JP6301249B2 - Photosensitive composition - Google Patents

Description

  The present invention relates to a photosensitive composition containing a silane coupling agent comprising a blocked isocyanate silane, a colored photosensitive composition obtained by adding a colorant to the photosensitive composition, and a black matrix using the colored photosensitive composition. Specifically, the present invention relates to a colored photosensitive composition having excellent adhesion to a substrate and a black matrix using the same.

  The photosensitive resin composition is a photocurable resin composition, and a typical composition includes a compound having an ethylenically unsaturated bond and a photopolymerization initiator. Since this photosensitive resin composition can be polymerized and cured by irradiation with ultraviolet rays or electron beams, it is used in photocurable inks, photosensitive printing plates, printed wiring plates, various photoresists, and the like.

  In particular, a colored photosensitive resin composition using carbon black as a pigment is useful as a black matrix provided at a boundary portion between R, G, and B colored layers of a color filter in order to enhance display contrast and color development effect.

  With respect to such a colored photosensitive composition, the black pattern (black matrix) obtained through exposure, development and post-cure and the adhesion of the transparent substrate are not sufficient, and a peeling process for forming a black pattern is performed. In the course of repetition, some of the previously formed colored patterns are peeled off at the same time, and there are problems that the pattern may be lost or the exposed and cured part may not remain on the transparent substrate.

Patent Document 1 discloses a colored pixel containing a compound having both a functional group chemically bonded to a transparent substrate and a functional group of a component in the photosensitive coloring material and a polymerizable functional group, particularly a silane coupling agent. A photosensitive coloring material for pattern formation is disclosed.
Patent Documents 2 to 4 disclose silane coupling agents composed of a blocked isocyanate silane having a specific structure.

JP 2004-191724 A JP 08-291186 A JP-A-10-067787 JP 2009-144255 A

  However, the invention described in Patent Document 1 is limited to pattern formation by dry development using a dry film, and there is still room for improvement in adhesiveness with a substrate. In addition, cited references 2 to 4 do not describe or suggest that the silane coupling agents described in the respective references are used for the photosensitive resin composition.

  Therefore, the objective of this invention is providing the photosensitive composition which can form a desired pattern, and the colored photosensitive composition which improved the adhesiveness to the base material of a colored pattern.

  As a result of intensive studies to solve the above problems, the present inventors have found that a photosensitive composition containing a silane coupling agent composed of a predetermined blocked isocyanate silane can achieve the above-described object, Further, the present inventors have found that a colored photosensitive composition obtained by adding a colorant to the photosensitive composition is suitable for a black matrix, and have reached the present invention.

（式中、Ｒ^１は、炭素原子数１〜８のアルキル基を表し、ｎは１〜１０の数であり、ａは１〜３の数であり、ｂは０〜２の数であり、ａ＋ｂ＝３である。） That is, the photosensitive composition of the present invention contains a silane coupling agent comprising a blocked isocyanate silane which is a reaction product of an isocyanate compound represented by the following general formula (I) and a blocking agent. The blocking agent is an oxime compound or pyrazole other than fluorenone oxime.

(In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms, n is a number of 1 to 10, a is a number of 1 to 3, b is a number of 0 to 2, a + b = 3.)

  Moreover, the photosensitive composition of this invention contains the silane coupling agent which consists of the said block isocyanate silane. Furthermore, the colored photosensitive composition of the present invention is characterized in that a colorant is added to the photosensitive composition.

  The photosensitive composition and colored photosensitive composition of the present invention preferably contain a polymerizable compound having an ethylenically unsaturated bond and a photopolymerization initiator.

  Moreover, it is preferable that the colored photosensitive composition of this invention contains a black pigment.

  Moreover, it is preferable that the photosensitive composition and colored photosensitive composition of this invention are alkali developability.

  The black matrix of the present invention is a cured product of the colored photosensitive composition on a substrate.

  The color filter of the present invention comprises the above black matrix.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive composition which can form a desired pattern can be provided, the coloring photosensitive composition which improved the adhesiveness to the base material of a coloring pattern, and a black matrix using the same are provided. It becomes possible. The cured product of the colored photosensitive composition of the present invention is suitable for a color filter for a display device, a liquid crystal display panel, and an organic EL display panel.

  Hereinafter, the photosensitive composition and colored photosensitive composition of this invention are demonstrated based on preferable embodiment.

The photosensitive composition of the present invention comprises a blocked isocyanate silane obtained by reacting the isocyanate compound represented by the general formula (I) with a blocking agent. As other components, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and the like are preferable, but not limited thereto.
Further, the colored photosensitive composition of the present invention is obtained by adding a colorant to the photosensitive composition of the present invention. The colorant preferably contains a black pigment such as carbon black. By containing a black pigment, it becomes useful as a photosensitive composition for forming a black matrix. Furthermore, since it can develop without burdening the environment, it is preferably alkaline developability.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹ in the general formula (I) include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, and pentyl. , Iso-pentyl, tert-pentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso- Examples include octyl and tert-octyl.

In the above general formula (I), R ¹ is preferably methyl, ethyl or propyl from the viewpoint of easy availability of raw materials.
Moreover, it is preferable from the point of a boiling point that n is 2-4. The boiling point is preferably higher than the pre-bake temperature or the post-bake temperature.
Moreover, it is preferable from the point of adhesiveness that a is 3 and b is 0.

