CN105487336A - Resin composition, black matrix, optical filter and its manufacturing method, and display device - Google Patents

Abstract

The invention provides a resin composition capable of forming a black matrix with good adhesion and good hardness, a black matrix, an optical filter and a manufacturing method thereof, and a display device. The photosensitive resin composition comprises an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), a multi-branched polymer (D), a solvent (E), and a black pigment (F). The alkali-soluble resin (a) includes a first alkali-soluble resin (a-1) represented by formula (1). The multi-branched polymer (D) is formed by reacting a multi-mercapto compound with a multi-functional (meth) acrylate.

Description

Resin composition, black matrix, optical filter, manufacturing method thereof, and display device

technical field

The invention relates to a photosensitive resin composition for a black matrix, a black matrix, a color filter, a manufacturing method thereof, and a liquid crystal display device.

Background technique

In recent years, with the vigorous development of various liquid crystal display device technologies, in order to improve the contrast and display quality of current liquid crystal display devices, stripes and dots (Stripe) and dots ( Dot) place a black matrix (BlackMatrix) in the gap. The above-mentioned black matrix can prevent problems such as a decrease in contrast (Contrast Ratio) and a decrease in color purity (Color Purity) caused by light leakage (Light Leakage) between pixels.

Generally speaking, the materials used in the black matrix are mainly evaporated films containing chromium or chromium oxide. However, when the above-mentioned evaporated film is used as the material of the black matrix, there are disadvantages such as complicated manufacturing process and expensive materials. In order to solve this problem, a technique of forming a black matrix by using a photosensitive resin composition through photolithographic printing (PhotoLithographic) has been proposed previously.

As the light-shielding properties of the black matrix are increasingly required, one of the solutions is to increase the amount of black pigment used, thereby improving the light-shielding properties of the black matrix. For example, Japanese Patent Laid-Open No. 2006-259716 discloses a photosensitive resin composition for a black matrix, which includes a high amount of black pigment, an alkali-soluble resin, a photopolymerization initiator, and a Reactive monomers and organic solvents. It is worth noting that reactive monomers with two functional groups can improve the reaction between compounds to form fine patterns (FinePattern). Thereby, in the photosensitive resin composition, while increasing the light-shielding property by increasing the usage amount of the black pigment, the sensitivity of the photosensitive resin composition can still be maintained.

In addition, Japanese Patent Laid-Open No. 2008-268854 discloses a photosensitive resin composition for a black matrix. The above-mentioned photosensitive resin composition includes an alkali-soluble resin having a carboxylic acid group and an unsaturated group, a photopolymerizable monomer having an ethylenically unsaturated group, a photopolymerization initiator, and a high amount of black pigment. In the said photosensitive resin composition for black matrices, the resolution of the photosensitive resin composition of the high usage-amount black pigment is improved by using specific alkali-soluble resin.

Although in the prior art, the photosensitive resin composition in which the amount of black pigment is used can increase the light-shielding property. However, the adhesion and hardness of the black matrix formed by the above-mentioned conventional photosensitive resin composition are not good.

Therefore, how to provide a photosensitive resin composition for a black matrix capable of forming a black matrix with good adhesion and hardness is an urgent problem for those skilled in the art.

Contents of the invention

In view of this, the present invention provides a photosensitive resin composition for a black matrix, a black matrix, a color filter and a manufacturing method thereof, and a liquid crystal display device, which can improve the problems of poor adhesion and hardness of the above-mentioned black matrix .

The invention provides a photosensitive resin composition for a black matrix, which comprises an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), and a multi-branched polymer (D) , a solvent (E) and a black pigment (F).

In detail, the alkali-soluble resin (A) includes the first alkali-soluble resin (A-1) represented by formula (1).

In formula (1), A represents phenylene or phenylene with substituents, wherein the substituents are alkyl groups with 1 to 5 carbon atoms, halogen atoms or phenyl groups; B represents -CO-, _-SO2 -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9,9-fluorenylene or single bond; L ¹ represents a fluorine-containing tetravalent carboxylic acid residue or a fluorine-free tetravalent carboxylic acid residue; Y ¹ represents a fluorine-containing divalent carboxylic acid residue or a fluorine-free divalent carboxylic acid residue R ¹ represents a hydrogen atom or a methyl group; a represents an integer from 1 to 20; L ¹ and Y ¹ , at least one of which contains a fluorine atom.

The multibranched polymer (D) is formed by reacting a polymercapto compound represented by formula (II) with a polyfunctional (meth)acrylate represented by formula (I).

Specifically, the polyfunctional (meth)acrylate represented by formula (I) is as follows.

In formula (I), R ² represents a hydrogen atom or an alkyl group with a carbon number of 1 to 4;

R ³ represents a residue after esterification of n hydroxyl groups in a hydroxyl-containing compound having m hydroxyl groups, wherein m≧n, n represents an integer from 2 to 20,

The above hydroxyl-containing compounds are R ⁴ (OH) _m or R ⁴ (OH) _m modified by propylene oxide, epichlorohydrin, alkyl, alkoxy or hydroxypropyl acrylate. qualitative compounds,

R ⁴ (OH) _m is a polyalcohol having a carbon number of 2 to 18, polyhydric alcohol ethers formed from the above polyols, esters formed by reacting the above polyols with acids, or silicon Ketones (silicone).

Polymercapto compounds represented by formula (II) are shown below.

In formula (II), R ⁵ represents a single bond, a hydrocarbon group with a carbon number of 1, or a straight-chain or branched chain hydrocarbon group with a carbon number of 2 to 22, and the skeleton of R ⁵ may also include a sulfur atom or form an ester group. the oxygen atom,

p represents an integer of 2 to 6, wherein when R ⁵ represents a single bond, p represents 2; when R ⁵ represents a hydrocarbon group with a carbon number of 1, p represents an integer of 2 to 4; when R ⁵ represents a carbon number of 2 to 4 22 linear or branched hydrocarbon groups, p represents an integer of 2 to 6.

In one embodiment of the present invention, in the above-mentioned multi-branched polymer (D), the mercapto group of the polymercapto compound represented by formula (II) is relative to the polyfunctional (meth)acrylate represented by formula (I) The addition molar ratio of the carbon-carbon double bond is 1/200 to 1/2.

In one embodiment of the present invention, the above-mentioned multi-branched polymer (D) is left after the reaction of the polymercapto compound represented by the formula (II) and the polyfunctional (meth)acrylate represented by the formula (I) The (meth)acrylate group is formed by further reacting with a mercapto compound having a carboxyl group represented by formula (III).

In formula (III), R ⁶ represents an alkylene group having 1 to 12 carbon atoms, and q represents an integer of 1 to 3.

In one embodiment of the present invention, in the above-mentioned multi-branched polymer (D), the polythiol compound represented by formula (II) and the thiol group of the thiol compound having a carboxyl group represented by formula (III) are different from those represented by formula The addition molar ratio of the carbon-carbon double bond of the polyfunctional (meth)acrylate represented by (I) is 1/200 to 1/2.

In one embodiment of the present invention, the above-mentioned alkali-soluble resin (A-1) is obtained by reacting the first mixture, and the first mixture includes a diol compound (a-1) containing a polymerizable unsaturated group, four Carboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its acid anhydride (a-3). Tetracarboxylic acid or its acid dianhydride (a-2) includes tetracarboxylic acid or its acid dianhydride (a-2-1) containing fluorine atom, except tetracarboxylic acid or its acid dianhydride (a-2) containing fluorine atom Other than 2-1) other tetracarboxylic acid or its acid dianhydride (a-2-2) or a combination of both. Dicarboxylic acids or their anhydrides (a-3) include fluorine atom-containing dicarboxylic acids or their anhydrides (a-3-1), except for fluorine atom-containing dicarboxylic acids or their anhydrides (a-3-1) other dicarboxylic acid anhydrides or dicarboxylic acid compounds (a-3-2) or a combination of the above two. It should be noted that at least one of tetracarboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its acid anhydride (a-3) contains a fluorine atom.

In one embodiment of the present invention, the above-mentioned tetracarboxylic acid containing fluorine atom or its acid dianhydride (a-2-1) is selected from the tetracarboxylic acid compound containing fluorine atom represented by formula (2-1) and the A group consisting of tetracarboxylic dianhydride compounds containing fluorine atoms represented by formula (2-2). Among them, the fluorine atom-containing tetracarboxylic acid compound represented by formula (2-1) and the fluorine atom-containing tetracarboxylic dianhydride compound represented by formula (2-2) are shown below.

In formula (2-1) and formula (2-2), L ² is selected from one of the groups represented by formula (L-1) to formula (L-6).

In formula (L-1) to formula (L-6), E each independently represents a fluorine atom or a trifluoromethyl group, and * represents a bonding position with a carbon atom.

In one embodiment of the present invention, the above-mentioned dicarboxylic acid containing fluorine atom or its anhydride (a-3-1) is selected from the dicarboxylic acid compound containing fluorine atom represented by formula (3-1) and the compound represented by formula ( 3-2) is a group consisting of dicarboxylic anhydride compounds containing fluorine atoms. Among them, the fluorine atom-containing dicarboxylic acid compound represented by formula (3-1) and the fluorine atom-containing dicarboxylic anhydride compound represented by formula (3-2) are shown below.

In formula (3-1) and formula (3-2), X ¹ represents an organic group having 1 to 100 carbon atoms containing a fluorine atom.

In one embodiment of the present invention, the number of moles of the diol compound (a-1) containing a polymerizable unsaturated group, the number of moles of a tetracarboxylic acid containing a fluorine atom or its acid dianhydride (a-2-1) And the molar number of the dicarboxylic acid containing fluorine atom or its anhydride (a-3-1) satisfies the relational formula [(a-2-1)+(a-3-1)]/(a-1)=0.4～ 1.6.

In one embodiment of the present invention, based on 100 parts by weight of the alkali-soluble resin (A), the first alkali-soluble resin (A-1) is used in an amount of 10 to 100 parts by weight. The usage amount of the saturated group compound (B) is 15 parts by weight to 200 parts by weight, the usage amount of the photoinitiator (C) is 5 parts by weight to 55 parts by weight, and the usage amount of the multi-branch polymer (D) is 3 parts by weight. Parts by weight to 35 parts by weight, solvent (E) used in an amount of 1000 parts by weight to 5000 parts by weight, and black pigment (F) used in an amount of 60 parts by weight to 600 parts by weight.

In one embodiment of the present invention, the aforementioned compound (B) having an ethylenically unsaturated group includes a compound (B-1) having an acidic group and at least three ethylenically unsaturated groups.

In one embodiment of the present invention, based on 100 parts by weight of the alkali-soluble resin (A), the amount of the compound (B-1) having an acidic group and at least three ethylenically unsaturated groups is 15 parts by weight to 150 parts by weight.

The present invention further provides a method for manufacturing a color filter, which comprises using the above-mentioned photosensitive resin composition for a black matrix to form a black matrix.

The present invention further provides a black matrix, which is formed from the above-mentioned photosensitive resin composition for a black matrix.

The present invention also provides a color filter, including the above-mentioned black matrix.

The present invention further provides a liquid crystal display device, comprising the above-mentioned color filter.

Based on the above, the photosensitive resin composition for black matrix of the present invention can improve the adhesion and hardness of the black matrix due to the alkali-soluble resin having an aromatic structure and a specific structure of fluorine and a multi-branched polymer (D). The problem, and then applicable to color filters and liquid crystal display devices.

In order to make the above-mentioned features and advantages of the present invention more comprehensible, the following specific embodiments are described in detail as follows.

detailed description

In the following, (meth)acrylic acid is used to represent acrylic acid and/or methacrylic acid, and (meth)acrylate is used to represent acrylate and/or methacrylate; similarly, (meth)acryloyl group is used to represent acrylic acid Acyl and/or methacryloyl.

<Photosensitive resin composition for black matrix>

The present invention provides a photosensitive resin composition for a black matrix (hereinafter also referred to as "photosensitive resin composition"), which includes an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photosensitive Initiator (C), multibranched polymer (D), solvent (E) and black pigment (F). In addition, the photosensitive resin composition may further include an additive (G), if necessary. Each component of the photosensitive resin composition used in the present invention will be described in detail below.

Alkali soluble resin (A)

The alkali-soluble resin (A) includes the first alkali-soluble resin (A-1). In addition, the alkali-soluble resin (A) may optionally include a second alkali-soluble resin (A-2) and other alkali-soluble resins (A-3).

