing silane coupling agent to process.
As spreading agent, use following DP-A and DP-B, prepare carbon black dispersion liquid by the following method.
DP-A: carbamate system macromolecule dispersing agent (BYK-167, Japanese BYK Co., Ltd. manufacture)
DP-B: polyamic acid (pyromellitic acid anhydride (PMDA) and 4,1/1 (mol ratio) reactant of 4 '-diamino-diphenyl ether (ODA), matter average molecular weight: 14000)
[carbon black dispersion liquid preparation example]
The spreading agent 3g of the kind recorded in untreated or carbon black 20g after utilizing the silane coupling agent of kind recorded in table 1 to process, table 1 and acetic acid 3-methoxybutyl 50g is mixed.Obtained mixed liquor is stirred, makes carbon black dispersion.Then, utilize acetic acid 3-methoxybutyl that the suspending liquid comprising scattered carbon black is diluted to solid component concentration 22 quality %, obtain carbon black dispersion liquid.
(alkali soluble resin)
As alkali soluble resin, use following A-1.
A-1: the resin (solid constituent 55%, solvent: acetic acid 3-methoxybutyl) obtained by following method
[alkali soluble resin synthesis example]
First, bisphenol fluorene type epoxy resin (epoxide equivalent 235) 235g, tetramethyl ammonium chloride 110mg, 2 is added in 500ml four-hole boiling flask, 6-di-tert-butyl-4-methy phenol 100mg and acrylic acid 72.0g, be blown into air wherein with the speed of 25ml/ minute while at 90 ~ 100 DEG C heating for dissolving.Then, slowly heat up under the state that solution is gonorrhoea, be heated to 120 DEG C, make it dissolve completely.Now, solution becomes clear viscous gradually, continues in this case to stir.During this period, measure acid number, continue to add thermal agitation until acid number is less than 1.0mgKOH/g.Until acid number reaches desired value need 12 hours.Then, be cooled to room temperature, obtain water white transparency and the bisphenol fluorene type epoxy acrylate represented by following formula (a-4) of solid shape.
[changing 26]
Then, in the above-mentioned bisphenol fluorene type epoxy acrylate 307.0g obtained in a manner described, add acetic acid 3-methoxybutyl 600g and make it dissolve, then mix benzophenone tetracarboxylic dianhydride 80.5g and tetraethylammonium bromide 1g, slowly heat up, at 110 ~ 115 DEG C, make it react 4 hours.After confirming anhydride group disappearance, mixing 1,2,3,6-tetrabydrophthalic anhydride 38.0g, makes it react 6 hours, obtains resin (A-1) at 90 DEG C.IR spectrum is utilized to confirm the disappearance of anhydride group.
It should be noted that, this resin (A-1) is equivalent to the resin represented by above-mentioned formula (a-1).
(photopolymerization monomer)
DPHA: dipentaerythritol acrylate
(Photoepolymerizationinitiater initiater)
OXE02: ethyl ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base], 1-(O-acetyl group oxime) (" IRGACUREOXE02 " that BASF manufactures)
For the solidfied material of the patterning that the photosensitive polymer combination of each embodiment of obtained use and comparative example is formed, by the following method, the surface resistance after fine rule adaptation, initial surface resistivity and thermal treatment is evaluated.These evaluation results are remembered in table 2.
[evaluation of fine rule adaptation]
Use spin coater to be coated on by photosensitive polymer combination after on glass substrate (100mm × 100mm), prebake 120 seconds at 90 DEG C, forms the coated film of thickness 1.0 μm.Then, use mirror surface projection to aim at exposer (ProductName: TME-150RTO, Co., Ltd. TOPCON system), exposing clearance is set to 50 μm, across negative mask with 30mJ/cm 2exposure to coated film irradiation ultraviolet radiation, wherein, described negative mask is designed to: be formed with the line and gap (ラ イ Application ア Application De ス ペ ー ス: Line-and-space) pattern that possess in the scope of 5 μm ~ 20 μm, make width 16 kinds of lines of each change 1 μm from 5 μm.Coated film after exposure, is cured after carrying out 30 minutes at 230 DEG C after 50 seconds with the 0.04 quality %KOH aqueous development of 26 DEG C, thus formation line and space pattern.
The line utilizing observation by light microscope to be formed and space pattern, evaluate fine rule adaptation according to following benchmark.
◎: all the line of width does not find to peel off.
Zero: the line of width 5 μm and 6 μm finds to peel off, but the line of width more than 7 μm does not find stripping.
△: the line that width is 5 ~ 8 μm finds to peel off, but the line of width more than 9 μm does not find to peel off.
×: the line that width is 5 ~ 12 μm finds to peel off.
[evaluation of initial surface resistivity and thermal treatment rear surface resistance]
In the same manner as the evaluation of fine rule adaptation, at the upper film forming thickness 1.0 μm of glass substrate (100mm × 100mm).Then, use mirror surface projection aim at exposer (ProductName: TME-150RTO, Co., Ltd. TOPCON system), make exposing clearance be set to 50 μm, not across photomask to film irradiation ultraviolet radiation.Exposure is set as 100mJ/cm 2.Utilize the 0.04 quality %KOH aqueous development of 26 DEG C after 50 seconds the film after exposure, cure 30 minutes after at 230 DEG C, produce cured film thus.Determine the sheet resistance value of this cured film as initial surface resistivity.After this cured film is at 230 DEG C, cure 3 hours further, measure the sheet resistance value of the cured film after implementing further thermal treatment as thermal treatment rear surface resistance.