As the blocking agent used for obtaining the blocked isocyanate silane used in the present invention, those conventionally used can be used. For example, carboxylic acid esters such as dimethyl malonate and diethyl malonate: active methylene compounds such as malonic acid, acetylacetone, acetoacetate (methyl acetoacetate, ethyl acetoacetate, etc.); formamide oxime, acetamide oxime, acetoxime, Oxime compounds such as diacetyl monooxime, benzophenone oxime, cyclohexanone oxime, methyl ethyl ketoxime (MEK oxime), methyl isobutyl ketoxime (MIBK oxime), dimethyl ketoxime, diethyl ketoxime; methanol, ethanol, propanol, butanol, 2-ethylhexanol , Monohydric alcohols such as heptanol, hexanol, octanol, isononyl alcohol, stearyl alcohol, benzyl alcohol Are these isomers; methyl glycol, ethyl glycol, ethyl diglycol, ethyl triglycol, butyl glycol, butyl diglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, etc. Glycol derivatives; phenols such as phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, octylphenol, nonylphenol, nitrophenol, chlorophenol or their isomers: hydroxyl-containing esters such as methyl lactate and amyl lactate; dibutylamine, Diisopropylamine, di-tert-butylamine, di-2-ethylhexylamine, dicyclohexyl Amine compounds such as silamine, benzylamine, diphenylamine, aniline and carbazole; imine compounds such as ethyleneimine and polyethyleneimine; alcohol amines such as monomethylethanolamine, diethylethanolamine and triethylethanolamine; α-pyrrolidone, β-butyrolactam, β -Lactams such as propiolactam, γ-butyrolactam, δ-valerolactam, ε-caprolactam; mercaptans such as butyl mercaptan, hexyl mercaptan, dodecyl mercaptan; imidazoles such as imidazole and 2-ethylimidazole; acetanilide, acrylamide, Acid amides such as acetic acid amide and dimer acid amide; acid imides such as succinimide, maleic acid imide and phthalic acid imide; urea, thiourea, ethyl Examples include urea compounds such as lenurea; benzotriazoles; pyrazoles such as 3,5-dimethylpyrazole, and the like. These may be used alone or in combination of two or more.
Among the above blocking agents, those having a dissociation temperature of 100 to 200 ° C. are preferable because they exist stably during pre-baking and react during post-baking, and oxime compounds are particularly preferable.

  The blocking reaction for obtaining the blocked isocyanate silane is performed by a known reaction method. The addition amount of the blocking agent is usually 1 to 2 equivalents, preferably 1.05 to 1.5 equivalents, relative to the free isocyanate group. The reaction temperature of the blocking reaction is usually 50 to 150 ° C, preferably 60 to 120 ° C. The reaction time is preferably about 1 to 7 hours. Moreover, you may add a catalyst and a solvent (Aromatic hydrocarbon type | system | group, ester type | system | group, ether type, a ketone type | system | group, these 2 or more types of mixed solvents, etc.).

  In the photosensitive composition of the present invention, the content of the silane coupling agent is 0.1 to 30% by mass, particularly 0.5 to 10% by mass in terms of solid content in the photosensitive composition of the present invention. . When the content of the silane coupling agent is less than 0.1% by mass, the adhesion may be insufficient. When the content is greater than 30% by mass, the silane coupling agent is precipitated in the photosensitive composition. There is.

  A polymerizable compound having an ethylenically unsaturated bond can be used in the photosensitive composition of the present invention. The polymerizable compound having an ethylenically unsaturated bond is not particularly limited, and those conventionally used in photosensitive compositions can be used. For example, ethylene, propylene, butylene, isobutylene, vinyl chloride can be used. , Unsaturated aliphatic hydrocarbons such as vinylidene chloride, vinylidene fluoride, tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, highmic acid, crotonic acid, Isocrotonic acid, vinyl acetate, allyl acetate, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω- Carboxypolycaprolactone mono (meth) acrylate has carboxy group and hydroxyl group at both ends Mono (meth) acrylate of polymer; having hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or one carboxyl group and two or more (meth) acryloyl groups Unsaturated polybasic acids such as polyfunctional (meth) acrylates; (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, glycidyl (meth) acrylate, the following compound No. A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meta ) Ethylhexyl acrylate, (meth) acrylic acid Enoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-anhydrous Acid anhydrides of unsaturated polybasic acids such as rain acid adducts, dodecenyl succinic anhydride, methyl hymic anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyvalent amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyl toluene, vinyl benzoic acid, vinyl Unsaturated aromatic compounds such as ruphenol, vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; maleimide, N-phenylmaleimide, N -Unsaturated imides such as cyclohexylmaleimide; Indenes such as indene and 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene Macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, etc .; vinyl chloride, vinylidene chloride, divinyl succi Narate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomer and polyisocyanate compound vinyl urethane compound, hydroxyl group content The vinyl epoxy compound of a vinyl monomer and a polyepoxy compound is mentioned.

Compound No. A1

Compound No. A2

Compound No. A3

Compound No. A4

  Examples of the polymerizable compound having an ethylenically unsaturated bond include acrylic ester copolymers, phenol and / or cresol novolac epoxy resins, polyphenylmethane type epoxy resins having polyfunctional epoxy groups, and epoxy acrylate resins. A resin obtained by allowing an unsaturated monobasic acid to act on an epoxy compound such as an epoxy compound represented by the following general formula (II), and further causing a polybasic acid anhydride to act thereon can also be used. Among these, a resin obtained by allowing an unsaturated monobasic acid to act on an epoxy compound such as an epoxy compound represented by the following general formula (II) and further causing a polybasic acid anhydride to act thereon is preferable. Moreover, it is preferable that these compounds contain 0.2-1.0 equivalent of unsaturated groups.