The first alkali soluble resin (A-1)

The first alkali-soluble resin (A-1) is a compound represented by formula (1):

In formula (1), A represents phenylene or phenylene with substituents, wherein the substituents are alkyl groups with 1 to 5 carbon atoms, halogen atoms or phenyl groups; B represents -CO-, -SO ₂ - , -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9,9-fluorenylene or single bond; L ¹ Represents a tetravalent carboxylic acid residue containing a fluorine atom or a tetravalent carboxylic acid residue not containing a fluorine atom; ^Y1 represents a divalent carboxylic acid residue containing a fluorine atom or a divalent carboxylic acid residue not containing a fluorine atom; R ¹ represents a hydrogen atom or a methyl group; m represents an integer from 1 to 20; at least one of L ¹ and Y ¹ contains a fluorine atom.

It is worth noting that L can be ^a tetravalent carboxylic acid residue containing fluorine atoms or a tetravalent carboxylic acid residue not containing fluorine atoms, preferably a tetravalent aromatic group with fluorine, and more preferably a tetravalent aromatic group with Fluorine benzene ring.

Specifically, the alkali-soluble resin (A-1) is obtained by reacting the first mixture. The first mixture contains a polymerizable unsaturated group-containing diol compound (a-1), tetracarboxylic acid or its acid dianhydride (a-2), and dicarboxylic acid or its acid anhydride (a-3). At least one of tetracarboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its acid anhydride (a-3) needs to contain a fluorine atom. The individual components of the first mixture are described below.

Polymerizable unsaturated group-containing diol compound (a-1)

The diol compound (a-1) containing a polymerizable unsaturated group is composed of a bisphenol compound (a-1-i) having two epoxy groups and having at least one carboxylic acid group and at least one ethylenically unsaturated group The compound (a-1-ii) reaction is prepared. The reactant for synthesizing the polymerizable unsaturated group-containing diol compound (a-1) may contain other compounds.

The bisphenol compound (a-1-i) having two epoxy groups can be obtained, for example, by dehydrohalogenating a bisphenol compound and a halogenated propylene oxide in the presence of an alkali metal hydroxide.

Specific examples of bisphenols used to synthesize the bisphenol compound (a-1-i) having two epoxy groups include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-bis Methylphenyl) ketone, bis(4-hydroxy-3,5-dichlorophenyl) ketone, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl) Sulfone, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane , Bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)di Methylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane , Bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylbenzene base) propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis( 4-hydroxy-3-chlorophenyl) propane, bis(4-hydroxyphenyl) ether, bis(4-hydroxy-3,5-dimethylphenyl) ether, bis(4-hydroxy-3,5- Dichlorophenyl) ether, etc.; 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-dimethylphenyl)fluorene, 9,9-bis(4- Hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9- Bis(4-hydroxy-3,5-dimethylphenyl)fluorene or a combination of the above compounds.

Specific examples of the halogenated propylene oxide used to synthesize the bisphenol compound (a-1-i) having two epoxy groups include 3-chloro-1,2-propylene oxide, 3-bromo-1,2- Propylene oxide or a combination of the above compounds. Based on the total equivalents of the hydroxyl groups in the above-mentioned bisphenol compounds being 1 equivalent, the amount of the above-mentioned halogenated propylene oxide can be 1 equivalent to 20 equivalents, and preferably 2 equivalents to 10 equivalents.

Specific examples of alkali metal hydroxides include sodium hydroxide, potassium hydroxide, or combinations thereof. Based on the total equivalent of hydroxyl groups in the above-mentioned bisphenol compounds being 1 equivalent, the amount of alkali metal hydroxide added in the above-mentioned dehydrohalogenation reaction can be 0.8 to 15 equivalents, and preferably 0.9 to 11 equivalents .

It should be noted that alkali metal hydroxides such as sodium hydroxide and potassium hydroxide may be added in advance or during the reaction process before the dehydrohalogenation reaction. The operating temperature of the dehydrohalogenation reaction ranges from 20°C to 120°C, and the operating time ranges from 1 hour to 10 hours.

In one embodiment, the aqueous solution of the alkali metal hydroxide added in the above dehydrohalogenation reaction can also be used. In this embodiment, while continuously adding the above-mentioned alkali metal hydroxide aqueous solution into the dehydrohalogenation reaction system, water and halogenated propylene oxide can be continuously distilled out under reduced pressure or normal pressure, thereby separating and removing water, and at the same time, the halogenated propylene oxide can be continuously refluxed into the reaction system.

Before the above-mentioned dehydrohalogenation reaction proceeds, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzyl ammonium chloride may be added as a catalyst. Next, react at 50° C. to 150° C. for 1 hour to 5 hours, and then add alkali metal hydroxide or its aqueous solution. Then, at a temperature of 20° C. to 120° C., it is allowed to react for 1 hour to 10 hours to perform dehydrohalogenation reaction.

In addition, in order to smoothly proceed the above-mentioned dehydrohalogenation reaction, in addition to alcohols such as methanol and ethanol, an aprotic polar solvent such as dimethyl sulfone and dimethyl sulfoxide may be added to carry out the reaction. In the case of using alcohols, based on 100% by weight of the total amount of the above-mentioned halogenated propylene oxides, the alcohols may be used in an amount of 2 to 20% by weight, and preferably 4 to 15% by weight. In the example of using an aprotic polar solvent, based on 100% by weight of the total amount of halogenated propylene oxide, the usage amount of the aprotic polar solvent can be 5% by weight to 100% by weight, preferably 10% by weight. % by weight to 90% by weight.

After the dehydrohalogenation reaction is completed, a water washing treatment may be optionally performed. Afterwards, by heating and reducing pressure, for example, at a temperature of 110°C to 250°C and a pressure of 1.3kPa (10mmHg) or less, the halogenated propylene oxide, alcohols, and aprotic polar solvents are removed.

In order to prevent the formed epoxy resin from containing hydrolytic halogen, the solution after the dehydrohalogenation reaction can be added to solvents such as benzene, toluene, methylisobutylketone (methylisobutylketone), and alkalis such as sodium hydroxide and potassium hydroxide can be added. Aqueous metal hydroxide solution for dehydrohalogenation reaction again. In the dehydrohalogenation reaction, based on the total equivalent of hydroxyl groups in the bisphenol compounds being 1 equivalent, the amount of alkali metal hydroxide used may be 0.01 to 1 mole, preferably 0.05 to 0.9 mole. In addition, the operating temperature of the above dehydrohalogenation reaction ranges from 50° C. to 120° C., and the operating time ranges from 0.5 hours to 2 hours.

After the dehydrohalogenation reaction is completed, the salts are removed through steps such as filtration and water washing. In addition, solvents such as benzene, toluene, and methyl isobutyl ketone can be distilled off by heating and depressurizing to obtain a bisphenol compound (a-1-i) having two epoxy groups.

The bisphenol compound (a-1-i) having two epoxy groups is preferably a bisphenol compound having two epoxy groups represented by the following formula (1-1), or represented by the following formula ( The bisphenol compound having two epoxy groups represented by 1-2) is a polymer obtained by polymerizing monomers.

In formula (1-1) and formula (1-2), A ¹ to A ⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group. B stands for -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9,9 -fluorenylene or a single bond. m1 may represent an integer of 1 to 10, and m1 may represent an integer of 1 to 2 more preferably.

The bisphenol compound having two epoxy groups represented by the formula (1-1) is particularly preferably a bisphenol compound represented by the following formula (1-3) having two epoxy groups.

In formula (1-3), A ¹ , A ² , A ³ , A ⁴ , A ⁷ and A ⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

The bisphenol compound with two epoxy groups represented by formula (1-3) is, for example, a bisphenol fluorene compound (bisphenolfluorene) reacted with a halogenated propylene oxide (epihalohydrin) and has two epoxy groups. Bisphenol fluorene compounds.

Specific examples of bisphenol fluorene-type compounds include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4- Hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9- Bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3, 5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene or a combination of the above compounds.

Specific examples of the halogenated propylene oxide include 3-chloro-1,2-epoxypropylene (epichlorohydrin), 3-bromo-1,2-epoxypropylene (epibromohydrin), or a combination of the above-mentioned compounds.

Specific examples of bisphenol fluorene compounds having an epoxy group include (1) products manufactured by Nippon Steel Chemical: such as ESF-300 or the like; (2) products manufactured by Osaka Gas: such as PG-100, EG- 210 or the like; or (3) products manufactured by S.M.S Technology Co.: for example, SMS-F9PhPG, SMS-F9CrG, SMS-F914PG or the like.

The compound (a-1-ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group is at least one compound selected from the group consisting of the following compounds: acrylic acid, methacrylic acid, 2-methylpropene Acyloxyethylsuccinic acid, 2-methacryloyloxybutylsuccinic acid, 2-methacryloyloxyethyladipate, 2-methacryloyloxybutyladipate, 2-methacryloyloxybutyladipate Acryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxypropylmaleic acid, 2-methacryloyloxybutylmaleic acid acid, 2-methacryloxypropyl succinic acid, 2-methacryloyloxypropyl adipic acid, 2-methacryloyloxypropyl tetrahydrophthalic acid, 2-methacryloyl Oxypropyl phthalic acid, 2-methacryloyloxybutyl phthalic acid, or 2-methacryloyloxybutyl hydrogen phthalic acid; compound consisting of hydroxyl-containing (meth)acrylate and dibasic carboxylic acid The compound obtained from the reaction, wherein the dicarboxylic acid compound includes but not limited to adipic acid, succinic acid, maleic acid, phthalic acid; it is obtained by the reaction of hydroxyl-containing (meth)acrylate and carboxylic anhydride compound Half-ester compounds, wherein hydroxyl-containing (meth)acrylates include but are not limited to 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl Methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, or pentaerythritol trimethacrylate, etc. In addition, the specific examples of the carboxylic anhydride compound described here can be combined with the specific examples of tetracarboxylic dianhydrides in the following other tetracarboxylic acids or their acid dianhydrides (a-2-2) and the following other dicarboxylic acids or The specific examples of the dicarboxylic acid anhydride in the acid anhydride (a-3-2) are the same, so no further description is given.

Tetracarboxylic acid or its dianhydride (a-2)

Tetracarboxylic acids or their acid dianhydrides (a-2) include tetracarboxylic acids or their acid dianhydrides (a-2-1) containing fluorine atoms, except for the tetracarboxylic acids or their acid dianhydrides containing fluorine atoms ( Other tetracarboxylic acids or acid dianhydrides (a-2-2) other than a-2-1), or a combination of both.

The tetracarboxylic acid containing fluorine atom or its acid dianhydride (a-2-1) is selected from the tetracarboxylic acid compound containing fluorine atom represented by formula (2-1) and the compound containing fluorine atom represented by formula (2-2). A group of tetracarboxylic dianhydride compounds. Specifically, the fluorine atom-containing tetracarboxylic acid compound represented by formula (2-1) and the fluorine atom-containing tetracarboxylic dianhydride compound represented by formula (2-2) are as follows.

In formula (2-1) and formula (2-2), L ² is a tetravalent aromatic group with fluorine, and preferably has a benzene ring. Specifically, one selected from the groups represented by formula (L-1) to formula (L-6) is preferable.

In formula (L-1) to formula (L-6), E each independently represents a fluorine atom or a trifluoromethyl group, and * represents a bonding position with a carbon atom.

Specifically, specific examples of tetracarboxylic acids containing fluorine atoms or their acid dianhydrides (a-2-1) include 4,4'-hexafluoroisopropylidene diphthalic acid, 1,4-difluoro Fluorine-containing aromatic tetracarboxylic acids such as 1,4-difluoropyromellitic acid, 1-monofluoropyromellitic acid, 1,4-bis(trifluoromethyl)pyromellitic acid, or the above-mentioned tetracarboxylic acids An acid dianhydride compound, or a combination of the above compounds.

Specific examples of tetracarboxylic acids containing fluorine atoms or their acid dianhydrides (a-2-1) also include 3,3'-hexafluoroisopropylidene diphthalic acid (3,3'-(hexafluoroisopropylidene) diphthalic acid ), 5,5'-[2,2,2-trifluoro-1-[3-(trifluoromethyl)phenyl]ethylene]diphthalic acid, 5,5'-[2,2 ,3,3,3-Pentafluoro-1-(trifluoromethyl)propylene]diphthalic acid, 5,5'-oxybis[4,6,7-trifluoro-pyromellitic acid ](5,5'-oxybis[4,6,7-trifluoro-pyromellitic acid], 3,6-bis(trifluoromethyl)pyromellitic acid, 4-(trifluoromethyl)pyromellitic acid, 1 , fluorine-containing tetracarboxylic acids such as 4-bis(3,4-dicarboxylic acid trifluorophenoxy)tetrafluorobenzene, or dianhydride compounds of the above-mentioned tetracarboxylic acids, or a combination of the above-mentioned compounds.

Other tetracarboxylic acids or their acid dianhydrides (a-2-2) include saturated straight-chain hydrocarbon tetracarboxylic acids, alicyclic tetracarboxylic acids, aromatic tetracarboxylic acids, or dianhydride compounds of the above-mentioned tetracarboxylic acids, or combination.

