JP6634291B2 - Photosensitive resin composition, photocurable pattern formed therefrom, and image display device having the same - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a photo-curing pattern formed therefrom, and an image display device provided with the same, and more particularly, to an effective CD-Bias control, and a pattern T / B ratio value. The present invention relates to a photosensitive resin composition capable of forming a pattern having excellent adhesiveness, a photocurable pattern formed therefrom, and an image display device including the same.

  In the display field, a photosensitive resin composition is used for forming various photo-curing patterns such as a photoresist, an insulating film, a protective film, a black matrix, and a column spacer. Specifically, the photosensitive resin composition is selectively exposed and developed by a photolithography process to form a desired photo-cured pattern. In this process, the yield in the process is improved, and the physical properties of the application target are improved. In order to improve the sensitivity, a photosensitive resin composition having high sensitivity is required.

  The pattern formation of the photosensitive resin composition is performed by photolithography, that is, a change in polarity of a polymer caused by a photoreaction and a crosslinking reaction. In particular, a change characteristic of solubility in a solvent such as an aqueous alkali solution after exposure is used.

  Pattern formation using the photosensitive resin composition is classified into a positive type and a negative type depending on the solubility of the exposed portion in development. In the positive type photoresist, a pattern is formed by exposing exposed portions to be dissolved by a developing solution, and in the negative type photoresist, exposing portions are not dissolved by a developing solution and unexposed portions are dissolved by a developing solution. It is a method. The positive type and the negative type are different from each other depending on a binder resin, a crosslinking agent, and the like to be used.

  The conventional photosensitive resin composition has a problem that a change in thickness occurs before and after the heating step, formation of a fine pattern is difficult, and developability is not sufficient.

  In recent years, in order to solve such a problem, a method of adding an inorganic powder to a photosensitive resin composition is disclosed in Japanese Patent Application Laid-Open No. 2000-095896. However, there is a problem that the content of the inorganic powder cannot be sufficiently increased due to a problem of a decrease in compatibility between the photosensitive resin composition and the inorganic powder and a decrease in developability due to adhesion to a substrate. Therefore, there is a limit that the above-mentioned problem of the photosensitive resin composition cannot be sufficiently solved.

Japanese Patent Laid-Open No. 2000-095896

  An object of the present invention is to provide a photosensitive resin composition capable of forming a fine pattern and controlling CD-Bias by improving the T / B ratio value of a pattern.

  Another object of the present invention is to provide a photosensitive resin composition having improved developability by improving adhesion to a substrate.

  Another object of the present invention is to provide a photosensitive resin composition having excellent mechanical properties of a pattern.

  Another object of the present invention is to provide a photocurable pattern formed from the photosensitive resin composition.

  1. An alkali-soluble resin (A) including a first resin having a repeating unit represented by the following chemical formula 1 and a second resin having a repeating unit represented by the following chemical formula 2, a polymerizable compound (B), and biimidazole A photosensitive resin composition comprising a system initiator (C1), an oxime ester-based initiator (C2), an ultraviolet absorber (D) represented by the following chemical formula 3, and a solvent (E).

[In the formula, n is an integer of 1 or more, R ₁ is hydrogen or a methyl group, and R ₂ is hydrogen or an alkyl group having 1 to 6 carbon atoms. ]

[Wherein, m is an integer of 1 or more, and R ₃ is hydrogen or a methyl group. ]

Wherein R ₁₄ and R ₁₅ are each independently an alkoxy group having 1 to 5 carbon atoms. ]

  2. In the above item 1, the photosensitive resin composition, wherein a mixing weight ratio of the first resin and the second resin is 20:80 to 80:20.

  3. 2. The photosensitive resin composition according to item 1, wherein the first resin has a weight average molecular weight of 10,000 to 30,000.

  4. In the above item 1, the photosensitive resin composition, wherein the weight average molecular weight of the second resin is 2,000 to 20,000.

  5. In the above item 1, the photosensitive resin composition, wherein the first resin has a repeating unit represented by the following chemical formula 1-1.