（式中、Ｘ^１は直接結合、メチレン基、炭素原子数１〜４のアルキリデン基、炭素原子数３〜２０の脂環式炭化水素基、Ｏ、Ｓ、ＳＯ_２、ＳＳ、ＳＯ、ＣＯ、ＯＣＯ又は下記式（ｉ）、（ｉｉ）若しくは（ｉｉｉ）で表される置換基を表し、上記アルキリデン基はハロゲン原子で置換されていてもよく、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子、炭素原子数１〜５のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数２〜５のアルケニル基又はハロゲン原子を表し、上記アルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されていてもよく、ｍは０〜１０の整数であり、ｍが０で無いときに存在する光学異性体は、どの異性体でもよい。）

(In the formula, X ¹ is a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, O, S, SO ₂ , SS, SO, CO, It represents a substituent represented by OCO or the following formula (i), (ii) or (iii), the alkylidene group may be substituted with a halogen atom, and R ² , R ³ , R ⁴ and R ⁵ are Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a halogen atom, and the above alkyl group, alkoxy group, and The alkenyl group may be substituted with a halogen atom, m is an integer of 0 to 10, and the optical isomer present when m is not 0 may be any isomer.)

（式中、Ｚ^１は水素原子、炭素原子数１〜１０のアルキル基若しくは炭素原子数１〜１０のアルコキシ基により置換されていてもよいフェニル基、又は炭素原子数１〜１０のアルキル基若しくは炭素原子数１〜１０のアルコキシ基により置換されていてもよい炭素原子数３〜１０のシクロアルキル基を示し、Ｙ^１は炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のアルケニル基又はハロゲン原子を示し、上記アルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されていてもよく、ｂは０〜５の整数である。）

(In the formula, Z ¹ represents a hydrogen atom, a phenyl group optionally substituted by an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, or A cycloalkyl group having 3 to 10 carbon atoms which may be substituted by an alkoxy group having 1 to 10 carbon atoms, Y ¹ is an alkyl group having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms Group, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and b is an integer of 0 to 5).

（式中、Ｙ^２及びＺ^２は、それぞれ独立して、ハロゲン原子で置換されていてもよい炭素原子数１〜１０のアルキル基、ハロゲン原子で置換されていてもよい炭素原子数６〜２０のアリール基、ハロゲン原子で置換されていてもよい炭素原子数６〜２０のアリールオキシ基、ハロゲン原子で置換されていてもよい炭素原子数６〜２０のアリールチオ基、ハロゲン原子で置換されていてもよい炭素原子数６〜２０のアリールアルケニル基、ハロゲン原子で置換されていてもよい炭素原子数７〜２０のアリールアルキル基、ハロゲン原子で置換されていてもよい炭素原子数２〜２０の複素環基、又はハロゲン原子を表し、上記アルキル基及びアリールアルキル基中のアルキレン部分は、不飽和結合、−Ｏ−又は−Ｓ−で中断されていてもよく、Ｚ^２は、隣接するＺ^２同士で環を形成していてもよく、ｐは０〜４の整数を表し、ｑは０〜８の整数を表し、ｒは０〜４の整数を表し、ｓは０〜４の整数を表し、ｒとｓの数の合計は２〜４の整数である。）

Wherein Y ² and Z ² are each independently an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or 6 to 20 carbon atoms which may be substituted with a halogen atom. An aryloxy group having 6 to 20 carbon atoms which may be substituted with a halogen atom, an arylthio group having 6 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom An arylalkenyl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms that may be substituted with a halogen atom, or a complex having 2 to 20 carbon atoms that may be substituted with a halogen atom Represents a cyclic group, or a halogen atom, and the alkylene moiety in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, ^2, may form a ring with the adjacent ^{Z 2} together, p represents an integer of 0 to 4, q represents an integer of 0 to 8, r represents an integer of 0 to 4, s is The integer of 0-4 is represented, and the sum total of the number of r and s is an integer of 2-4.)

  Examples of the unsaturated monobasic acid that acts on the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl Acrylate / malate, dicyclopentadiene / malate, and the like.

  In addition, the polybasic acid anhydride to be acted after the unsaturated monobasic acid is allowed to act is biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, Trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydrophthalic anhydride , Methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene -1,2-dicarboxylic anhydride, trialkyl tet Anhydride - maleic acid adduct, dodecenyl succinic anhydride, and anhydride and methyl high Mick acid.

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows.
That is, in the epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound, the hydroxyl group of the epoxy adduct is 1 It is preferable that the acid anhydride structure of the polybasic acid anhydride has a ratio of 0.1 to 1.0.
Reaction of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride can be performed in accordance with a conventional method.

  As the polymerizable compound having an ethylenically unsaturated bond, a polymer represented by the following general formula (III) can also be used.

（式中、Ｘ_１１は水素原子又はメチル基を表し、Ｙ_１１は、二価の結合基であり、Ｒ_１１は、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜２０のアリールアルキル基を表し、該アルキル基、アリール基及びアリールアルキル基は、ハロゲン原子、水酸基又はニトロ基で置換されていてもよく、該アルキル基及びアリールアルキル基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−又は−ＮＨ−、あるいはこれらの組み合わせの結合基で中断されていてもよく、Ｒ_１２、Ｒ_１３及びＲ_１４は、それぞれ独立に、水素原子又は炭素原子であり、０．１≦ｔ≦０．６５、０．３≦ｍ≦０．８、０≦ｎ≦０．２であり、ｔ＋ｍ＋ｎ＝１である。）

(In the formula, X ₁₁ represents a hydrogen atom or a methyl group, Y ₁₁ is a divalent linking group, R ₁₁ is an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Or an arylalkyl group having 7 to 20 carbon atoms, and the alkyl group, aryl group and arylalkyl group may be substituted with a halogen atom, a hydroxyl group or a nitro group, The methylene group may be interrupted by a linking group of —O—, —S—, —CO—, —COO—, —OCO— or —NH—, or a combination thereof, R ₁₂ , R ₁₃ and R ₁₄ are each independently a hydrogen atom or a carbon atom, 0.1 ≦ t ≦ 0.65, 0.3 ≦ m ≦ 0.8, 0 ≦ n ≦ 0.2, and t + m + n = 1. .)