Specific examples of the saturated linear hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, or a combination of the above compounds. The saturated linear hydrocarbon tetracarboxylic acid may have a substituent.

Specific examples of the alicyclic tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, norbornane tetracarboxylic acid, or combinations thereof. Alicyclic tetracarboxylic acid may have a substituent.

Specific examples of the aromatic tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, 1,2,3,6 - Tetrahydrophthalic acid, or a combination of the above compounds. Aromatic tetracarboxylic acid may have a substituent.

Dicarboxylic acid or its anhydride (a-3)

The dicarboxylic acid or its anhydride (a-3) includes the dicarboxylic acid or its anhydride (a-3-1) containing a fluorine atom, except the dicarboxylic acid or its anhydride (a-3-1) containing a fluorine atom other dicarboxylic acids or their anhydrides (a-3-2) or a combination of the above two.

The dicarboxylic acid containing fluorine atom or its anhydride (a-3-1) is selected from the dicarboxylic acid compound containing fluorine atom represented by formula (3-1) and the dicarboxylic acid compound containing fluorine atom represented by formula (3-2). A group of carboxylic acid anhydride compounds. Specifically, the fluorine atom-containing dicarboxylic acid compound represented by formula (3-1) and the fluorine atom-containing dicarboxylic anhydride compound represented by formula (3-2) are as follows.

In formula (3-1) and formula (3-2), X ¹ represents an organic group having 1 to 100 carbon atoms containing a fluorine atom.

Specific examples of dicarboxylic acids containing fluorine atoms or their anhydrides (a-3-1) include 3-fluorophthalic acid, 4-fluorophthalic acid, tetrafluorophthalic acid, 3,6-difluorophthalic acid, Phthalic acid, tetrafluorosuccinic acid, or anhydride compounds of the above-mentioned dicarboxylic acids, or a combination of the above-mentioned compounds.

Specific examples of other dicarboxylic acids or their anhydrides (a-3-2) include saturated linear hydrocarbon dicarboxylic acids, saturated cyclic hydrocarbon dicarboxylic acids, unsaturated dicarboxylic acids, or anhydrides of the above dicarboxylic acid compounds, or Combinations of the above compounds.

Specific examples of saturated straight-chain hydrocarbon dicarboxylic acids include succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxopentadioic acid, acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, or combinations thereof. The hydrocarbyl groups in the saturated straight-chain hydrocarbon dicarboxylic acids may also be substituted.

Specific examples of the saturated cyclic hydrocarbon dicarboxylic acid include hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, hexahydrotrimellitic acid, or combinations thereof. combination. The saturated cyclic hydrocarbon dicarboxylic acid may also be a saturated hydrocarbon substituted alicyclic dicarboxylic acid.

Specific examples of unsaturated dicarboxylic acids include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methylendo-methylenetetrahydrophthalic acid, chlorendic acid (chlorendic acid), trimellitic acid, or combinations thereof.

Specific examples of other dicarboxylic acids or their anhydrides (a-3-2) include trimethoxysilylpropyl succinic anhydride, triethoxysilylpropyl succinic anhydride, methyldimethoxysilylpropyl succinic anhydride, methyldimethoxysilylpropyl succinic anhydride, methyldiethoxysilylpropylsuccinic anhydride, methyldiethoxysilylpropylsuccinic anhydride, trimethoxysilylbutylsuccinic anhydride, triethoxysilylbutylsuccinic anhydride, methyldiethoxysilyl Butylsuccinic anhydride, p-(trimethoxysilyl)phenylsuccinic anhydride, p-(triethoxysilyl)phenylsuccinic anhydride, p-(methyldimethoxysilyl)phenylbutanedioic anhydride Anhydride, p-(methyldiethoxysilyl)phenylsuccinic anhydride, m-(trimethoxysilyl)phenylsuccinic anhydride, m-(triethoxysilyl)phenylsuccinic anhydride, m-( Dicarboxylic anhydrides such as methyldiethoxysilyl)phenylsuccinic anhydride, or dicarboxylic acid compounds of the above-mentioned dicarboxylic anhydrides, or combinations of the above-mentioned compounds.

The dicarboxylic acid compound is preferably succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, trimellitic acid or a combination of the above compounds, more preferably succinic acid , itaconic acid, tetrahydrophthalic acid or combinations thereof.

The dicarboxylic anhydride is preferably succinic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrotrimellitic anhydride, phthalic anhydride, trimellitic anhydride or a combination of the above compounds.

The synthesis method of the alkali-soluble resin (A-1) is not particularly limited, as long as the diol compound (a-1) containing a polymerizable unsaturated group, tetracarboxylic dianhydride or its tetracarboxylic acid (a-2) and It can be obtained by reacting dicarboxylic acid anhydride or its dicarboxylic acid (a-3).

When preparing the above-mentioned alkali-soluble resin (A-1), in order to accelerate the reaction, a basic compound is usually added to the reaction solution as a reaction catalyst. Specific examples of the above-mentioned reaction catalyst include triphenylphosphine (triphenylphosphine), triphenylstibine (triphenylstibine), triethylamine, triethanolamine, tetramethylammonium chloride, benzyltriethylammonium chloride or the above-mentioned reaction catalyst The combination. The above-mentioned reaction catalysts can be used alone or in combination.

In addition, in order to control the degree of polymerization, a polymerization inhibitor is usually added to the reaction solution. Specific examples of the above-mentioned polymerization inhibitors include methoxyphenol, methylhydroquinone (methylhydroquinone), hydroquinone (hydroquinone), 2,6-di-tert-butyl-p-cresol (2,6-di-tert-butyl- p-cresol), phenothiazine or analogues thereof. The above-mentioned polymerization inhibitors can be used individually or in combination of multiple types.

In preparing the above-mentioned alkali-soluble resin (A-1), a polymerization reaction solvent may be used as necessary. The specific example of above-mentioned polymerization reaction solvent comprises: the alcohol compound of ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, ethylene glycol or the like; Methyl ethyl ketone, cyclohexane Ketones or ketone compounds of their analogues; aromatic hydrocarbon compounds of toluene, xylene or their analogues; cellosolve compounds of butylcellosolve or their analogues ; carbiturates, butylcarbitols or their analogues; propylene glycol monomethyl ether or their analogues; propylene glycol monomethyl ether or their analogues; dipropylene glycol monomethyl ether or their analogues; Ethyl ether compounds; ethyl acetate, butyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate or similar acetate compounds; ethyl lactate, butyl lactate or Alkyl lactate compounds of its analogues; or dialkyl glycol ethers; or methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate (EEP), ethyl ethoxyacetate and other esters. The above-mentioned polymerization reaction solvents may be used alone or in combination. In addition, the acid value of the alkali-soluble resin (A-1) is 50 mgKOH/g to 200 mgKOH/g, preferably 60 mgKOH/g to 180 mgKOH/g.

In addition, as the synthesis method, for example, as described in JP-A-9-325494, a known method of reacting a diol compound with a tetracarboxylic dianhydride at a reaction temperature of 90° C. to 140° C. can be employed. In addition, the first mixture is uniformly dissolved and reacted at a reaction temperature of 90°C to 130°C, followed by reaction and aging at a reaction temperature of 40°C to 80°C.

The alkali-soluble resin (A-1) obtained by reacting the first mixture is an alkali-soluble resin containing a fluorine atom, and preferably an alkali-soluble resin containing an aromatic structure having fluorine.

On the other hand, among the components of the first mixture forming the alkali-soluble resin (A-1), among the tetracarboxylic acid or its acid dianhydride (a-2) and the dicarboxylic acid or its acid anhydride (a-3), At least one of them contains a fluorine atom, and it is preferable that both the tetracarboxylic acid or its acid dianhydride (a-2) and the dicarboxylic acid or its acid anhydride (a-3) contain a fluorine atom. When none of the tetracarboxylic acid or its acid dianhydride (a-2) or the dicarboxylic acid or its acid anhydride (a-3) contains fluorine atoms, the resolution and development resistance of the photosensitive resin composition are not good. Specifically, when tetracarboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its acid anhydride (a-3) all contain fluorine atoms, tetracarboxylic acid or its acid dianhydride (a-2) includes Tetracarboxylic acids containing fluorine atoms or their acid dianhydrides (a-2-1), and dicarboxylic acids or their anhydrides (a-3) include dicarboxylic acids or their anhydrides (a-3-1) containing fluorine atoms .

Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the first alkali-soluble resin (A-1) may be 10 parts by weight to 100 parts by weight, preferably 12 parts by weight to 100 parts by weight, and More preferably, it is 15 parts by weight to 100 parts by weight.

It should be noted that when the alkali-soluble resin (A) does not contain the first alkali-soluble resin (A-1), the adhesion of the photosensitive resin composition is not good. Further, when the photosensitive resin composition comprises the first alkali-soluble resin (A-1), since the fluorine atom can effectively improve the water repellency (waterrepellency) of the alkali-soluble resin, during the subsequent developing step, the exposed part It is not easy to cause lateraletching and fall off, thereby solving the problem of poor adhesion of the photosensitive resin composition.

In addition, the number of moles of the diol compound (a-1) containing a polymerizable unsaturated group, the number of moles of a tetracarboxylic acid containing a fluorine atom or its acid dianhydride (a-2-1), and the number of moles of a dicarboxylic acid containing a fluorine atom The number of moles of the acid or its anhydride (a-3-1) is preferably such that the relational formula [(a-2-1)+(a-3-1)]/(a-1)=0.4-1.6 can be satisfied. When [(a-2-1)+(a-3-1)]/(a-1)=0.4-1.6, the adhesiveness of a photosensitive resin composition can be improved further.

The second alkali soluble resin (A-2)

The second alkali-soluble resin (A-2) includes a derivative unit having a structure represented by formula (4).

In formula (4), R ² and R ³ are each independently a hydrogen atom, a linear or branched chain alkyl group with 1 to 5 carbon atoms, a phenyl group or a halogen atom.

The second alkali-soluble resin (A-2) is obtained by reacting a compound having a structure represented by formula (4) with another copolymerizable compound. The compound having a structure represented by formula (4) may be a bisphenol fluorene type compound containing two epoxy groups represented by formula (5) or a bisphenol fluorene compound containing two hydroxyl groups represented by formula (6) type compounds.

In formula (5), R ⁴ is the same as R ² in formula (4); R ⁵ is the same as R ³ in formula (4), and will not be repeated here.

In formula (6), R ⁶ is the same as R ² in formula (4); R ⁷ is the same as R ³ in formula (4), and will not be described in detail here; R ⁸ and R ⁹ each independently represent a carbon number of 1 to 20 An alkylene group or an alicyclic group; p and q each independently represent an integer of 1 to 4.

Specific examples of other copolymerizable compounds include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyl tetrahydrophthalic acid, methyl hexahydrophthalic acid, methyl endomethylene tetrahydrophthalic acid, chlorinated Dicarboxylic acids such as dicarboxylic acid and glutaric acid and their anhydrides; tricarboxylic acids such as trimellitic acid and their anhydrides; and pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl tetracarboxylic acid, Tetracarboxylic acids such as phenylene ether tetracarboxylic acid and their anhydrides, or combinations of the above compounds.

The second alkali-soluble resin (A-2) is preferably made by Nippon Steel Chemical Co., Ltd., and its product names are V259ME, V301ME and other products.

Based on 100 parts by weight of the alkali-soluble resin (A), the second alkali-soluble resin (A-2) can be used in an amount of 0 to 90 parts by weight, preferably 0 to 88 parts by weight, and More preferably, it is 0 to 85 parts by weight.

Other Alkali Soluble Resins (A-3)

The alkali-soluble resin (A) may optionally include other alkali-soluble resins (A-3). Other alkali-soluble resins (A-3) are resins other than the first alkali-soluble resin (A-1) and the second alkali-soluble resin (A-2). Other alkali-soluble resins (A-3) are, for example, resins having carboxylic acid groups or hydroxyl groups, but are not limited to resins having carboxylic acid groups or hydroxyl groups. Specific examples of other alkali-soluble resins (A-3) include resins such as acrylic resins, urethane resins, and novolac resins.

Based on 100 parts by weight of the alkali-soluble resin (A), the usage-amount of other alkali-soluble resins (A-3) is 0 to 30 parts by weight, preferably 0 to 20 parts by weight, and more preferably 0 to 10 parts by weight.

Compound (B) having an ethylenically unsaturated group

The compound (B) having an ethylenically unsaturated group may include a compound (B-1) having an acidic group and at least three ethylenically unsaturated groups. In addition, the compound (B) which has an ethylenically unsaturated group may further include the compound (B-2) which has another ethylenically unsaturated group.

A compound (B-1) having an acidic group and at least three ethylenically unsaturated groups

The acidic group in the compound (B-1) having an acidic group and at least three ethylenically unsaturated groups can react with an alkaline developer. Specific examples of acidic groups include carboxyl groups, sulfonic acid groups, or phosphoric acid groups, among which the acidic groups are preferably carboxyl groups that can have a good effect on alkaline developer.