[Wherein, R ₄ , R ₅ , R ₆ , and R ₇ are each independently a hydrogen or a methyl group;
R ₈ represents benzyl (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, (2-phenyl) phenoxyethoxy (meth) acrylate, 2-hydroxy- (2-phenyl) phenolpropyl (meth) ) Acrylate, 2-hydroxy- (3-phenyl) phenoxypropyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, (meth) styrene, vinyltoluene, vinylnaphthalene, N-benzylmaleimide, methyl (meth) acrylate, ethyl ( (Meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, meth A structure derived from a monomer selected from the group consisting of xetitaethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and tetrahydrofuryl (meth) acrylate;
R ₉ is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (7);

R ₁₀ represents (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, and 2- (meth) A structure derived from a monomer selected from the group consisting of acryloyloxyethyl succinate,
R ₁₁ is hydrogen or an alkyl group having 1 to 6 carbon atoms,
a = 20-60 mol%, b = 5-30 mol%, c = 10-50 mol%, d = 5-30 mol%. ]

  6. In the above item 1, the photosensitive resin composition, wherein the second resin has a repeating unit represented by the following chemical formula 2-1.

[Wherein, R ₁₂ and R ₁₃ are each independently a hydrogen or a methyl group;
R ₁₄ is a structure derived from a monomer represented by the following formula (8):

R ₁₅ represents (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, and 2- (meth) A structure derived from a monomer selected from the group consisting of acryloyloxyethyl succinate,
e = 50-95 mol% and f = 5-50 mol%. ]

  7. In the above item 1, the biimidazole-based initiator (C1) is a photosensitive resin composition represented by the following chemical formula 4.

[In the formula, L _{3 to} L ₂₀ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom. ]

  8. In the above item 1, the oxime ester-based initiator (C2) is a compound represented by the following chemical formula 5, wherein the photosensitive resin composition is:

[Wherein, L ₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, L ₂ is hydrogen, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and L ₃ is hydrogen, an alkyl group having 1 to 6 carbon atoms, an aryl group, or _-SC 6 _{H 5} having 6 to 12 carbon atoms. ]

  9. A photocurable pattern formed of the photosensitive resin composition according to any one of the items 1 to 8.

  10. In the above item 9, the photocurable pattern is a photocurable pattern selected from the group consisting of an array flattening film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, and a column spacer pattern.

  11. Item 10. An image display device provided with the photocurable pattern according to Item 9.

  The photosensitive resin composition of the present invention exhibits a T / B ratio value and can form a pattern with improved accuracy.

  In addition, the photosensitive resin composition of the present invention has excellent developability, is capable of controlling CD-Bias of a pattern manufactured therefrom, and is capable of forming a fine pattern, and improves mechanical properties and adhesion to a substrate. be able to.

It is the drawing which showed the definition of T / B ratio roughly.

  The present invention provides an alkali-soluble resin (A) including a first resin having a repeating unit represented by Chemical Formula 1, and a second resin having a repeating unit represented by Chemical Formula 2, a polymerizable compound (B), By containing a biimidazole-based initiator (C1), an oxime ester-based initiator (C2), an ultraviolet absorber (D) represented by the chemical formula 3, and a solvent (E), excellent developability and fineness are achieved. The present invention relates to a photosensitive resin composition which can form a pattern and can form a pattern having excellent T / B ratio, mechanical properties, and adhesion.

  Hereinafter, the present invention will be described in detail.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention comprises an alkali-soluble resin (A), a polymerizable compound (B), a biimidazole initiator (C1), an oxime ester initiator (C2), and an ultraviolet absorber ( D) and a solvent (E).

Alkali-soluble resin (A)
The alkali-soluble resin (A) used in the present invention is a component that imparts solubility to an alkali developing solution used in a development step in forming a pattern, and has a repeating unit represented by the following chemical formula 1. 1 resin and a second resin having a repeating unit represented by the following chemical formula 2.

  Since the first resin according to the present invention has a repeating unit represented by the following chemical formula 1, photopolymerization is performed using a radical generated by a photopolymerization initiator in an exposure step. Further, the pattern formability and developability of the photosensitive resin composition can be improved.

[In the formula, n is an integer of 1 or more, R ₁ is hydrogen or a methyl group, and R ₂ is hydrogen or an alkyl group having 1 to 6 carbon atoms. ]

  The first resin according to the present invention may further have a repeating unit formed of another monomer known in the art in addition to the repeating unit of Formula 1, and may be formed only from the repeating unit of Formula 1. It may be done.