Examples of the divalent linking group represented by Y ₁₁ in the general formula (III) include a structure represented by the following formula (1).

（式中、Ｘ^１１は、−ＣＲ^２０Ｒ^２１−、−ＮＲ^２０−、二価の炭素原子数１〜３５の鎖状炭化水素基、二価の炭素原子数３〜３５の脂環式炭化水素基、二価の炭素原子数６〜３５の芳香族炭化水素基又は二価の炭素原子数２〜３５の複素環基、さらにこれらの基を複数組み合わせた基を表し、Ｒ^２０及びＲ^２１は、水素原子、炭素原子数１〜８のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜２０のアリールアルキル基を表し、Ｚ^１１及びＺ^１２は、それぞれ独立に、直接結合、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＳＯ−、−ＮＲ^１０−、−ＰＲ^１０−を表し、Ｒ^１０は、水素原子、炭素原子数１〜８のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜２０のアリールアルキル基を表し、該アルキル基、アリール基及びアリールアルキル基は、ハロゲン原子、水酸基又はニトロ基で置換されていてもよく、該アルキル基及びアリールアルキル基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−又は−ＮＨ−、あるいはこれらの組み合わせの結合基で中断されていてもよい。但し、上記一般式（１）で表される基は炭素原子数１〜３５の範囲内である。）

(In the formula, X ¹¹ is —CR ²⁰ R ²¹ —, —NR ²⁰ —, a divalent chain hydrocarbon group having 1 to 35 carbon atoms, and a divalent carbon atom having 3 to 35 alicyclic carbonization. Represents a hydrogen group, a divalent aromatic hydrocarbon group having 6 to 35 carbon atoms or a divalent heterocyclic group having 2 to 35 carbon atoms, and a group obtained by combining a plurality of these groups, and R ²⁰ and R ²¹ Represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, and Z ¹¹ and Z ¹² are each independently _{bond, -O -, - S -,} - SO 2 -, - SO -, - NR 10 -, - PR 10 - ^{represents, R 10} is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, carbon atoms Represents an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, The alkyl group, aryl group and arylalkyl group may be substituted with a halogen atom, a hydroxyl group or a nitro group, and the methylene group in the alkyl group and arylalkyl group may be represented by —O—, —S—, —CO—. , —COO—, —OCO—, —NH—, or a combination thereof may be interrupted, provided that the group represented by the general formula (1) has a range of 1 to 35 carbon atoms. Within.)

Among the polymerizable compounds having an ethylenically unsaturated bond, when a compound having an acid value is used, alkali developability can be imparted to the photosensitive composition of the present invention. When using the compound which has the said acid value, it is preferable to make the usage-amount become 50-99 mass% of the whole polymeric compound which has the said ethylenically unsaturated bond.
The compound having an acid value can be used after adjusting the acid value by further reacting with a monofunctional or polyfunctional epoxy compound. The alkali developability of the photosensitive resin can be improved by adjusting the acid value of the compound having an acid value. The compound having an acid value (that is, a polymerizable compound having an ethylenically unsaturated bond imparting alkali developability) preferably has a solid content acid value in the range of 5 to 120 mgKOH / g, and is monofunctional or polyfunctional. The amount of the functional epoxy compound used is preferably selected so as to satisfy the acid value.

  Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl. Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidylate , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether Ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinyl Cyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, propylene oxide, the above compound No.A2, No. A3 etc. are mentioned.

As the polyfunctional epoxy compound, it is preferable to use one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers because a colored photosensitive resin composition with better characteristics can be obtained.
As the bisphenol-type epoxy compound, an epoxy compound represented by the general formula (II) can be used, and for example, a bisphenol-type epoxy compound such as a hydrogenated bisphenol-type epoxy compound can also be used.
Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl Ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-to (Glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) can be used such as methane.
Other novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxies such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl P-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as pentadiene dioxide; naphthalene type epoxy compounds; triphenylmethane type epoxy compounds; dicyclopentadiene type epoxy compounds can also be used.

  In addition, the photosensitive composition of the present invention may contain a compound that does not have an ethylenically unsaturated bond and imparts alkali developability. As such a compound, an alkaline aqueous solution can be obtained by having an acid value. Although it is not particularly limited as long as it is a compound soluble in water, a typical example is an alkali-soluble novolak resin (hereinafter simply referred to as “novolak resin”). The novolak resin is obtained by polycondensation of phenols and aldehydes in the presence of an acid catalyst.

  Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2- Methyl resorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester and the like are used. Among these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,5-xy Nord, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methyl resorcinol and bisphenol A are preferred. These phenols are used alone or in combination.

  Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o -Chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p N-butylbenzaldehyde and the like are used, and among these compounds, formal Dehydr, acetaldehyde and benzaldehyde are preferred. These aldehydes may be used alone or in combination of two or more. Aldehydes are preferably used in a proportion of 0.7 to 3 mol, particularly preferably 0.7 to 2 mol, per mol of phenol.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, or organic acids such as formic acid, oxalic acid, and acetic acid. The amount of these acid catalysts used is preferably 1 × 10 ^{−4 to} 5 × 10 ⁻¹ mol per mole of phenols. In the condensation reaction, water is usually used as a reaction medium. However, if the phenols used in the condensation reaction do not dissolve in an aqueous solution of aldehydes and become heterogeneous from the beginning of the reaction, the reaction medium is hydrophilic. A solvent can also be used. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol and butanol, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 to 1000 parts by mass per 100 parts by mass of the reaction raw material. Although the reaction temperature of a condensation reaction can be suitably adjusted according to the reactivity of a reaction raw material, it is 10-200 degreeC normally, Preferably it is 70-150 degreeC. After completion of the condensation reaction, in order to remove unreacted raw materials, acid catalyst and reaction medium present in the system, the internal temperature is generally increased to 130 to 230 ° C., and the volatile component is distilled off under reduced pressure. Next, the melted novolac resin is collected on a steel belt or the like.
After completion of the condensation reaction, the reaction mixture is dissolved in the hydrophilic solvent and added to a precipitating agent such as water, n-hexane or n-heptane to precipitate a novolak resin, and the precipitate is separated and dried by heating. It can also be recovered by doing so.

  Examples of compounds other than the novolak resin that do not have an ethylenically unsaturated bond and impart alkali developability include polyhydroxystyrene or a derivative thereof, a styrene-maleic anhydride copolymer, and polyvinylhydroxybenzoate. It is done.

  A photopolymerization initiator can be used in the photosensitive composition of the present invention. As the photopolymerization initiator, conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethyl ketal, 1-benzyl-1-dimethyl Amino-1- (4′-morpholinobenzoyl) propane, 2-morpholyl-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone, 4 -Benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4'-isopropyl) benzoylpropane, 4-butylbenzene Zoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9'-acridinyl) heptane, 9-n-butyl-3,6-bis (2'-morpholinoisobutyroyl) carbazole, 2 -Methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s -Triazine, 2,2-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1-2'-biimidazole, 4,4-azobisisobutyronitrile, triphenylphosphine, Examples include camphorquinone and benzoyl peroxide. Commercially available products include N-1414, N-1717, N-1919, and PZ. 408, (manufactured by (Corporation) ADEKA Corporation) NCI-831, NCI-930, IRGACURE369, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02 (BASF (Co.) Co., Ltd.).

  In the photosensitive composition of the present invention, the content of the photopolymerization initiator is preferably 0.1 to 30% by mass, particularly preferably 0.5 to 10% by mass in the photosensitive composition of the present invention. When the content of the photopolymerization initiator is less than 0.1% by mass, curing by exposure may be insufficient, and when it is greater than 30% by mass, the initiator may be precipitated in the photosensitive composition. is there.

  A colorant can be further added to the photosensitive composition of the present invention to obtain a colored photosensitive composition. Examples of the colorant include inorganic color materials and organic color materials. These color materials may be used alone or in combination of two or more.

Examples of the inorganic colorant and organic colorant include, for example, nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridones. Compound, anthanthrone compound, perinone compound, perylene compound, diketopyrrolopyrrole compound, thioindigo compound, dioxazine compound, triphenylmethane compound, quinophthalone compound, naphthalenetetracarboxylic acid; azo dye, metal complex compound of cyanine dye; lake pigment; Carbon black obtained by the method, channel method, thermal method, or carbon black such as acetylene black, ketjen black or lamp black; -Bon black adjusted with epoxy resin, coated, carbon black previously dispersed with resin in solvent, 20-200 mg / g resin adsorbed, carbon black treated with acidic or alkaline surface, An average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, and a total oxygen amount calculated from CO and CO ₂ in a volatile content at 950 ° C. of 9 mg or more per 100 m ² of the surface area of carbon black; Graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin, chromium oxide green, miloli blue, cobalt green, Cobalt blue, man Cancer system, ferrocyanide, phosphate ultramarine, bitumen, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red rose (red iron (III) oxide), cadmium red, synthetic iron black Inorganic pigments such as amber or organic pigments can be used.

  Commercially available pigments can also be used as the inorganic color material and the organic color material, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 3, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, and the like.

  As the inorganic color material and organic color material, known dyes can be used. Known dyes include, for example, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, Examples thereof include phthalocyanine dyes and cyanine dyes.

  In the colored photosensitive composition of the present invention, the content of the colorant is preferably 0 to 350 parts by mass, more preferably 0 to 250 parts with respect to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. Part by mass. When the amount exceeds 350 parts by mass, the light transmittance of the cured product using the colored photosensitive composition of the present invention and the color filter for display device is lowered, and the luminance of the display device is lowered.

  A solvent can be further added to the photosensitive composition and the colored photosensitive composition of the present invention. The solvent is usually a solvent that can dissolve or disperse the above-described components (the blocked isocyanate silane of the present invention) as necessary, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl Ketones such as isobutyl ketone, cyclohexanone, 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate Ester solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol Cellosolve solvents such as ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, pentyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl Ether ester solvents such as ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene; hexane, heptane and octane Aliphatic hydrocarbon solvents such as cyclohexane, terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits, swazol # 310 (Cosmo pine Petroleum Corporation), Solvesso # 100 (Exxon Chemical Co., Ltd.) and other paraffinic solvents; carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane and other halogenated aliphatic hydrocarbon solvents; chlorobenzene Halogenated aromatic hydrocarbon solvents such as carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl A sulfoxide, water, etc. are mentioned, These solvents may be used individually by 1 type, and may use 2 or more types together. Among these, ketones, ether ester solvents, etc., especially propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc. are used when the photosensitive composition contains a polymerizable compound having an ethylenically unsaturated bond. This is preferable because the compatibility between the compound having an ethylenically unsaturated bond and the photopolymerization initiator is good.