The compound (B-1) having an acidic group and at least three ethylenically unsaturated groups includes (1) modifying a polyfunctional (meth)acrylate having a hydroxyl group with a dibasic carboxylic acid anhydride or a dibasic acid to Synthesizing carboxyl-containing polyfunctional (meth)acrylates; and (2) modifying aromatic polyfunctional (meth)acrylates with concentrated sulfuric acid or fuming sulfuric acid to synthesize sulfonic acid-containing polyfunctional Functional (meth)acrylate.

The compound (B-1) having an acidic group and at least three ethylenically unsaturated groups preferably has a structure represented by formula (IV) or (V).

In formula (IV), B ¹ represents -CH ₂ -, -OCH ₂ -, -OCH ₂ CH ₂ -, -OCH ₂ CH ₂ CH ₂ - or -OCH ₂ CH ₂ CH ₂ CH ₂ -; B ² represents The structure represented by formula (IV-1) or formula (IV-2); B ³ represents the structure represented by formula (IV-3), formula (IV-4) or formula (IV-5), wherein formula (IV- 5) The benzene ring in the represented structure can also be tetrahydrogenated or hexahydrogenated, c represents an integer from 1 to 8; b represents an integer from 0 to 14. When there are ^a plurality of B1 and ^B2 , each ^of B1 and ^B2 may be the same or different.

In formula (V), B ¹ , B ² , B ³ and b are synonymous with B ¹ , B ² , B ³ and b in formula (IV), and will not be repeated here; B ⁴ represents -O- or A structure represented by formula (V-1). When there are ^a plurality of B1 and ^B2 , each ^of B1 and ^B2 may be the same or different.

In formula (V-1), d represents an integer of 1 to 8.

The compound (B-1) having an acidic group and at least three ethylenically unsaturated groups represented by formula (IV) or formula (V) above is, for example, a compound having an acidic group and three ethylenically unsaturated groups or a compound having Compounds with acidic groups and five ethylenically unsaturated groups.

Specific examples of compounds having an acidic group and three ethylenically unsaturated groups include monohydroxy oligomeric acrylates such as pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, or dipentaerythritol pentamethacrylate. Or a carboxyl group-containing monoester compound formed of monohydroxy oligomeric methacrylate and diacids such as malonic acid, succinic acid, glutaric acid, isophthalic acid, terephthalic acid, or phthalic acid. Specific examples of commercially available compounds having an acidic group and three ethylenically unsaturated groups include TO-756 (manufactured by Toagosei Co., Ltd.), PE3A-MS, PE3A-MP (manufactured by Kyoeisha Chemical Co., Ltd.), or A combination of the above commercially available products.

Specific examples of commercially available compounds having an acidic group and five ethylenically unsaturated groups include TO-1382, TO-1385 (manufactured by Toagosei Co., Ltd.), DPE6A-MS, and DPE6A-MP (manufactured by Kyoeisha Chemical Co., Ltd. system), or a combination of the above commercially available products.

Specific examples of the compound (B-1) having an acidic group and at least three ethylenically unsaturated groups are preferably pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate or dipentaerythritol pentamethacrylate A carboxyl-containing monoester compound formed with succinic acid or phthalic acid.

The compound (B-1) which has the said acidic group and at least three ethylenically unsaturated groups can be used individually or in combination of several types.

Based on the amount of the alkali-soluble resin (A) being 100 parts by weight, the amount of the compound (B-1) having an acidic group and at least three ethylenically unsaturated groups can be 15 parts by weight to 150 parts by weight, preferably 20 parts by weight to 140 parts by weight, more preferably 25 parts by weight to 130 parts by weight.

It should be noted that the van der Waals distance between the black matrix formed by the photosensitive resin composition and the substrate (such as glass) can be increased due to the acidic group of the compound (B-1) having an acidic group and at least three ethylenically unsaturated groups. Force (VanderWaalsforce), and at least three ethylenically unsaturated groups can participate in photochemical reactions to increase the crosslinking density of the cured product (black matrix), thereby improving the adhesion and the black matrix produced by the photosensitive resin composition hardness.

Other compounds with ethylenically unsaturated groups (B-2)

Other compounds (B-2) having an ethylenically unsaturated group include compounds having one ethylenically unsaturated group, compounds having two or more ethylenically unsaturated groups, or a combination of both.

Specific examples of compounds having one ethylenically unsaturated group include, but are not limited to, (meth)acrylamide ((meth)acrylamide), (meth)acrylmorpholine ((meth)acrylmorpholine), (meth)acrylic acid- 7-amino-3,7-dimethyloctyl ester, isobutoxymethyl (meth)acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, ( 2-ethylhexyl methacrylate, ethyl diethylene glycol (meth)acrylate, tert-octyl (meth)acrylamide, diacetone (meth)acrylamide, diacetone (meth)acrylic acid Methylamino ethyl ester, dodecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N,N-dimethyl (Meth)acrylamide, tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, Tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl (meth)acrylate Esters, 2-tribromophenoxyethyl (meth)acrylate, 2-hydroxy-ethyl (meth)acrylate, 2-hydroxy-propyl (meth)acrylate, vinyl caprolactam, N-vinyl Pyrrolidone, Phenoxyethyl (meth)acrylate, Pentachlorophenyl (meth)acrylate, Pentabromophenyl (meth)acrylate, Polyethylene glycol mono(meth)acrylate, Polymono(meth)acrylate Propylene glycol acrylate, bornyl (meth)acrylate, or combinations thereof. The compound which has one ethylenically unsaturated group can be used individually or in combination of several types.

Specific examples of compounds having two or more ethylenically unsaturated groups include, but are not limited to, ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol di(methyl) Acrylates, tetraethylene glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanate di(meth)acrylate, tris(2-hydroxyethyl)isocyanate tri(methyl) Acrylate, tri(2-hydroxyethyl)isocyanate tri(meth)acrylate modified by caprolactone, trimethylolpropyl tri(meth)acrylate, ethylene oxide (referred to as EO ) modified trimethylolpropyl tri(meth)acrylate, trimethylolpropyl tri(meth)acrylate modified by propylene oxide (referred to as PO), tripropylene glycol di(meth)acrylate , Neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyester di(meth)acrylate Acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, modified with caprolactone Dipentaerythritol hexa(meth)acrylate modified by caprolactone, dipentaerythritol penta(meth)acrylate modified by caprolactone, di(trimethylolpropane)tetra(meth)acrylate ) acrylate), bisphenol A di(meth)acrylate modified with ethylene oxide, bisphenol A di(meth)acrylate modified with propylene oxide, hydrogenation modified with ethylene oxide Bisphenol A di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate modified with propylene oxide, bisphenol F di(meth)acrylate modified with ethylene oxide, phenolic Varnish Polyglycidyl ether (meth)acrylate, or combinations thereof. The compound which has two or more ethylenically unsaturated groups can be used individually or in combination of several types.

Other specific examples of compounds (B-2) having ethylenically unsaturated groups preferably include trimethylolpropyl triacrylate, trimethylolpropyl triacrylate modified with ethylene oxide, epoxy-modified trimethylolpropyl Propane-modified trimethylolpropyl triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone-modified dipentaerythritol Hexaacrylate, ditrimethylolpropyl tetraacrylate, glyceryl triacrylate modified with propylene oxide, or combinations thereof.

Based on the amount of the alkali-soluble resin (A) being 100 parts by weight, the amount of the compound (B) having an ethylenically unsaturated group can be 15 parts by weight to 200 parts by weight, preferably 20 parts by weight to 190 parts by weight, More preferably, it is 25 parts by weight to 180 parts by weight.

Photoinitiator (C)

The photoinitiator (C) is, for example, acetophenone, biimidazole, acyloxime or a combination of the above compounds.

Specific examples of acetophenone-based compounds include p-dimethylaminoacetophenone, α,α'-dimethoxyazoacetophenone oxide, 2,2'-dimethyl-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-nitro, nitrogen-dimethylamine -1-(4-morpholinophenyl)-1-butanone or a combination of the above compounds.

Specific examples of diimidazole compounds include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-fluorophenyl) )-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2 ,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-ethylphenyl)-4,4' ,5,5'-tetraphenyldiimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis( 2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4, 4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole or the above compounds combination.

Specific examples of acyloxime compounds include ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9hydro-carbazole-3-substituent]-1-(oxygen-acetyl Oxime) [Ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime), as manufactured by Ciba Specialty Chemicals OXE-02, whose structure is represented by formula (7)], 1-(4-(phenylthio)phenyl)-octane-1,2-dione-2-oxime-oxygen-benzoate [1-(4-phenyl-thio-phenyl)-octane-1,2-dion-2-oxime-O-benzoate, such as OXE-01 manufactured by Ciba Specialty Chemical Co., Ltd., its structure is represented by formula (8) Show], Ethanone, 1-[9-Ethyl-6-(2-chloro-4-benzyl-thio-benzoyl)-9hydro-carbazole-3-substituent]-,1 -(Oxo-acetyloxime)[Ethanone,1-[9-ethyl-6-(2-cholro-4-benzyl-thio-benzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime) , manufactured by Asahi Denka Corporation, whose structure is represented by formula (9)] or a combination of the above-mentioned compounds.

The photoinitiator (C) is preferably 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-nitro, nitrogen-di Methylamine-1-(4-morpholinophenyl)-1-butanone, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9hydro-carbazole-3-substituent]-, 1-(oxy-acetyloxime) or combinations of the above .

The photoinitiator (C) can further add the following compounds if necessary: thioxanthone (thioxanthone), 2,4-diethylthioxanthone, thioxanthone-4-sulfone, benzophenone, 4,4 '-Bis(dimethylamine) benzophenone, 4,4'-bis(diethylamine) benzophenone and other benzophenone compounds; benzil, acetyl ) and other α-diketones (α-diketone); ketone alcohols (acyloin) such as benzoin; benzoinmethylether, benzoinethylether, diphenyl Keto alcohol ethers such as benzoinisopropylether; 2,4,6-trimethyl-benzoyl-diphenyl-phosphine oxide (2,4,6-trimethyl-benzoyl-diphenyl-phosphineoxide), bis-( 2,6-dimethoxybenzoyl)-2,4,4-trimethylphenylphosphine oxide [bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethyl-benzyl-phosphineoxide ] and other acylphosphine oxides; quinones such as anthraquinone and 1,4-naphthoquinone; phenacylchloride and tribromomethyl-phenylsulfone ), tris(trichloromethyl)-s-triazine [tris(trichloromethyl)-s-triazine] and other halides; di-tertbutylperoxide and other peroxides; or the above compounds combination. The compound added to the photoinitiator (C) is preferably a benzophenone-based compound, and more preferably 4,4'-bis(diethylamine)benzophenone.

Based on 100 parts by weight of the alkali-soluble resin (A), the photoinitiator (C) can be used in an amount of 5 parts by weight to 55 parts by weight, preferably 7 parts by weight to 50 parts by weight, and more preferably 10 parts by weight to 45 parts by weight.

Multibranched Polymer (D)

The multi-branched polymer (D) may be a polymer formed by Michael Addition Reaction (MichaelAdditionReaction) of a polymercapto compound represented by formula (II) and a multifunctional (meth)acrylate represented by formula (I) .

Specifically, the polyfunctional (meth)acrylate represented by formula (I) is as follows.

In formula (I), R ² represents a hydrogen atom or an alkyl group with a carbon number of 1 to 4; R ³ represents the residue after esterification of n hydroxyl groups in a hydroxyl-containing compound having m hydroxyl groups, wherein m≧ n, n represents an integer of 2 to 20.

The above hydroxyl-containing compound is a compound in which R ⁴ (OH) _m or R ⁴ (OH) _m is modified by propylene oxide, epichlorohydrin, alkyl, alkoxy or hydroxypropyl acrylate.

R ⁴ (OH) _m is a polyol having a carbon number of 2 to 18, a polyol ether formed from the above polyol, an ester formed by reacting the above polyol with an acid, or silicone.

In addition, polymercapto compounds represented by formula (II) are shown below.

In formula (II), R ⁵ represents a single bond, a hydrocarbon group with a carbon number of 1, or a straight-chain or branched chain hydrocarbon group with a carbon number of 2 to 22, and the skeleton of R ⁵ may further include a sulfur atom or form an ester group. Oxygen atom (that is, R5 is a single bond, a hydrocarbon group with a carbon number of 1, a straight-chain or branched chain hydrocarbon group with a carbon number of 2 to 22 containing a sulfur atom or an oxygen atom, or a carbon group that does not contain a sulfur atom or an oxygen atom number is 2 to 22 linear or branched hydrocarbon groups); p represents an integer of 2 to 6, wherein when R ⁵ represents a single bond, p represents 2; when R ⁵ represents a hydrocarbon group with a carbon number of 1, p represents An integer of 2 to 4; when R ⁵ represents a linear or branched hydrocarbon group with a carbon number of 2 to 22, p represents an integer of 2 to 6.