  The first resin according to the present invention is not particularly limited as long as it has a repeating unit represented by Chemical Formula 1, and can have, for example, a repeating unit represented by Chemical Formula 1-1 below.

[Wherein, R ₄ , R ₅ , R ₆ , and R ₇ are each independently a hydrogen or a methyl group;
R ₈ represents benzyl (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, (2-phenyl) phenoxyethoxy (meth) acrylate, 2-hydroxy- (2-phenyl) phenolpropyl (meth) ) Acrylate, 2-hydroxy- (3-phenyl) phenoxypropyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, (meth) styrene, vinyltoluene, vinylnaphthalene, N-benzylmaleimide, methyl (meth) acrylate, ethyl ( (Meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, meth A structure derived from a monomer selected from the group consisting of xetitaethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and tetrahydrofuryl (meth) acrylate;
R ₉ is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (7);

R ₁₀ represents (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, and 2- (meth) A structure derived from a monomer selected from the group consisting of acryloyloxyethyl succinate,
R ₁₁ is hydrogen or an alkyl group having 1 to 6 carbon atoms,
a = 20-60 mol%, b = 5-30 mol%, c = 10-50 mol%, d = 5-30 mol%. ]

  In the present invention, "(meth) acryl-" refers to "methacryl-", "acryl-" or both.

  In the present invention, each repeating unit represented by Chemical Formulas 1-1 and 1-2 and Chemical Formulas 2-1 and 2-2 is represented by Chemical Formulas 1-1 and 1-2 and Chemical Formulas 2-1 and 2-2. It should not be construed as limiting, as the repeated subunits in parentheses may be freely located anywhere in the chain within the stated mole% range. That is, each parenthesis in Chemical Formulas 1-1 and 1-2 and Chemical Formulas 2-1 and 2-2 is represented by one block to indicate mol%, but each repeating subunit is represented within the corresponding resin. If present, without limitation, they can be located in blocks or each separately.

  Preferred examples of the repeating unit represented by the formula 1-1 according to the present invention include a repeating unit represented by the following formula 1-2.

[Wherein, R ₁₆ , R ₁₇ , R ₁₈ , and R ₁₉ are each independently hydrogen or a methyl group, a = 20 to 60 mol%, b = 5 to 30 mol%, c = 10 to 50 mol% , D = 5 to 30 mol%. ]

  The weight average molecular weight of the first resin is preferably 10,000 to 30,000 from the viewpoint of exhibiting the most excellent pattern formability and developability. In the above-mentioned molecular weight range, the most excellent pattern formability and developability are exhibited.

  Since the second resin according to the present invention has a repeating unit represented by the following chemical formula 2, a thermosetting reaction is performed by a ring-opening polymerization reaction between an epoxy functional group and a carboxylic acid in a post-baking step. Therefore, the pattern formed by the photosensitive resin composition of the present invention can be formed even harder by radical polymerization of the first resin and thermosetting reaction of the second resin.

[Wherein, m is an integer of 1 or more, and R ₃ is hydrogen or a methyl group. ]

  The second resin according to the present invention may further have a repeating unit formed of another monomer known in the art in addition to the repeating unit of Formula 2, and may be formed only from the repeating unit of Formula 2. It may be done.

The second resin according to the present invention is not particularly limited as long as it has a repeating unit represented by Chemical Formula 2, and may have, for example, a repeating unit represented by Chemical Formula 2-1.

[Wherein, R ₁₂ and R ₁₃ are each independently a hydrogen or a methyl group;
R ₁₄ is a structure derived from a monomer represented by the following formula (8):

R ₁₅ represents (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, and 2- (meth) A structure derived from a monomer selected from the group consisting of acryloyloxyethyl succinate,
e = 50-95 mol% and f = 5-50 mol%. ]

  Preferred examples of the compound of Formula 2-1 according to the present invention include a compound of Formula 2-2 below.

[Wherein, R ₂₀ and R ₂₁ are each independently a hydrogen or a methyl group, and e = 50 to 95 mol% and f = 5 to 50 mol%. ]

  From the aspect of further improving the adhesion, the weight average molecular weight of the second resin is preferably from 2,000 to 20,000.