  In the photosensitive composition of the present invention, the solvent is preferably used so that the concentration (solid content) of the composition other than the solvent is 5 to 30% by mass. If the amount is less than 5% by mass, it is difficult to increase the film thickness and the desired wavelength light may not be sufficiently absorbed. If the amount exceeds 30% by mass, the composition is preserved by precipitation of the photosensitive composition component. This is not preferable because the properties may decrease or the viscosity may increase and handling may decrease.

  The photosensitive composition of the present invention can further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; lamellar clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper Among these, titanium oxide, silica, layered clay mineral, silver and the like are preferable. In the photosensitive composition of the present invention, the content of the inorganic compound is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. ˜20 parts by mass. These inorganic compounds may be used individually by 1 type, and may use 2 or more types together.

By containing an inorganic compound in the photosensitive composition of the present invention, it can be used as a photosensitive paste composition. The photosensitive paste composition is used to form a fired product pattern such as a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.
These inorganic compounds are also suitably used as, for example, fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellent agents, and the like.

  In the colored photosensitive composition of the present invention, when a color material such as a pigment or an inorganic compound is used, a dispersant can be added. As the dispersant, any colorant or inorganic compound can be used as long as it can disperse and stabilize, and commercially available dispersants such as BYK series manufactured by BYK Chemie can be used, and polyester having a basic functional group, Polymer dispersant made of polyether, polyurethane, having a nitrogen atom as a basic functional group, the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof, and an amine value of 1 to 100 mgKOH / g Those are preferably used.

  In addition, the photosensitive composition of the present invention includes, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; a plasticizer; an adhesion promoter; a filler; Conventional additives such as a foaming agent, a leveling agent, a surface conditioner, an antioxidant, an ultraviolet absorber, a dispersion aid, a coagulation inhibitor, a catalyst, an effect accelerator, a cross-linking agent, and a thickener can be added.

  In the photosensitive composition of the present invention, the content of optional components other than the blocked isocyanate silane, the polymerizable compound having an ethylenically unsaturated bond, and the photopolymerization initiator (excluding the solvent) depends on the purpose of use. Although it selects suitably and it does not restrict | limit in particular, Preferably it shall be 50 mass parts or less in total with respect to 100 mass parts of polymerizable compounds which have the said ethylenically unsaturated bond.

Moreover, the characteristic of the hardened | cured material which consists of the photosensitive composition of this invention can also be improved by using another organic polymer with the polymeric compound which has the said ethylenically unsaturated bond. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate. Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin, etc. are mentioned. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, epoxy resin are used. Masui.
When using another organic polymer, the usage-amount is preferably 10-500 mass parts with respect to 100 mass parts of polymeric compounds which have the said ethylenically unsaturated bond.

  In the photosensitive composition of the present invention, a monomer having an unsaturated bond, a chain transfer agent, a sensitizer, a surfactant, melamine and the like can be used in combination.

  Examples of the monomer having an unsaturated bond include: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, acrylic acid Methoxyethyl, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, methacrylic acid Tertiary butyl, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, penta Rithritol tetraacrylate, pentaerythritol triacrylate, bisphenol A diglycidyl ether (meth) acrylate, bisphenol F diglycidyl ether (meth) acrylate, bisphenol Z diglycidyl ether (meth) acrylate, tripropylene glycol di (meth) acrylate, etc. Can be mentioned.

  As the chain transfer agent and sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- Mercapto compounds such as mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Alkyl compound, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, the following compound no. C1, aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, Showen Denko Karenz MT BD1, PE1, NR1, and the like.

Compound No. C1

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

Examples of the melamine compound include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Mention may be made of compounds in which (at least two) are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used. Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.

  The photosensitive composition of the present invention is a known method such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, quartz glass, semiconductor substrate, metal, paper, plastic. It can be applied on a supporting substrate such as. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

  Moreover, as the light source of the active light used when curing the photosensitive composition of the present invention, one that emits light having a wavelength of 300 to 450 nm can be used, for example, ultrahigh pressure mercury, mercury vapor arc, carbon An arc, a xenon arc, or the like can be used.

  Furthermore, by using laser light as the exposure light source, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used, but an argon ion laser, a helium neon laser, a YAG laser, a semiconductor laser, etc. are visible to infrared region. Those that emit light are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.

  The photosensitive composition of the present invention (or a cured product thereof) is a photocurable paint or varnish, a photocurable adhesive, a printed circuit board, or a color display liquid crystal such as a color television, a PC monitor, a portable information terminal, or a digital camera. Color filters for display panels, color filters for CCD image sensors, touch panels, electrode materials for plasma display panels, powder coatings, printing inks, printing plates, adhesives, dental compositions, resin for stereolithography, gel coats, electronics For manufacturing photoresists, electroplating resists, etching resists, both liquid and dry films, solder resists, insulating films, color filters for various display applications, or plasma display panels, electroluminescent display devices, and LCDs Seal resist, electrical and electronic components to form structures in the manufacturing process 3D by composition, solder resist, magnetic recording material, micro mechanical parts, waveguide, optical switch, plating mask, etching mask, color test system, glass fiber cable coating, stencil for screen printing, stereolithography Materials for manufacturing objects, holographic recording materials, image recording materials, fine electronic circuits, decoloring materials, decoloring materials for image recording materials, decoloring materials for image recording materials using microcapsules, for printed wiring boards It can be used for various applications such as photoresist material, photoresist material for UV and visible laser direct image system, photoresist material used for dielectric layer formation in sequential lamination of printed circuit boards, or protective film, etc. There is no restriction | limiting in particular in an application.