In addition, the multi-branched polymer (D) of the present invention is preferably a (meth)acrylate remaining after the reaction of the polymercapto compound represented by the formula (II) and the polyfunctional (meth)acrylate represented by the formula (I). ) acrylate group, and a polymer formed by further reacting a mercapto compound having a carboxyl group represented by formula (III).

The mercapto compounds having a carboxyl group represented by formula (III) are shown below.

In formula (III), R ⁶ represents an alkylene group having 1 to 12 carbon atoms, and q represents an integer of 1 to 3.

Specifically, the mercapto group contained in the polymercapto compound represented by formula (II) and the mercapto compound having a carboxyl group represented by formula (III) is added to the polyfunctional group represented by formula (I) through photoreaction ( on the carbon-carbon double bond of the meth)acrylate. In general, among the carbon-carbon double bonds of the polyfunctional (meth)acrylate represented by formula (I), the photoreactive carbon-carbon double bonds are preferably 0.1% relative to all carbon-carbon double bonds to 50%.

Further, the mercapto group of the polymercapto compound represented by the formula (II), or the mercapto group of the polymercapto compound represented by the formula (II) and the mercapto compound having a carboxyl group represented by the formula (III), is relatively I) The addition molar ratio of the carbon-carbon double bond of the polyfunctional group (meth) acrylate can be 1/200 to 1/2, preferably 1/100 to 1/3, more preferably 1/2 50 to 1/5, more preferably 1/20 to 1/8.

The multibranched polymer (D) preferably has sufficient photopolymerizable functional groups, such as carbon-carbon double bonds. Specifically, the molecular weight of the multibranched polymer (D) per 1 mole of carbon-carbon double bonds is preferably 100 to 100,000. The molecular weight of the multibranched polymer (D) is preferably from 1,000 to 50,000, more preferably from 1,500 to 40,000, particularly preferably from 2,000 to 30,000.

In addition, in order to produce an alkali-developable photosensitive resin composition, the multi-branched polymer (D) preferably has sufficient carboxyl groups. Specifically, the molecular weight of the multi-branched polymer (D) corresponding to 1 mole of carboxyl groups is preferably from 200 to 20,000, more preferably from 250 to 6,000.

The number (n) of acrylate groups contained in the polyfunctional (meth)acrylate represented by formula (I) is preferably 2-20, more preferably 2-10, and still more preferably 2-6. When R ² in formula (I) represents an alkyl group having 1 to 4 carbon atoms, R ² may be methyl, ethyl, propyl or butyl, preferably methyl. Also, R ⁴ (OH) _m has a carbon number of preferably 2-18, more preferably 2-14, particularly preferably 4-12.

Specific examples of the polyfunctional (meth)acrylate represented by formula (I) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, base) acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, modified with ethylene oxide Trimethylolpropane tri(meth)acrylate modified with propylene oxide, trimethylolpropane tri(meth)acrylate modified with propylene oxide, trimethylolethane tri(meth)acrylate, pentaerythritol Di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa( Meth)acrylate, tripentaerythritol hepta(meth)acrylate, pentaerythritol tri(meth)acrylate modified by caprolactone, pentaerythritol tetra(meth)acrylate modified by caprolactone, Lactone-modified dipentaerythritol hexa(meth)acrylate, epichlorohydrin-modified hexahydrophthalic acid di(meth)acrylate, hydroxypivalate neopentyl glycol di(methyl) Acrylate (hydroxypivalicacidneopentylglycodi(meth)acrylate), neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate modified with ethylene oxide, neopentyl glycol di(meth)acrylate modified with propylene oxide Pentylene Glycol Di(meth)acrylate, Caprolactone-modified Hydroxypivalate Neopentyl Glycol Di(meth)acrylate, Stearic Acid-modified Pentaerythritol Di(meth)acrylate, Epichlorohydrin-modified di(meth)acrylate phthalate, poly(ethylene glycol tetramethylene glycol) di(meth)acrylate, poly(propylene glycol tetramethylene glycol) Di(meth)acrylate, polyester(meth)acrylate, polyethylene glycol di(meth)acrylate, polyethylene glycol polypropylene glycol polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate (meth)acrylate, propylene glycol di(meth)acrylate modified by epichlorohydrin, bisphenol A diglycidyl ether di(meth)acrylate modified by propylene oxide, silicone di( Meth)acrylate, Tricyclodecane Dimethanol Di(meth)acrylate, Neopentyl Glycol Modified Trimethylolpropane Di(meth)acrylate, Tripropylene Glycol Di(meth)acrylate , tripropylene glycol di(meth)acrylate modified by ethylene oxide, triglycerin di(meth)acrylate, dipropylene glycol di(meth)acrylate, glycerol triglyceride modified by epichlorohydrin ( Meth)acrylate, glycerol tri(meth)acrylate modified with ethylene oxide, glycerol tri(meth)acrylate modified with propylene oxide, phosphoric acid tri(meth)acrylate modified with ethylene oxide Meth) acrylate, trimethylolpropane tri(meth)acrylate modified by caprolactone, trimethylolpropane tri(methyl) modified by hydroxypropyl acrylate (HPA) Acrylic, Cyclic Trimethylolpropane tri(meth)acrylate modified with ethylene oxide, trimethylolpropane tri(meth)acrylate modified with propylene oxide, trimethylolpropane benzoate (meth)acrylate base) acrylate, tris((meth)acryloylethyl)isocyanurate, alkoxy-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol poly(meth)acrylic acid (meth)acrylate esters, alkyl-modified dipentaerythritol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, etc., or a combination of the above compounds.

R ⁵ in the polymercapto compound represented by formula (II) preferably has a carbon number of 0 to 22 (when the carbon number is 0, R ⁴ is a single bond, and formula (II) represents HS-CH ₂ - CH ₂ -SH), more preferably 1-16, particularly preferably 2-12. Specific examples of polymercapto compounds represented by formula (II) include 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, bisdimercaptoethanethiol (HS- CH ₂ CH ₂ -S-CH ₂ CH ₂ -SH), dimercaptotriethylene glycol, trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(mercaptopropionate), pentaerythritol tetrakis( mercaptoacetate), pentaerythritol tris(mercaptoacetate), pentaerythritol tetrakis(mercaptopropionate), dipentaerythritol hexa(mercaptopropionate), dipentaerythritol hexa(mercaptopropionate), or combinations thereof.

The alkylene group having a carbon number of 1 to 12 that R ⁶ in the mercapto compound having a carboxyl group represented by formula (III) may be a linear or branched alkylene group. Specifically, the alkylene group is, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, deca A group such as an alkyl group or a dodecylene group. Examples of the mercapto compound having a carboxyl group represented by formula (III) include thioglycolic acid.

In the present invention, the above-mentioned addition reaction can firstly mix the polyfunctional (meth)acrylate (monomer) represented by formula (I) with the polymercapto compound represented by formula (II), at room temperature to 100 ° C , and add a basic catalyst to carry out. The reaction time is usually 30 minutes to about 6 hours. In this way, a multi-branched polymer can be obtained.

Next, a mercapto compound having a carboxyl group represented by formula (III) may be added to the multibranched polymer, and an addition reaction may be performed again. In this way, a multi-branched polymer with carboxyl groups can be obtained.

In addition, the completion of the synthesis of the multibranched polymer (D) can be confirmed using a general analytical instrument such as liquid chromatography (liquid chromatography) or gel filtration chromatography (gelfiltration chromatography).

In addition, when synthesizing the multibranched polymer (D), a polymerization inhibitor may be added as necessary. As the polymerization inhibitor, a hydroquinone compound, a phenol compound, or a combination thereof, which are generally used to inhibit the polymerization of (meth)acrylate compounds, can be used. Specific examples of polymerization inhibitors include, but are not limited to, hydroquinone, methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol, dibutylhydroxytoluene, 2,4,6 - Tri-tert-butylphenol (BHT), or a combination of the above compounds.

Based on the usage amount of alkali-soluble resin (A) being 100 parts by weight, the usage amount of multi-branched polymer (D) can be 3 parts by weight to 35 parts by weight, preferably 4 parts by weight to 30 parts by weight, and more preferably 5 parts by weight to 25 parts by weight.

It should be noted that when the photosensitive resin composition does not contain the multi-branched polymer (D), the adhesion and hardness of the photosensitive resin composition are not good. Specifically, when the photosensitive resin composition comprises a multi-branched polymer (D), the mercapto group of the multi-branched polymer (D) can increase the black matrix formed by the photosensitive resin composition and the substrate (such as glass). Affinity, thereby solving the problem of poor adhesion of the black matrix produced by the photosensitive resin composition. In addition, the multi-branched polymer also has an ethylenically unsaturated group, which can increase the crosslinking density of the cured product, thereby solving the problem of poor hardness of the black matrix.

Again, when the multi-branched polymer (D) has a carboxyl group, it can increase the Van der Waals force between the black matrix formed by the photosensitive resin composition and the substrate (such as glass), and the carboxyl group can participate in the photochemical reaction to increase the hardened product ( The crosslinking density of the black matrix) can further improve the adhesion and hardness of the black matrix produced by the photosensitive resin composition.

Solvent (E)

The solvent (E) means that the alkali-soluble resin (A), the compound (B) having an ethylenically unsaturated group (B), the photoinitiator (C), the multi-branched polymer (D) and the black pigment (F) can be dissolved, However, it is an organic solvent that does not react with the above-mentioned components, and is preferably one with appropriate volatility.

The solvent (E) is, for example, (poly)alkylene glycol monoalkyl ethers, (poly)alkylene glycol monoalkyl ether acetates, other ethers, ketones, alkyl lactates, other esters, Aromatic hydrocarbons, carboxylic acid amides or a combination of the above solvents.

Specific examples of (poly)alkylene glycol monoalkyl ethers include ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol Alcohol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n- Butyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether or a combination of the above solvents.

Specific examples of (poly)alkylene glycol monoalkyl ether acetates include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate or a combination of the above solvents.

Specific examples of other ethers include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, or a combination of the above solvents.

Specific examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone or a combination of the above solvents.

Specific examples of alkyl lactates include methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, or combinations of the above solvents.

Specific examples of other esters include methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxypropionate Ethyl ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate (Ethyl3-ethoxypropionate, referred to as EEP), ethyl ethoxyacetate, ethyl glycolate, 2-hydroxy-3-methyl methyl butyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate Esters, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate , methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxybutyrate or a combination of the above solvents.

Specific examples of aromatic hydrocarbons include toluene, xylene, or combinations thereof.

Specific examples of carboxylic acid amides include N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or combinations of the above solvents.

The solvent (E) is preferably propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate or a combination of the above solvents. The said solvent (E) can be used individually or in combination of multiple types.

Based on 100 parts by weight of the alkali-soluble resin (A), the usage amount of the solvent (E) can be 1000 parts by weight to 5000 parts by weight, preferably 1200 parts by weight to 4500 parts by weight, and more preferably 1400 parts by weight to 4000 parts by weight.

Black Pigment (F)

The black pigment (F) is preferably a black pigment having heat resistance, light resistance, and solvent resistance.

Specific examples of black pigments (F) include: black organic pigments such as perylene black, cyanine black, or aniline black; red, blue, green, purple, yellow, cyanine, etc. Among pigments such as cyanine or magenta, two or more pigments are selected and mixed to form a mixed-color organic pigment close to black; carbon black, chromium oxide, iron oxide, titanium black (titaniumblack) or graphite and other light-shielding materials, wherein specific examples of the above-mentioned carbon black include C.I. , #1000, #2350 or #2650). The said black pigment (F) can be used individually or in combination of multiple types.

The black pigment (F) is preferably carbon black or C.I. Pigment Black 7, and the carbon black is, for example, commercially available MA100 or MA230 manufactured by Mitsubishi Chemical.

Based on 100 parts by weight of the alkali-soluble resin (A), the used amount of the black pigment (F) can be 60 parts by weight to 600 parts by weight, preferably 80 parts by weight to 500 parts by weight, and more preferably 100 parts by weight parts to 400 parts by weight.

Additive (G)

On the premise of not affecting the efficacy of the present invention, the photosensitive resin composition of the present invention may further optionally add an additive (G). Specific examples of the additive (G) include surfactants, fillers, polymers (polymers other than the above-mentioned alkali-soluble resin (A)), adhesion promoters, antioxidants, ultraviolet absorbers, or anti-coagulation agents.