  If necessary, the first resin and the second resin according to the present invention may be, independently of each other, any other monomer known in the art in addition to the repeating units of the formulas 1-1 and 2-1. It may further have a repeating unit formed in a body, and may be formed only from the repeating units of Chemical Formula 1-1 and Chemical Formula 2-1.

  Examples of the monomer that forms a repeating unit in addition to the chemical formulas 1-1 and 2-1 include, but are not particularly limited to, monocarboxylic acids such as crotonic acid; and dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid. And anhydrides thereof; mono- (meth) acrylates of polymers having carboxy groups and hydroxyl groups at both terminals such as ω-carboxypolycaprolactone mono (meth) acrylate; vinyltoluene, p-chlorostyrene, o-methoxystyrene, m -Methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether Such as aromatic bi N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, N-substituted maleimide compounds such as Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide; methyl ( (Meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, etc. (C) alkyl (meth) acrylates; finger ring (meth) acrylates such as cyclopentyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and 2-dicyclopentanyloxyethyl (meth) acrylate; phenyl (meth) acrylate Aryl (meth) acrylates such as 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyl) Unsaturated oxetane compounds such as oxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane; methyl glycidyl (meth) Unsaturated oxirane compounds such as acrylate; cycloalkane or di cycloalkane ring having 4 to 16 carbon atoms which is substituted in the (meth) acrylate; and the like. These can be used alone or in combination of two or more.

  In the alkali-soluble resin according to the present invention, the mixing weight ratio of the first resin and the second resin may be 20: 80-80: 20, and preferably 30: 70-70: 30. . In the above range, the most excellent adhesion, developability and T / B ratio are exhibited.

  The alkali-soluble resin (A) preferably has an acid value in the range of 20 to 200 (KOH mg / g). When the acid value is within the above range, excellent developability and stability over time can be obtained.

  The content of the alkali-soluble resin (A) is not particularly limited, but is, for example, 10 to 90 parts by mass, preferably 25 to 70 parts by mass based on 100 parts by mass of the photosensitive resin composition based on the solid content. Parts may be included. When the content is within the above range, the solubility in a developer is sufficient, so that the developability is good and a photocurable pattern having excellent mechanical properties can be formed.

Polymerizable compound (B)
The polymerizable compound (B) used in the photosensitive resin composition of the present invention can increase the crosslink density during the manufacturing process and enhance the mechanical properties of the photocurable pattern.

  The polymerizable compound (B) can be used without any particular limitation as long as it is used in the art, and is, for example, a monofunctional monomer, a difunctional monomer, or another polyfunctional monomer. . The type is not particularly limited, but examples include the following compounds.

  Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and bisphenol. Bis (acryloyloxyethyl) ether of A, 3-methylpentanediol di (meth) acrylate and the like can be mentioned. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate Acrylate and the like. Among them, a bifunctional or higher polyfunctional monomer is preferably used.

  The content of the polymerizable compound (B) is not particularly limited, for example, 10 to 90 parts by mass, preferably 100 parts by mass, based on 100 parts by mass of the alkali-soluble resin based on the solid content in the photosensitive resin composition, It is used in the range of 30 to 80 parts by mass. When the polymerizable compound (B) is contained in the above content range, excellent durability can be obtained, and the developability of the composition can be improved.

Photopolymerization initiator (C)
The photopolymerization initiator according to the present invention is a component capable of polymerizing the polymerizable compound (B), and includes a biimidazole initiator (C1) and an oxime ester initiator (C2).

The biimidazole-based initiator (C1) can be used without any particular limitation as long as it contains two or more imidazole groups. Specific examples include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4,4' , 5,5'-Tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2- chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxy) biimidazole, 2,2-bis _(2, 6-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1, Examples include 2′-biimidazole or an imidazole compound in which the phenyl group at the 4,4 ′, 5,5 ′ position is substituted with a carboalkoxy group, and these can be used alone or in combination of two or more. Preferably, a compound represented by the following chemical formula 4 is used.

[In the formula, L _{3 to} L ₂₀ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom. ]

  The biimidazole-based initiator (C1) functions as an initiator for curing the surface of the coating film, and cures the surface of the coating film on which light is incident in the exposure step.