The colored photosensitive composition of the present invention is used for the purpose of forming a black matrix. The black matrix is particularly useful for color filters for display devices for image display devices such as liquid crystal display panels.
Moreover, the color filter for display devices of the present invention may have red, green, blue, orange, purple and black optical elements in addition to the cured product of the present invention.

The black matrix includes (1) a step of forming a coating film of the colored photosensitive composition of the present invention (particularly a colored alkali-developable photosensitive composition) on a substrate, and (2) a predetermined pattern shape on the coating film. It is preferably formed by a step of irradiating active light through a mask having, (3) a step of developing a film after exposure with a developer (particularly an alkali developer), and (4) a step of heating the film after development. The In addition, the colored photosensitive composition of the present invention is also useful as a coloring composition for an ink jet system or a transfer system without a development step.
Manufacture of color filters for use in liquid crystal display panels, etc. is made by repeating the above steps (1) to (4) using the present invention or other colored compositions and combining patterns of two or more colors. Can do.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

[Production Example 1] Blocked isocyanate silane No. 1 Synthesis of 1 In a four-necked flask, 500 parts by mass of methyl ethyl ketone oxime and 100 parts by mass of propylene glycol-1-monomethyl ether-2-acetate (PGMEA) were charged in a nitrogen atmosphere, and methyl ethyl ketone oxime was dissolved in PGMEA. Next, while maintaining the internal temperature at 40 ° C. or lower, 200 parts by mass of 3-isocyanatotriethoxypropylsilane was added over 1 hour while stirring, and then stirred at an internal temperature of 40 ° C. for 1 hour. It was confirmed by IR that the peak of the isocyanate group had disappeared. 1 was obtained.

[Production Example 2] Blocked isocyanate silane no. Synthesis of 2 In a nitrogen atmosphere, 500 parts by mass of 3,5-dimethylpyrazole and 100 parts by mass of propylene glycol-1-monomethyl ether-2-acetate (PGMEA) were charged, and methyl ethyl ketone oxime was dissolved in PGMEA. Next, while maintaining the internal temperature at 40 ° C. or lower, 200 parts by mass of 3-isocyanatotriethoxypropylsilane was added over 1 hour while stirring, and then stirred at an internal temperature of 40 ° C. for 1 hour. It was confirmed by IR that the peak of the isocyanate group had disappeared, and blocked isocyanate silane No. 2 was obtained.

[Production Example 3] Alkali-developable photosensitive resin No. 3 Preparation of 1 30.0 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 7.52 g of acrylic acid, 0.080 g of 2,6-di-t-butyl-p-cresol Then, 0.183 g of tetrabutylammonium chloride and 11.0 g of PGMEA were charged and stirred at 90 ° C. for 1 hour, 105 ° C. for 1 hour and 120 ° C. for 17 hours. After cooling to room temperature, 8.11 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride and 11.1 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 12.0 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 0.080 g of 2,6-di-t-butyl-p-cresol and 0.600 g of PGMEA were added. After stirring at 90 ° C. for 90 minutes and at 120 ° C. for 5 hours, 24.0 g of PGMEA was added to obtain an alkali-developable photosensitive resin No. 1 as a PGMEA solution. 1 was obtained (Mw = 4900, Mn = 2250, acid value (solid content) 47 mg · KOH / g).

[Production Example 4] Alkali-developable photosensitive resin No. 4 Preparation of 2 184 g of bisphenolfluorene type epoxy resin (epoxy equivalent 231), 58 g of acrylic acid, 0.26 g of 2,6-di-tert-butyl-p-cresol, 0.11 g of tetra-n-butylammonium bromide and 23 g of PGMEA were charged. , And stirred at 120 ° C. for 16 hours. The reaction solution was cooled to room temperature, 35 g of PGMEA, 59 g of biphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 120 ° C. for 4 hours. Furthermore, after adding 20 g of tetrahydrophthalic anhydride, stirring at 120 ° C. for 4 hours, 100 ° C. for 3 hours, 80 ° C. for 4 hours, 60 ° C. for 6 hours, and 40 ° C. for 11 hours, PGMEA 90 g was added to add PGMEA solution As alkali-developable photosensitive resin No. 2 (Mw = 5000, Mn = 2100, acid value (solid content) 92.7 mgKOH / g).

[Production Example 5] Alkali-developable photosensitive resin no. Preparation of 3 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane 43 g, acrylic acid 11 g, 2,6-di-tert-butyl-p- 0.05 g of cresol, 0.11 g of tetrabutylammonium acetate and 23 g of PGMEA were charged and stirred at 120 ° C. for 16 hours. After cooling to room temperature, 35 g of PGMEA and 9.4 g of biphenyltetracarboxylic dianhydride were added and stirred at 120 ° C. for 8 hours. Further, 6.0 g of tetrahydrophthalic anhydride was added and stirred at 120 ° C. for 4 hours, at 100 ° C. for 3 hours, at 80 ° C. for 4 hours, at 60 ° C. for 6 hours, and at 40 ° C. for 11 hours, and then added with PGMEA 29 g to obtain a PGMEA solution As an object, an alkali-developable photosensitive resin No. 3 (Mw = 4000, Mn = 2100, acid value (solid content) 86 mgKOH / g).

[Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1-2] Colored photosensitive composition No. 1-No. 7, photosensitive composition no. 8 and comparative colored photosensitive composition no. 1-No. 2. Preparation of colored photosensitive composition No. 2 in accordance with the formulation of Table 1 and Table 2 below. 1-No. 7 (corresponding to Example 1-1 to Example 1-7, respectively), photosensitive composition no. 8 (corresponding to Example 1-8) and comparative colored photosensitive composition No. 1-No. 2 (corresponding to Comparative Example 1-1 and Comparative Example 1-2, respectively) was obtained. In addition, a number represents a mass part.