A surfactant contributes to the improvement of the applicability of a photosensitive resin composition. Specific examples of surfactants include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane-based surfactants, fluorine-based surfactants, or the above-mentioned surfactants. combination of agents.

Specifically, surfactants such as polyethoxy dodecyl ether, polyethoxy stearyl ether, polyethoxy oleyl ether and other polyethoxyalkyl ethers (polyoxyethylenealkylethers); Polyethoxyalkylphenylene ethers such as octylphenyl ether and polyethoxynonylphenylene ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate class; sorbitan fatty acid esters; fatty acid modified polyesters; or tertiary amine modified polyurethanes. The above-mentioned surfactants can be used alone or in combination.

Specific examples of surfactants include KP products manufactured by Shin-Etsu Chemical Industry, SF-8427 products manufactured by Dow Corning Toray Co., Ltd., and Preflon manufactured by Kyoeisha Oleochemical Industry. (Polyflow) products, Aifdorp (F-Top) products manufactured by Tochem Products Co., Ltd. (Tochem Products Co., Ltd.), Megafac products manufactured by Dainippon Ink Chemical Industry, Fluorade products manufactured by Sumitomo 3M, AsahiGuard products manufactured by Asahi Glass or Surflon products manufactured by Asahi Glass Corporation.

Specific examples of the filler include glass, aluminum, and the like.

Specific examples of the polymer include polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, or a combination of the above polymers.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-amine N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-epoxypropyl Alcohol propyltrimethoxysilane, 3-glycidyl propylmethyldiethoxysilane, 3-glycidyl propylmethyldimethoxysilane, 2-(3,4-epoxy Hexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methylpropionyloxypropyltrimethoxysilane, 3-mercapto Propyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or a combination of the above compounds.

Specific examples of antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, or combinations thereof.

Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenylazide, alkoxyphenone, or a combination of the above compounds.

Specific examples of the anti-coagulation agent include sodium polyacrylate and the like.

Based on 100 parts by weight of the alkali-soluble resin (A), the usage amount of the additive (G) is 0.1 parts by weight to 10 parts by weight, preferably 0.5 parts by weight to 8 parts by weight, and more preferably 1 part by weight to 6 parts by weight.

<Method for producing photosensitive resin composition>

The method that can be used for preparing photosensitive resin composition is for example: with alkali soluble resin (A), compound (B) with ethylenically unsaturated group, photoinitiator (C), multi-branched polymer (D), solvent ( E) and the black pigment (F) are placed in a stirrer and stirred to make them uniformly mixed into a solution state. Additive (G) can also be added if necessary, and after being uniformly mixed, a photosensitive resin composition in a solution state can be obtained.

Moreover, the preparation method of a photosensitive resin composition is not specifically limited. The preparation method of the photosensitive resin composition is, for example, first dispersing a part of the alkali-soluble resin (A) and a compound (B) having an ethylenically unsaturated group in a part of the solvent (E) to form a dispersion solution; and then mixing The remaining alkali-soluble resin (A), compound (B) with ethylenically unsaturated group, photoinitiator (C), multi-branched polymer (D), solvent (E) and black pigment (F) are prepared.

Alternatively, the photosensitive resin composition may also be formed by first dispersing a part of the black pigment (F) in a mixture composed of part of the alkali-soluble resin (A) and a part of the solvent (E) to form a black pigment dispersion; and It is prepared by adding an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), a multibranched polymer (D), a solvent (E) and a black pigment (F). Moreover, the dispersion|distribution process of the said black pigment (F) can be performed, for example by mixing with a mixer, such as a bead mill (beads mill) or a roll mill (roll mill).

<Manufacturing method of black matrix>

The manufacturing method of the black matrix includes pre-baking, exposing, developing and post-baking the photosensitive resin composition on the substrate in sequence. The black matrix is used to isolate each pixel layer. Moreover, when the film thickness of the black matrix is 1 μm, the optical density range can be above 3.0, preferably 3.2 to 5.5, and more preferably 3.5 to 5.5. The manufacturing method of the black matrix is described in detail below.

First, a photosensitive resin composition in a solution state is uniformly coated on a substrate by a coating method such as spin coating or cast coating to form a coating film. Specific examples of the above-mentioned base material include: non-alkali glass, soda lime glass, hard glass (Pileus glass), quartz glass used for liquid crystal display devices, etc., and those on which a transparent conductive film is attached; or used for solid Photoelectric conversion device substrates (such as silicon substrates) of imaging devices, etc.

After the coating film is formed, most of the solvent is removed by drying under reduced pressure, and then the residual solvent is completely removed by pre-bake to form a pre-bake coating film. It should be noted that the conditions of reduced-pressure drying and pre-baking vary according to the types and ratios of the components. Generally speaking, drying under reduced pressure is performed under a pressure of less than 200 mmHg for 1 second to 20 seconds, and pre-baking is performed at a temperature of 70° C. to 110° C. for 1 minute to 15 minutes.

Next, the above-mentioned prebaked coating film is exposed with a photomask having a specific pattern. The light used in the exposure process is preferably ultraviolet light such as g-line, h-line or i-line, and the ultraviolet irradiation device can be (ultra) high pressure mercury lamp or metal halide lamp.

Then, at a temperature of 23±2°C, immerse the above-mentioned exposed pre-baked coating film in a developing solution to remove the above-mentioned unexposed part of the pre-baked coating film, thereby forming a specific patterns.

The developing solution is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methyl silicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, Basic compounds such as tetramethylamine hydroxide, tetraethylamine hydroxide, choline, pyrrole, piperidine, or 1,8-diazabicyclo[5.4.0]-7-undecene, etc. The concentration of the developer is generally 0.001% by weight to 10% by weight, preferably 0.005% by weight to 5% by weight, and more preferably 0.01% by weight to 1% by weight.

After the pre-baked coating film is developed, the substrate with the specific pattern is washed with water, and then the above-mentioned specific pattern is air-dried with compressed air or compressed nitrogen. Then, a post-baking process is performed with a heating device such as a hot plate or an oven. The post-bake temperature is generally 150 to 250° C., with a heating time of 5 minutes to 60 minutes using a hot plate and a heating time of 15 minutes to 150 minutes using an oven. After the above processing steps, a black matrix can be formed on the substrate.

<Method of manufacturing pixel layer and color filter>

The manufacturing method of the pixel layer is similar to the manufacturing method of the black matrix. Specifically, the photosensitive composition for the color filter is coated on the substrate on which the black matrix has been formed, and then subjected to pre-baking, exposure, development and post-baking in sequence. However, in the conditions of the reduced-pressure drying, the reduced-pressure drying is performed under a pressure of 0 mmHg to 200 mmHg for 1 second to 60 seconds. After the above-mentioned processing steps, a specific pattern can be fixed to form a pixel layer. And, repeat the above steps to sequentially form pixel layers such as red, green, and blue on the substrate, and then obtain the substrate on which the black matrix and the pixel layer are formed (ie, the color filter with the pixel layer).

<Manufacturing method of liquid crystal display device>

First, the color filter formed by the above-mentioned manufacturing method of the color filter and the substrate provided with a thin film transistor (thinfilmtransistor; TFT for short) are arranged oppositely, and a gap (cell interval, cell gap). Next, the color filter and the peripheral portion of the above-mentioned substrate are bonded together with an adhesive agent, and an injection hole is left. Then, liquid crystal is injected through the injection hole into the gap separated by the surface of the substrate and the adhesive, and finally the injection hole is sealed to form a liquid crystal layer. Subsequently, a liquid crystal display device was fabricated by providing a polarizing plate on the other side of the color filter contacting the liquid crystal layer and the other side of the substrate contacting the liquid crystal layer. The liquid crystals used above, that is, liquid crystal compounds or liquid crystal compositions, are not particularly limited here. However, any liquid crystal compound and liquid crystal composition can be used.

In addition, the liquid crystal alignment film used in the production of color filters is used to restrict the alignment of liquid crystal molecules, and there is no special limitation, any inorganic or organic matter can be used, and the present invention is not limited thereto.

Preparation Example of Polymerizable Unsaturated Group-Containing Diol Compound (a-1)

Preparation Examples 1 to 6 of the diol compound (a-1) containing a polymerizable unsaturated group are described below:

Preparation Example 1

First, 100 parts by weight of fluorene epoxy compound (model ESF-300, manufactured by Nippon Steel Chemical; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 parts by weight of Parts of 2,6-di-tert-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were added to a 500 ml four-necked flask in a continuous manner. The feed rate was controlled at 25 parts by weight/min, and the temperature during the reaction was maintained at 100°C to 110°C. After 15 hours of reaction, a light yellow transparent mixed liquid with a solid content concentration of 50% by weight could be obtained. Next, subject the above-mentioned pale yellow transparent mixed liquid to the steps of extraction, filtration, and heating and drying to obtain the diol compound containing polymerizable unsaturated groups (a-1- 1).

Preparation example 2

First, 100 parts by weight of fluorene epoxy compound (model PG-100, manufactured by Osaka Gas; epoxy equivalent 259), 35 parts by weight of methacrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 parts by weight Parts of 2,6-di-tert-butyl-p-cresol and 135 parts by weight of propylene glycol monomethyl ether acetate were added to a 500 ml four-necked flask in a continuous manner. The feed rate is controlled at 25 parts by weight/min, and the temperature during the reaction is maintained at 100°C to 110°C. After 15 hours of reaction, a light yellow transparent mixed liquid with a solid content of 50% by weight can be obtained. The above-mentioned light yellow transparent mixed liquid is subjected to the steps of extraction, filtration, and heating and drying to obtain the diol compound (a-1-2) containing a polymerizable unsaturated group in Preparation Example 2 with a solid content of 99.9% by weight. .

Preparation example 3

With 100 parts by weight of fluorene epoxy compound (model ESF-300, manufactured by Nippon Steel Chemical; epoxy equivalent 231), 100 parts by weight of 2-methacryloylethoxysuccinate, 0.3 parts by weight of chlorine Benzyltriethylammonium, 0.1 parts by weight of 2,6-di-tert-butyl-p-cresol and 200 parts by weight of propylene glycol monomethyl ether acetate were continuously added into a 500 ml four-necked flask. The feed rate is controlled at 25 parts by weight/min, and the temperature during the reaction is maintained at 100°C to 110°C. After 15 hours of reaction, a light yellow transparent mixed liquid with a solid content of 50% by weight can be obtained. The above light yellow transparent mixed liquid was subjected to the steps of extraction, filtration and heating and drying to obtain the diol compound (a-1-3) containing polymerizable unsaturated groups in Preparation Example 3 with a solid content of 99.9% by weight.

Preparation Example 4

First, in a 1000 ml three-necked flask equipped with mechanical stirring, a thermometer and a reflux condenser, add 0.3 moles of bis(4-hydroxyphenyl)sulfone, 9 moles of 3-chloro-1,2-epoxypropane and 0.003 moles of tetramethylammonium chloride. Next, it heated to 105 degreeC, stirring, and was made to react at 105 degreeC for 9 hours. Then, unreacted 3-chloro-1,2-propylene oxide was distilled off under reduced pressure. After that, the reaction system was lowered to room temperature, and 9 moles of benzene and 0.5 moles of sodium hydroxide (30% by weight aqueous solution dissolved in water) were added with stirring. Then, the temperature was raised to 60° C. and maintained for 3 hours. Then, the reaction solution was washed repeatedly with water until there was no chloride ion (checked with silver nitrate). The solvent benzene was distilled off under reduced pressure, followed by drying at 75° C. for 24 hours to obtain an epoxy compound of bis(4-hydroxyphenyl)sulfone.

100 parts by weight of two (4-hydroxyphenyl) sulfone epoxy compounds (epoxy equivalent 181), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 parts by weight of 2, 6-di-tert-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were continuously added into a 500 ml four-necked flask. The feed rate is controlled at 25 parts by weight/min, and the temperature during the reaction is maintained at 100°C to 110°C. After 15 hours of reaction, a light yellow transparent mixed liquid with a solid content of 50% by weight can be obtained. The diol compound (a-1-4) containing a polymerizable unsaturated group of Preparation Example 4 with a solid content of 99.9% by weight can be obtained by subjecting the above-mentioned light yellow transparent mixed liquid to the steps of extraction, filtration, and heating and drying .

Preparation Example 5

Add 0.3 moles of bis(4-hydroxyphenyl)hexafluoropropane, 9 moles of 3-chloro-1,2-epoxypropane and 0.003 moles of tetramethylammonium chloride. Next, it heated to 105 degreeC, stirring, and was made to react at 105 degreeC for 9 hours. Next, unreacted 3-chloro-1,2-propylene oxide was distilled off under reduced pressure. After that, the reaction system was lowered to room temperature, and 9 moles of benzene and 0.5 moles of sodium hydroxide (30% by weight aqueous solution dissolved in water) were added with stirring. Then, the temperature was raised to 60° C. and maintained for 3 hours. Then, the reaction solution was washed repeatedly with water until there was no chloride ion (checked with silver nitrate). The solvent benzene was distilled off under reduced pressure, followed by drying at 75° C. for 24 hours to obtain an epoxy compound of bis(4-hydroxyphenyl)hexafluoropropane.