  The photosensitive resin composition of the present invention further includes an oxime ester-based initiator (C2) that functions as an initiator for curing the inside of the coating film. Accordingly, the lower portion of the coating film can be sufficiently cured, the coating film is prevented from being lifted off, and the adhesion of the pattern can be further increased.

  The oxime ester initiator (C2) can be used without any particular limitation as long as it contains an oxime ester group. Specific examples include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, 1,2-octanedione, 1- (4-phenylthio) phenyl, 2- (o-benzoyloxime), ethanone, 1- (9-ethyl) -6- (2-methylbenzoyl-3-yl), 1- (o-acetyloxime) and the like, and as commercial products, CGI-124 (Ciba-Geigy), CGI-224 ( Ciba Geigy), Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (Adeka), NCI-831 (Adeka) and the like, alone or as a mixture of two or more. Can be used. Preferably, a compound represented by the following chemical formula 5 is used.

[Wherein, L ₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, L ₂ is hydrogen, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and L ₃ is hydrogen, an alkyl group having 1 to 6 carbon atoms, an aryl group, or _-SC 6 _{H 5} having 6 to 12 carbon atoms. ]

  Further, the photopolymerization initiator (C) may further include a photopolymerization initiation aid in order to improve the sensitivity of the photosensitive resin composition of the present invention. The sensitivity of the photosensitive resin composition according to the present invention can be further increased by including the photopolymerization initiation auxiliary agent, and the productivity can be improved.

  Examples of the photopolymerization initiation aid include at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group.

  Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoyl-2-ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (Diethylamino) benzophenone and the like, and it is preferable to use an aromatic amine compound.

  Specific examples of the carboxylic acid compound are preferably aromatic heteroacetic acids, such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxyphenylthioacetic acid. Examples include acetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

  Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol Examples thereof include tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate).

  The mixing weight ratio of the biimidazole initiator (C1) and the oxime ester initiator (C2) according to the present invention is not particularly limited, but is, for example, 20:80 to 80:20, preferably 30:70. ７０70: 30. When the content is in the above range, the residual film ratio indicating the crosslinking density in the radical reaction of the photosensitive resin composition is excellent, and the T / B ratio value of the pattern is excellent.

  The content of the photopolymerization initiator (C) is not particularly limited. For example, the content is 0.1 to 20 parts by mass based on 100 parts by mass of the photosensitive resin composition based on the solid content. And preferably in an amount of 0.1 to 10 parts by mass. When the above range is satisfied, since the exposure time is shortened by increasing the sensitivity of the photosensitive resin composition, productivity is improved, high resolution can be maintained, and the intensity of the formed pixel portion and the pixel portion are improved. This is preferable in that the surface has good smoothness.

UV absorber (D)
Since the photosensitive resin composition of the present invention contains an ultraviolet absorber (D) represented by the following chemical formula 3, it absorbs ultraviolet light having a long wavelength, reduces CD-bias by diffraction, and can form a fine pattern. It is. Further, the T / B ratio can be improved, and the mechanical properties of the pattern can be improved.

Wherein R ₁₄ and R ₁₅ are each independently an alkoxy group having 1 to 5 carbon atoms. ]

  The compound represented by Formula 3 according to the present invention can mainly absorb a long-wavelength i-line even in the ultraviolet wavelength region, suppress the expansion of the bottom line width of the pattern, and form a fine pattern as a whole. I have to. Further, since the bottom line width is shortened and the top line width is relatively long, the T / B ratio can be improved to improve the elastic recovery rate of the pattern.

  Although the content of the ultraviolet absorbent (D) is not particularly limited, for example, 0.1 to 10 parts by mass, preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the alkali-soluble resin based on the solid content in the photosensitive resin composition. Is used in the range of 0.1 to 6 parts by mass, more preferably 1 to 5 parts by mass. When the ultraviolet absorber (D) is contained in the above content range, the T / B ratio and mechanical properties of the formed pattern can be further improved.

Solvent (E)
The solvent (E) can be used without any limitation as long as it is commonly used in the art.

  Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl. Diethylene glycol dialkyl ethers such as ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetate such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol monopropyl ether and propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl And propylene glycol dialkyl ethers such as propylene glycol ethyl propyl ether; propylene glycol alkyl such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate Ether propionates; butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol, butoxybutyl alcohol; butanediol monoalkyl such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, butoxybutyl acetate; Alkyl ether acetates; methoxybu Butanediol monoalkyl ether propionates such as tyl propionate, ethoxybutyl propionate, propoxybutyl propionate, butoxybutyl propionate; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl Dipropylene glycol dialkyl ethers such as ether; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; ethanol, propanol, butanol, hexanol , Cyclohexanol, ethylene glycol, glycerin and other alcohols; methyl acetate, ethyl acetate, propyl acetate, butyl acetate , Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, lactic acid Propyl, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate , Propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, propoxy Butyl acetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2- Methyl ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, 2-butoxy Butyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate Ethyl onate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3-butoxypropion Esters such as methyl acrylate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate; cyclic ethers such as tetrahydrofuran and pyran; cyclic esters such as γ-butyrolactone. The solvents mentioned here can be used alone or in combination of two or more.

  In consideration of coatability and drying property, the solvent is selected from alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate. Esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. May be used.

  The content of the solvent (E) may be included in an amount of 40 to 95 parts by mass, preferably 45 to 85 parts by mass based on 100 parts by mass of the photosensitive resin composition. When the above range is satisfied, the coatability becomes good when applied with a coater such as a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a “die coater” or a “curtain flow coater”), or an inkjet. Therefore, it is preferable.

Sensitizer (F)
The photosensitive resin composition of the present invention may further contain a sensitizer (F). The sensitizer (F) according to the present invention promotes the radical generation reaction of the photopolymerization initiator, improves the reactivity of radical polymerization, improves the crosslink density, and improves the adhesion of the photocured pattern to the substrate. Can be improved.

  The sensitizer (F) is not particularly limited as long as it can promote the radical generation reaction of the photopolymerization initiator. Specific examples include 9,10-dibutoxyanthracene, 9-hydroxymethylanthracene, thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, anthraquinone, and 1,2-dihydroxy Anthraquinone, 2-ethylanthraquinone, 1,4-diethoxynaphthalene, p-dimethylaminoacetophenone, p-diethylaminoacetophenone, p-dimethylaminobenzophenone, p-diethylaminobenzophenone, 4,4′-bis (dimethylamino) benzophenone, , 4'-bis (diethylamino) benzophenone, p-dimethylaminobenzaldehyde, p-diethylaminobenzaldehyde and the like. These can be used alone or in combination of two or more.

  The content of the sensitizer (F) is not particularly limited, but is, for example, 0.1 to 5 parts by mass based on 100 parts by mass of the photosensitive resin composition based on the solid content. And preferably in an amount of 0.1 to 3 parts by weight. When the above range is satisfied, since the exposure time is shortened by increasing the sensitivity of the photosensitive resin composition, productivity is improved, high resolution can be maintained, and the intensity of the formed pixel portion and the pixel portion are improved. This is preferable in that the surface has good smoothness.

Additive (G)
The photosensitive resin composition according to the present invention may contain, if necessary, additives such as fillers, other polymer compounds, curing agents, leveling agents, adhesion promoters, antioxidants, anti-agglomeration agents, and chain transfer agents. It may further include.

  Specific examples of the filler include glass, silica, and alumina.

  Specific examples of the other polymer compound include curable resins such as epoxy resin and maleimide resin; and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Is mentioned.

  The curing agent is used for deep curing and increasing mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

  Specific examples of the epoxy compound as the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, and other aromatic epoxy resins. Epoxy resin, alicyclic epoxy resin, glycidyl ester resin, glycidylamine resin, or a bromo derivative of such an epoxy resin, an aliphatic, alicyclic or aromatic epoxy compound other than the epoxy resin and its bromo derivative, Butadiene (co) polymer epoxy compound, isoprene (co) polymer epoxy compound, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like.

  Specific examples of the oxetane compound as the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  As the curing agent, a curing auxiliary compound capable of ring-opening polymerizing the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound can be used together with the curing agent. Examples of the curing auxiliary compound include polycarboxylic acids, polycarboxylic anhydrides, and acid generators.