A-1 Block isocyanate silane No. 1
A-2 Block isocyanate silane No. 2
A′-1 3-isocyanatopropyltriethoxysilane A′-2 3-glycidoxypropyltriethoxysilane B-1 Alkali-developable photosensitive resin No. 1 1
B-2 Alkali-developable photosensitive resin No. 2
B-3 Alkali-developable photosensitive resin No. 3
B-4 SPC-1000 (acrylic resin; manufactured by Showa Denko)
C-1 Irgacure 907 (photopolymerization initiator; manufactured by BASF)
C-2 NCI-831 (photopolymerization initiator; manufactured by ADEKA)
C-3 N-1919 (photopolymerization initiator; manufactured by ADEKA)
C-4 NCI-930 (photopolymerization initiator; manufactured by ADEKA)
D-1 Kayarad R-684 (Tricyclodecane dimethanol diacrylate; manufactured by Nippon Kayaku Co., Ltd.)
D-2 Aronix M-405 (polyfunctional acrylate; manufactured by Toa Gosei Co., Ltd.)
D-3 Aronix M-402 (polyfunctional acrylate; manufactured by Toa Gosei Co., Ltd.)
E Carbon black (MA100; manufactured by Mitsubishi Chemical Corporation)
F-1 Cyclohexanone F-2 PGMEA

[Example 2] Photothermal curing of photosensitive composition Blocked isocyanate silane No. 2 1.0 part by mass of No. 2, 58.8 parts by mass of NK oligo EA-1020 (bisphenol A type epoxy acrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.), 39 of Aronix M-313 (polyfunctional acrylate; manufactured by Toagosei Co., Ltd.) .2 parts by mass and 1.0 part by mass of NCI-930 were kneaded with three rolls and then stirred and defoamed with a planetary mixer. It apply | coated with the dispenser on the alkali free glass of 50 mm x 25 mmx thickness 4.0mm, and the glass of the same size was bonded together. A high pressure mercury lamp (750 W) that passed through a 400 nm short wavelength cut filter was irradiated with 3000 mJ / cm ² of 405 nm light and cured at 120 ° C. for 1 hour.

[Comparative Example 2] Photothermal curing of comparative photosensitive composition Blocked isocyanate silane no. The comparative photosensitive composition was cured in the same manner as in Example 2 except that 2 was not used.

[Evaluation Examples 1-1 to 1-8 and Comparative Evaluation Examples 1-1 to 1-2]
The colored photosensitive composition Nos. Obtained in Examples 1-1 to 1-7. 1-No. 7, the photosensitive composition No. obtained in Example 1-8. 8 and comparative colored photosensitive composition Nos. Obtained in Comparative Examples 1-1 to 1-2. 1-No. 2 was coated on a glass substrate under conditions of 410 rpm × 7 seconds and dried on a hot plate (90 ° C., 90 seconds). The obtained coating film was exposed (150 mJ / cm ² ) with an ultrahigh pressure mercury lamp. A 2.5% by mass aqueous sodium carbonate solution was used as a developing solution, developed for 45 seconds with a spin developing machine, washed well with water, and post-baked at 230 ° C. for 30 minutes to fix the pattern. The following evaluation was performed about the coating film after a post-baking. The results are shown in Tables 1 and 2.

(Adhesion test)
The post-baked coating film was cut by a cross-cut tape method (cross-cut method) according to JIS K5600-5-6, and the resulting test piece was placed in a pressure cooker tester at 120 ° C / 100. The treatment was performed for 2 hours under the condition of% RH / 2 atm. The adhesion test was made by peeling the tape and counting the number of peels per 100 grids.

[Evaluation Example 2 and Comparative Evaluation Example 2]
About the test piece obtained in Example 2 and Comparative Example 2, a universal testing machine HG-200 (manufactured by Shimadzu Science Co., Ltd.) was used, and the adhesive strength was measured. The results are shown in Table 3.

  From the above results, the colored photosensitive composition of the present invention containing a silane coupling agent made of blocked isocyanate silane is excellent in adhesion. Therefore, the colored photosensitive composition of the present invention is useful for a black matrix.

Claims (11)

A photosensitive composition containing a silane coupling agent comprising a blocked isocyanate silane which is a reaction product of an isocyanate compound represented by the following general formula (I) and a blocking agent,
A photosensitive composition, wherein the blocking agent is an oxime compound or a pyrazole excluding fluorenone oxime .

(In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms, n is a number of 1 to 10, a is a number of 1 to 3, b is a number of 0 to 2, a + b = 3.)   The photosensitive composition according to claim 1, wherein the blocking agent is methyl ethyl ketone oxime.   The photosensitive composition according to claim 1, wherein the blocking agent is 3,5-dimethylpyrazole.   The photosensitive composition as described in any one of Claims 1-3 containing the polymeric compound which has an ethylenically unsaturated bond, and a photoinitiator.   It is alkali developability, The photosensitive composition as described in any one of Claims 1-4.   A colored photosensitive composition, wherein a colorant is further added to the photosensitive composition according to any one of claims 1 to 5.   The colored photosensitive composition of Claim 6 containing the polymeric compound which has an ethylenically unsaturated bond, and a photoinitiator.   The colored photosensitive composition of Claim 6 containing a black pigment.   The colored photosensitive composition according to claim 6, which is alkali developable.   A black matrix obtained by curing the colored photosensitive composition according to claim 6 on a substrate.   A color filter comprising the black matrix according to claim 10.