[table 2]
According to embodiment 1 ~ 14: when using containing (A) alkali soluble resin, (B) photopolymerization monomer, (C) Photoepolymerizationinitiater initiater and comprise the photosensitive polymer combination of (D) opacifier of the carbon black after utilizing the silane coupling agent of the regulation structure represented by formula (1) to process, the black pattern that the adaptation of substrate and the excellent and insulativity of insulativity are not easily reduced because of heating can be formed.
According to embodiment 1 ~ 4 contrast with embodiment 5 ~ 8: (D) opacifier comprise utilize above-mentioned silane coupling agent to process the carbon black after implementing the process introducing acidic-group and obtain carbon black when, the easily black pattern of formation insulativity excellence.
Contrast according to the contrast of embodiment 2 and embodiment 4, embodiment 6 and embodiment 8: (D) opacifier comprises and uses polyamic acid as spreading agent when dispersed carbon black, especially easily suppresses the insulativity reduction caused because of heating of the black pattern formed.
According to embodiment 2 contrast with embodiment 13 and 14: the silane coupling agent used in independent of the process of carbon black, when making photosensitive polymer combination also comprise silane coupling agent as closely sealed promoter, the black pattern that the adaptation of fine rule is excellent especially can be formed.
According to comparative example 1,2,5 and 6: when using process and the photosensitive polymer combination based on (D) opacifier of the carbon black of the process of silane coupling agent not implementing to introduce acidic-group containing (A) alkali soluble resin, (B) photopolymerization monomer, (C) Photoepolymerizationinitiater initiater and comprising, define the black pattern of poor insulativity.
According to comparative example 3 and 4: use when implementing the process of introducing acidic-group containing (A) alkali soluble resin, (B) photopolymerization monomer, (C) Photoepolymerizationinitiater initiater and comprising but do not implement the photosensitive polymer combination of (D) opacifier of the carbon black of the process based on silane coupling agent, define the excellent black pattern that adaptation is obviously poor but then of insulativity.
According to the contrast of comparative example 2 with comparative example 7: even if the silane coupling agent of the structure beyond the formula of utilization (1) processes the carbon black contained in (D) opacifier, the insulativity of formed black pattern can not be improved.
More known according to comparative example 4 and comparative example 8: when (D) opacifier comprises the carbon black implementing the process introducing acidic-group, even if the silane coupling agent of the structure beyond the formula of utilization (1) processes carbon black, the insulativity of formed black pattern can not be improved.

Claims (10)

1. a photosensitive polymer combination, it comprises (A) alkali soluble resin, (B) photopolymerization monomer, (C) Photoepolymerizationinitiater initiater and (D) opacifier,
Described (D) opacifier comprises the carbon black after utilizing the silane coupling agent represented by following formula (1) to process,
R 1 pR 2 (3-p)Si-R 3-NH-C(O)-Y-R 4-X…(1)
In formula (1), R 1for alkoxy, R 2for alkyl, p is the integer of 1 ~ 3, R 3for alkylidene, Y is-NH-,-O-or-S-, R 4for singly-bound or alkylidene, X is the nitrogen-containing hetero aryl or do not have with substituent, monocycle or many rings, in X with-Y-R 4the ring of-bonding is nitrogenous hexa-atomic aromatic rings ,-Y-R 4-with the carbon atom bonding in described nitrogenous hexa-atomic aromatic rings.
2. photosensitive polymer combination as claimed in claim 1, wherein, described carbon black is the carbon black utilizing described silane coupling agent to process the carbon black after implementing the process introducing acidic-group.
3. photosensitive polymer combination as claimed in claim 2, wherein, described in implement the process introducing acidic-group after carbon black there is the functional group of more than a kind in the group being selected from and being made up of carboxylic acid group, carboxylate group, sulfonic group and sulphonate-base.
4. the photosensitive polymer combination according to any one of claims 1 to 3, wherein, described carbon black uses spreading agent to disperse, and described spreading agent contains polyamic acid.
5. photosensitive polymer combination as claimed in claim 1, wherein, the content of the carbon black after utilizing described silane coupling agent to carry out surface treatment is 25 ~ 70 quality % relative to the quality of the solid constituent in photosensitive polymer combination.
6. a formation method for the solidfied material of patterning, it comprises:
Photosensitive polymer combination according to claim 1 is coated on operation substrate being formed coated film;
The operation described coated film exposed regioselectivity; With
By the operation of the described coated film development after exposure.
7. a solidfied material for patterning, it uses the photosensitive polymer combination described in claim 1 to be formed.
8. the solidfied material of patterning as claimed in claim 7, it is black matrix or black column spacer.
9. a display device, it possesses and uses photosensitive polymer combination described in claim 1 and the black matrix that formed or black column spacer.
10. a carbon black, it is the carbon black after utilizing the silane coupling agent represented by following formula (1) to process,
R 1 pR 2 (3-p)Si-R 3-NH-C(O)-Y-R 4-X…(1)
In formula (1), R 1for alkoxy, R 2for alkyl, p is the integer of 1 ~ 3, R 3for alkylidene, Y is-NH-,-O-or-S-, R 4for singly-bound or alkylidene, X is the nitrogen-containing hetero aryl or do not have with substituent, monocycle or many rings, in X with-Y-R 4the ring of-bonding is nitrogenous hexa-atomic aromatic rings ,-Y-R 4-with the carbon atom bonding in described nitrogenous hexa-atomic aromatic rings.
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