The epoxy compound (epoxy equivalent weight 224) of 100 parts by weight of bis(4-hydroxyphenyl) hexafluoropropane, the methacrylic acid of 35 parts by weight, the benzyltriethylammonium chloride of 0.3 parts by weight, 0.1 parts by weight Parts of 2,6-di-tert-butyl-p-cresol and 135 parts by weight of propylene glycol monomethyl ether acetate were added to a 500 ml four-necked flask in a continuous manner. The feed rate is controlled at 25 parts by weight/min, and the temperature during the reaction is maintained at 100°C to 110°C. After 15 hours of reaction, a light yellow transparent mixed liquid with a solid content of 50% by weight can be obtained. The diol compound (a-1-5) containing a polymerizable unsaturated group in Preparation Example 5 with a solid content of 99.9% by weight can be obtained by subjecting the above-mentioned light yellow transparent mixed liquid to the steps of extraction, filtration, and heating and drying. .

Preparation example 6

Add 0.3 moles of bis(4-hydroxyphenyl)dimethylsilane, 9 moles of 3-chloro-1,2-epoxypropane and 0.003 moles of tetramethylammonium chloride. Next, it heated to 105 degreeC, stirring, and was made to react at 105 degreeC for 9 hours. Next, unreacted 3-chloro-1,2-propylene oxide was distilled off under reduced pressure. After that, the reaction system was lowered to room temperature, and 9 moles of benzene and 0.5 moles of sodium hydroxide (30% by weight aqueous solution dissolved in water) were added with stirring. Then, the temperature was raised to 60° C. and maintained for 3 hours. Then, the reaction solution was washed repeatedly with water until there was no chloride ion (checked with silver nitrate). The solvent benzene was distilled off under reduced pressure, and then dried at 75° C. for 24 hours to obtain an epoxy compound of bis(4-hydroxyphenyl)dimethylsilane.

The epoxy compound (epoxy equivalent weight 278) of the bis(4-hydroxyphenyl) dimethyl silane of 100 parts by weight, the 2-methacryloylethoxysuccinate of 100 parts by weight, the 0.3 part by weight of Benzyltriethylammonium chloride, 0.1 parts by weight of 2,6-di-tert-butyl-p-cresol and 200 parts by weight of propylene glycol monomethyl ether acetate were continuously added into a 500 ml four-neck flask. The feed rate is controlled at 25 parts by weight/min, and the temperature of the reaction process is maintained at 100°C to 110°C. After 15 hours of reaction, a light yellow transparent mixed liquid with a solid content of 50% by weight can be obtained. The diol compound (a-1-6) containing a polymerizable unsaturated group in Preparation Example 6 with a solid content of 99.9% by weight was obtained by subjecting the above-mentioned light yellow transparent mixed liquid to the steps of extraction, filtration, and heating and drying. .

Synthesis example of the first alkali-soluble resin (A-1)

Synthesis Example A-1-1 to Synthesis Example A-1-10 of the first alkali-soluble resin (A-1) are described below:

Synthesis Example A-1-1

First, 1.0 mol of polymerizable unsaturated group-containing diol compound (a-1-1), 0.1 mol of 4,4'-hexafluoroisopropylidene diphthalic dianhydride (a-2- 1-a), 0.2 mol of pyromellitic dianhydride (a-2-2-c), 0.4 mol of maleic acid (a-3-2-a), 1.0 mol of tetrahydrophthalic anhydride (a-3-2-b), 1.9 g of benzyltriethylammonium chloride, 0.6 g of 2,6-di-tert-butyl-p-cresol, and 750 g of propylene glycol monomethyl ether acetate were added simultaneously It was added to a 500 ml four-necked flask to form a reaction solution. Here, "simultaneous addition" means adding tetracarboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its acid anhydride (a-3) at the same reaction time. Next, the above reaction solution was heated to 110° C. and reacted for 2 hours to obtain the first alkali-soluble resin A-1-1 with an acid value of 129 mg KOH/g and a number average molecular weight of 2368.

Synthesis Example A-1-2

1.0 mole of diol compound (a-1-2) containing polymerizable unsaturated groups, 2.0 grams of benzyltriethylammonium chloride, 0.7 grams of 2,6-di-tert-butyl-p-cresol and 700 The propylene glycol methyl ether acetate of 5 grams is added in the 500 milliliter four-neck flask, to form reaction solution. Next, add 0.2 mol of 1,4-difluoropyromellitic dianhydride (a-2-1-b), 0.2 mol of benzophenone tetracarboxylic dianhydride (a-2-2-b), And react at 90° C. for 2 hours. Then, 1.2 mol of tetrahydrophthalic anhydride (a-3-2-b) was added, and it was made to react at 90 degreeC for 4 hours. Here, "staged addition" refers to adding tetracarboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its anhydride (a-3) respectively at different reaction times, that is, adding tetracarboxylic acid first or its acid dianhydride (a-2), and then add dicarboxylic acid or its acid anhydride (a-3). Through the above synthesis steps, the first alkali-soluble resin A-1-2 with an acid value of 125 mg KOH/g and a number average molecular weight of 3388 can be obtained.

Synthesis Example A-1-3, Synthesis Example A-1-5, Synthesis Example A-1-7 and Synthesis Example A-1-9

The first alkali-soluble resin of Synthesis Example A-1-3, Synthesis Example A-1-5, Synthesis Example A-1-7 and Synthesis Example A-1-9 is the same step as Synthesis Example A-1-1 To prepare, and its difference lies in: change the first alkali-soluble resin composition kind and usage amount, reaction time, reaction temperature and reactant addition time (as shown in Table 1).

Synthesis Example A-1-4, Synthesis Example A-1-6, Synthesis Example A-1-8 and Synthesis Example A-1-10

The first alkali-soluble resin of Synthesis Example A-1-4, Synthesis Example A-1-6, Synthesis Example A-1-8 and Synthesis Example A-1-10 is the same step as Synthesis Example A-1-2 To prepare, and its difference lies in: change the first alkali-soluble resin composition kind and usage amount, reaction time, reaction temperature and reactant addition time (as shown in Table 1).

The compounds corresponding to the abbreviations in Table 1 and Table 2 are as follows.

Table 1

Table 1 (continued)

Synthesis example of the second alkali-soluble resin (A-2)

Synthesis Example A-2-1 to Synthesis Example A-2-3 of the second alkali-soluble resin (A-2) are described below:

Synthesis Example A-2-1

1.0 mol of polymerizable unsaturated group-containing diol compound (a-1-1), 1.9 g of benzyltriethylammonium chloride and 0.6 g of 2,6-di-tert-butyl-p-cresol were dissolved in In 700 grams of propylene glycol methyl ether acetate, 0.3 moles of biphenyl tetracarboxylic acid (a-2-2-a) and 1.4 moles of maleic acid (a-3-2-a) were added simultaneously. Then, it was heated to 110° C. and reacted for 2 hours to obtain the second alkali-soluble resin A-2-1 with an acid value of 125 mg KOH/g and a number average molecular weight of 2455.

Synthesis Example A-2-2

The second alkali-soluble resin of Synthesis Example A-2-2 is prepared in the same steps as Synthesis Example A-2-1, and its difference lies in: changing the composition type and usage amount of the second alkali-soluble resin, reaction Time, reaction temperature and reactant addition time (as shown in Table 2). It should be noted that, here, "simultaneous addition" refers to the addition of tetracarboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its acid anhydride (a-3) at the same reaction time, while "stepwise addition "Refers to adding tetracarboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its acid anhydride (a-3) respectively at different reaction times, namely adding tetracarboxylic acid or its acid dianhydride (a-3) first -2), and then add dicarboxylic acid or its anhydride (a-3).

Table 2

Synthesis example of other alkali-soluble resin (A-3)

Synthesis Example A-3-1 to Synthesis Example A-3-3 of other alkali-soluble resins (A-3) are described below:

Synthesis Example A-3-1

A nitrogen inlet, a stirrer, a heater, a condenser tube and a thermometer are set on a four-necked flask with a volume of 1000 milliliters. After introducing nitrogen, add 30 parts by weight of 2-hydroxyethyl methacrylate (HEMA), 10 parts by weight of Benzyl methacrylate (BzMA), 60 parts by weight of CF9BuMA, 3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) (AMBN) and 300 parts by weight of diethylene glycol dimethyl Ether (Diglyme). Next, the above mixture was stirred slowly and the solution was allowed to warm to 80 °C. Next, polycondensation was carried out at 80° C. for 6 hours. Then, after the solvent is evaporated, another alkali-soluble resin A-3-1 can be obtained.

Synthesis Example A-3-2 to Synthesis Example A-3-3

Other alkali-soluble resins from Synthesis Example A-3-2 to Synthesis Example A-3-3 are prepared in the same steps as Synthesis Example Synthesis Example A-3-1, and the difference is: change the composition of other alkali-soluble resins Component types and their usage amounts, reaction time, reaction temperature, and reactant addition time (as shown in Table 3), wherein the compounds corresponding to the abbreviations in Table 3 are as follows.

table 3

Synthesis example of multibranched polymer (D)

Synthesis Example D-1 to Synthesis Example D-3 of the multibranched polymer (D) are illustrated below:

Synthesis example D-1

In a four-necked flask with a capacity of 1L, add 25 grams of trimethylolpropane tris(mercaptoacetate) (0.28 moles of mercapto groups), 177 grams of pentaerythritol tetraacrylate (2.01 moles of carbon-carbon double bonds), 0.1 grams of Hydroquinone and 0.01 g of benzyldimethylamine (as a photoinitiator, benzyldimethylamine) were reacted at 60° C. for 12 hours. For each reaction product, the disappearance of the sulfhydryl group was confirmed by iodine titration to obtain the multibranched polymer D-1. The molecular weight of the multibranched polymer D-1 measured by gel filtration chromatography was 4,400.

Synthesis example D-2

In a four-necked flask with a capacity of 1L, add 20 grams of pentaerythritol tetrakis (mercaptoacetate) (0.19 moles of mercapto groups), 212 grams of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate mixture (carbon-carbon double bond 2.12 mol), 0.1 gram of hydroquinone and 0.01 gram of benzyldimethylamine, and reacted at 60° C. for 12 hours. For each reaction product, the disappearance of the sulfhydryl group was confirmed by iodometric titration to obtain the multibranched polymer D-2. The molecular weight of multibranched polymer D-2 measured by gel filtration chromatography was 11,000.

Synthesis example D-3

In a four-necked flask with a capacity of 1L, add 20 grams of pentaerythritol tetrakis (mercaptoacetate) (0.19 moles of mercapto groups), a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (2.12 moles of carbon-carbon double bond) of 212 grams ), 58 grams of propylene glycol monomethyl ether acetate (as a solvent), 0.1 gram of hydroquinone and 0.01 gram of benzyldimethylamine, and reacted at 60° C. for 12 hours. For each reaction product, the intermediate product can be obtained by confirming the disappearance of the sulfhydryl group by iodometric titration. The molecular weight of the intermediate product measured by gel filtration chromatography was 11,000.

Next, in the four-necked flask, 20 g (0.22 mol) of thioglycolic acid was added, and reacted at 60° C. for 12 hours. For each reaction product, the disappearance of the sulfhydryl group was confirmed by iodometric titration to obtain the multibranched polymer D-3. The molecular weight of multibranched polymer D-3 measured by gel filtration chromatography was 12,000.

Examples of photosensitive resin

Embodiment 1 to embodiment 10 and comparative example 1 to comparative example 6 of photosensitive resin are illustrated below:

Example 1

a. Photosensitive resin composition

100 parts by weight of the first alkali-soluble resin A-1-1, 15 parts by weight of pentaerythritol triacrylate and esterified phthalic acid (abbreviated as B-1-1), 5 parts by weight of 1-[9 -Ethyl-6-(2-methylbenzoyl)-9 hydrogen-carbazole-3-substituent]-1-(oxygen-acetyl oxime) (abbreviated as C-1), 5 parts by weight of multi-branch Polymer D-1 (abbreviated as D-1) and 60 parts by weight of C.I. PigmentBK7 (referred to as F-1) were added to 1000 parts by weight of propylene glycol monomethyl ether acetate (referred to as E-1), and shaken After stirring evenly with a shaking type stirrer, the photosensitive resin composition of Example 1 can be prepared.

b. Film formation

The photosensitive resin composition of Example 1 was coated on a plain glass substrate (100 mm×100 mm×0.7 mm in size) by spin coating to form a coating film with a thickness of about 6 μm. Next, pre-bake the coating film at 90° C. for 2 to 3 minutes. Then, a photomask is placed between the exposure machine and the coating film, and the pre-baked coating film is patterned and exposed with 100mJ/cm2 of ultraviolet light (the exposure machine model is AG500-4N, manufactured by M&R Nanotechnology (M&RNanotechnology)) . The exposed coating film was immersed in a 0.05% potassium hydroxide aqueous solution for 45 to 90 seconds to remove unnecessary portions of the above exposed coating film. Then, the plain glass substrate was washed with water. Finally, the coating film was post-baked in an oven at 235° C. for 30 minutes to obtain a glass substrate on which the film of Example 1 was formed. Table 4 shows the results of evaluating the film of Example 1 by each evaluation method described below.

Example 2 to Example 10

The photosensitive resin composition and the film of embodiment 2 to embodiment 10 are prepared with the same steps as embodiment 1, and its difference is: change the component type and the usage amount of photosensitive resin composition (as shown in Table 4 shown), wherein the compounds corresponding to the abbreviations in Table 4 are as follows. The prepared film was evaluated by the following evaluation methods, and the results are shown in Table 4.

The compounds corresponding to the symbols in Table 4 and Table 5 are as follows.

Comparative Example 1 to Comparative Example 6

The photosensitive resin composition and film of Comparative Example 1 to Comparative Example 6 are prepared with the same steps as in Example 1, and the difference lies in: changing the composition type and usage amount of the photosensitive resin composition (as shown in Table 5 shown). The prepared film was evaluated by the following evaluation methods, and the results are shown in Table 5.

<Evaluation method>

a. Adhesion

Adhesion was evaluated by the cross-hatched measurement in 8.5.2 of JISK-5400-1990, 8.5 Adhesion test method. The films obtained in the above Examples and Comparative Examples were cut into 100 meshes with a knife. Then, stick it with adhesive tape and tear it off to observe the remaining mesh grid. The smaller the number of detached grids, the better the adhesion between the film and the substrate. Adhesion was evaluated according to the evaluation criteria shown below.

◎: 0%≦Number of meshes falling off≦3%

○: 3% < the number of mesh grids falling off ≦ 5%

△: 5%＜Number of fallen grids≦35%

╳: 35%＜Number of fallen grids≦100%

b.hardness

The films obtained in the above Examples and Comparative Examples were evaluated for their pencil hardness according to 8.4.1 of JIS K-5400-1990 pencil scratch test (pencil scratch test). The hardness of the film was evaluated according to the evaluation criteria shown below.

◎: 3H≦Pencil hardness

○: 1H≦Pencil hardness＜3H

△: HB≦Pencil hardness<1H

╳: pencil hardness < HB

Table 4

table 5

<Evaluation result>

From Table 4 and Table 5, it can be seen that the films formed with the photosensitive resin composition containing the first alkali-soluble resin (A-1) (containing the alkali-soluble resin having an aromatic structure having fluorine) (Example 1 to Implementation Example 10) compared with the film (comparative example 1, comparative example 2 and comparative example 6) formed by the photosensitive resin composition containing only the second alkali-soluble resin (A-2), only containing other alkali-soluble resin (A-2) -3) The adhesiveness of the film (comparative example 3 and comparative example 4) formed with the photosensitive resin composition was unsatisfactory.

In addition, compared with the films formed by the photosensitive resin composition containing the multi-branched polymer (D) (Example 1 to Example 10), the film formed by the photosensitive resin composition not containing the multi-branched polymer (D) The hardness of the film (Comparative Example 5 and Comparative Example 6) is not good.

Also, when the multi-branched polymer (D) contains carboxyl groups (Example 6 and Example 8), the adhesion and hardness of the film formed by the photosensitive resin composition are better.

In addition, when the number of moles of the diol compound (a-1) containing a polymerizable unsaturated group in the first alkali-soluble resin (A-1), the tetracarboxylic acid containing a fluorine atom or its acid dianhydride (a-2 -1) the number of moles and the number of moles of dicarboxylic acid containing fluorine atoms or its anhydride (a-3-1) satisfy the relational formula [(a-2-1)+(a-3-1)]/(a When -1)=0.4˜1.6 (that is, Example 4, Example 5, Example 6, Example 9 and Example 10), the adhesion of the film formed by the photosensitive resin composition is better.

Also, when the compound (B) having an ethylenically unsaturated group contains a compound (B-1) having an acidic group and at least three ethylenically unsaturated groups (Example 1, Example 2, Example 6 and Example 9), the adhesion and hardness of the film formed by the photosensitive resin composition are better.

In summary, the photosensitive resin composition of the present invention can effectively improve the problem of side etching and increase the distance between the black matrix and the substrate due to the alkali-soluble resin having an aromatic structure and a specific structure of fluorine and a multi-branched polymer (D). At the same time, it increases the cross-linking density in the black matrix, so it has the characteristics of good adhesion and good hardness, so it is suitable for making the black matrix of color filters.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than limiting them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: It is still possible to modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the various embodiments of the present invention. scope.

Claims (15)

1. a black matrix" photosensitive polymer combination, is characterized in that, comprising:

Alkali soluble resin (A);

There is the compound (B) of ethene unsaturated group;

Light initiator (C);

Multibranched polymers (D);

Solvent (E); And

Black pigment (F),

Wherein said alkali soluble resin (A) comprises the first alkali soluble resin (A-1) represented by formula (1),

In formula (1), A represents phenylene or has substituent phenylene, wherein said substituting group to be carbon number be 1 to 5 alkyl, halogen atom or phenyl; B represents-CO-,-SO ₂-,-C (CF ₃) ₂-,-Si (CH ₃) ₂-,-CH ₂-,-C (CH ₃) ₂-,-O-, 9,9-fluorenylidenes or singly-bound; L ¹represent the tetravalence carboxylic acid residues containing fluorine atom or the tetravalence carboxylic acid residues not containing fluorine atom; Y ¹represent the dibasic carboxylic acid residue containing fluorine atom or the dibasic carboxylic acid residue not containing fluorine atom; R ¹represent hydrogen atom or methyl; A represents the integer of 1 to 20; L ¹and Y ¹in, at least one contains fluorine atom;

Described multibranched polymers (D) is the many sulfhydryl compounds represented by formula (II) and multiple functional radical (methyl) acrylate reactions represented by formula (I) and is formed,

In formula (I), R ²represent that hydrogen atom or carbon number are the alkyl of 1 to 4;

R ³represent the residue of n hydroxyl after esterification had in the compound of the hydroxyl of m hydroxyl, wherein m≤n, n represent the integer of 2 to 20,

The compound of described hydroxyl is R ⁴(OH) _mor described R ⁴(OH) _mthrough the compound of epoxypropane, epichlorokydrin, alkyl, alkoxy or hydroxypropyl acrylate upgrading,

R ⁴(OH) _mfor having the polyvalent alcohol that carbon number is 2 to 18, the polyol ethers formed by described polyvalent alcohol, the ester class formed by described polyvalent alcohol and acid reaction or silicone,

In formula (II), R ⁵represent singly-bound, carbon number be 1 alkyl or carbon number be the alkyl of the straight or branched of 2 to 22, R ⁵skeleton in the oxygen atom that also can comprise sulphur atom or form in ester group,

P represents the integer of 2 to 6, wherein works as R ⁵when representing singly-bound, p represents 2; Work as R ⁵when representing that carbon number is the alkyl of 1, p represents the integer of 2 to 4; Work as R ⁵when representing that carbon number is the alkyl of the straight or branched of 2 to 22, p represents the integer of 2 to 6.

2. black matrix" photosensitive polymer combination according to claim 1, wherein, in described multibranched polymers (D), the sulfydryl of the described many sulfhydryl compounds represented by formula (II) is 1/200 to 1/2 relative to the addition molar ratio of the carbon-to-carbon double bond of described multiple functional radical (methyl) acrylate represented by formula (I).

3. black matrix" photosensitive polymer combination according to claim 1, wherein said multibranched polymers (D) is for by after described many sulfhydryl compounds of being represented by formula (II) and described multiple functional radical (methyl) acrylate reactions represented by formula (I) and remaining (methyl) is acrylate-based, react with the sulfhydryl compound with carboxyl represented by formula (III) further and formed

In formula (III), R ⁶represent that carbon number is the alkylidene of 1 to 12, q represents the integer of 1 to 3.

4. black matrix" photosensitive polymer combination according to claim 3, wherein, in described multibranched polymers (D), described many sulfhydryl compounds of being represented by formula (II) and the described sulfydryl with the sulfhydryl compound of carboxyl represented by formula (III) are 1/200 to 1/2 relative to the addition molar ratio of the carbon-to-carbon double bond of described multiple functional radical (methyl) acrylate represented by formula (I).

5. black matrix" photosensitive polymer combination according to claim 1, wherein said the first alkali soluble resin (A-1) represented by formula (1) is reacted by the first potpourri and obtains, and described first potpourri comprises:

Diol compound (a-1) containing polymerism unsaturated group;

Tetrabasic carboxylic acid or its acid dianhydride (a-2); And

Dicarboxylic acid or its acid anhydrides (a-3),

Described tetrabasic carboxylic acid or its acid dianhydride (a-2) comprise tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1), other tetrabasic carboxylic acids except described tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1) or its acid dianhydride (a-2-2) or the two combination;

Described dicarboxylic acid or its acid anhydrides (a-3) comprise dicarboxylic acid containing fluorine atom or its acid anhydrides (a-3-1), other dicarboxylic acid except described dicarboxylic acid containing fluorine atom or its acid anhydrides (a-3-1) or its acid anhydrides (a-3-2) or the two combination;

In described tetrabasic carboxylic acid or its acid dianhydride (a-2) and described dicarboxylic acid or acid anhydrides (a-3), at least one contains fluorine atom.

6. black matrix" photosensitive polymer combination according to claim 5, the tetracarboxylic compound containing fluorine atom that wherein said tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1) select free style (2-1) to represent and the group that the tetracarboxylic dianhydride's compound containing fluorine atom represented by formula (2-2) forms

In formula (2-1) and formula (2-2), L ²one of them in the group selecting free style (L-1) to formula (L-6) to represent;

Formula (L-1) is in formula (L-6), and E independently represents fluorine atom or trifluoromethyl separately, and * represents the position with carbon atom bond.

7. black matrix" photosensitive polymer combination according to claim 5, the dicarboxylic acid compound containing fluorine atom that wherein said dicarboxylic acid containing fluorine atom or its acid anhydrides (a-3-1) select free style (3-1) to represent and the group that the dicarboxylic anhydride compound containing fluorine atom represented by formula (3-2) forms

In formula (3-1) and formula (3-2), X ¹represent that carbon number is the organic group of the contain fluorine atoms of 1 to 100.

8. black matrix" photosensitive polymer combination according to claim 5, the molal quantity of the wherein said diol compound (a-1) containing polymerism unsaturated group, described containing the tetrabasic carboxylic acid of fluorine atom or the molal quantity of its acid dianhydride (a-2-1) and describedly meet relational expression [(a-2-1)+(a-3-1)]/(a-1)=0.4 ~ 1.6 containing the dicarboxylic acid of fluorine atom or the molal quantity of its acid anhydrides (a-3-1).

9. black matrix" photosensitive polymer combination according to claim 1, use amount wherein based on described alkali soluble resin (A) is 100 weight portions, the use amount of described first alkali soluble resin (A-1) is 10 weight portion to 100 weight portions, the described use amount with the compound (B) of ethene unsaturated group is 15 weight portion to 200 weight portions, the use amount of described smooth initiator (C) is 5 weight portion to 55 weight portions, the use amount of described multibranched polymers (D) is 3 weight portion to 35 weight portions, the use amount of described solvent (E) is 1000 weight portion to 5000 weight portions, and the use amount of described black pigment (F) is 60 weight portion to 600 weight portions.

10. black matrix" photosensitive polymer combination according to claim 1, the wherein said compound (B) with ethene unsaturated group comprises the compound (B-1) with acidic groups and at least three ethene unsaturated groups.

11. black matrix" photosensitive polymer combinations according to claim 10, use amount wherein based on described alkali soluble resin (A) is 100 weight portions, described in there is the compound (B-1) of acidic groups and at least three ethene unsaturated groups use amount be 15 weight portion to 150 weight portions.

The manufacture method of 12. 1 kinds of colored filters, is characterized in that, comprises and using by the black matrix" photosensitive polymer combination such as according to any one of claim 1 to 11 to form black matrix".

13. 1 kinds of black matrix"s, is characterized in that, are to be formed by the black matrix" photosensitive polymer combination as described in any one of claim 1 to 11.

14. 1 kinds of colored filters, is characterized in that, comprise black matrix" as claimed in claim 13.

15. 1 kinds of liquid crystal indicators, is characterized in that, comprise colored filter as claimed in claim 14.