  As the carboxylic anhydrides, those commercially available as epoxy resin curing agents can be used. Examples of the epoxy resin curing agent include Adeka Hardener EH-700 (trade name, manufactured by Adeka Industry Co., Ltd.), Rikashid HH (trade name, manufactured by Shin Nippon Rika Co., Ltd.), and MH-700 (trade name, Nippon Rika Co., Ltd.) Co., Ltd.). The curing agents exemplified above can be used alone or in combination of two or more.

  As the leveling agent, commercially available surfactants can be used, for example, silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric surfactants, and the like. You may use each independently or in combination of 2 or more types.

  Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethylene imines Other product names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-top (manufactured by Tochem Products Co., Ltd.), Megafac (manufactured by Dainippon Ink and Chemicals, Inc.) )), Florard (Sumitomo 3M), Asahi Guard, Surflon (all manufactured by Asahi Glass Co., Ltd.), Solsperse (Zeneca), EFKA (EFKA CHEMICALS), PB821 (Ajinomoto Co., Ltd.) )).

  As the adhesion promoter, a silane compound is preferable, and specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl Methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like. That.

  Specific examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and 2- [1- (2- Hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy ] -2,4,8,10-Tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphepin, 3,9-bis [2- {3- (3-tert-butyl) -4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2′-methyl Lenbis (6-tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol) ), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3, 3′-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,3 5-triazine-2,4,6 (1 H, 3H, 5H) -trione, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a , A ', a "-(mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and the like.

  Specific examples of the aggregation preventing agent include sodium polyacrylate.

  Specific examples of the chain transfer agent include dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene, and the like.

  The content of the additive (F) is 0.001 to 1 part by mass, preferably 0.001 to 0.01 part by mass, based on 100 parts by mass of the photosensitive resin composition. obtain.

<Light curing pattern and image display device>
It is an object of the present invention to provide a photocurable pattern manufactured using the photosensitive resin composition and an image display device including the photocurable pattern.

  The photo-cured pattern made of the photosensitive resin composition can control CD-Bias, and is excellent in T / B ratio value, developability, adhesion, and mechanical properties. Thereby, in an image display device, it can be used for various patterns, for example, an adhesive layer, an array flattening film, a protective film, an insulating film pattern, and used for a photoresist, a black matrix, a column spacer pattern, and the like. obtain. However, the present invention is not limited to this, and is particularly preferable as a spacer pattern.

  Examples of an image display device having such a photocurable pattern or using the pattern during a manufacturing process include a liquid crystal display device, an OLED, and a flexible display. However, the present invention is not limited to this, and includes all image display devices known in the art as applicable.

  The photocurable pattern can be produced by applying the above-described photosensitive resin composition of the present invention on a substrate and forming a photocurable pattern (after a development step as necessary).

  Specifically, first, the photosensitive resin composition is applied to a substrate, and then dried by heating to remove volatile components such as a solvent to obtain a smooth coating film.

  As a coating method, for example, spin coating, cast coating, roll coating, slit and spin coating, slit coating, or the like can be used. After application, heating and drying (prebaking) or drying under reduced pressure is followed by heating to evaporate volatile components such as a solvent. Here, the heating temperature is a relatively low temperature of 70 to 100 ° C. The thickness of the coating after heating and drying is usually about 1 to 8 μm. The coating film thus obtained is irradiated with ultraviolet light through a mask for forming a target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that a parallel light beam is uniformly irradiated on the entire exposed portion and accurate alignment between the mask and the substrate is performed. Irradiation with ultraviolet light cures the part irradiated with ultraviolet light.

  As the ultraviolet rays, g-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm) and the like can be used. The irradiation amount of the ultraviolet ray can be appropriately selected as needed, and is not limited in the present invention. If the cured coating film is brought into contact with a developing solution as needed, and the unexposed portion is dissolved and developed, a desired pattern shape can be formed.

  As the development method, any of a liquid addition method, a dipping method, a spray method, and the like may be used. Further, the substrate may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be any of inorganic and organic alkaline compounds. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate , Potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia and the like. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. And the like.

  These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass.

  As the surfactant in the alkali developer, at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant can be used.

  Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymer, and sorbitan fatty acid. Examples include esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

  Specific examples of the anionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and dodecyl. And alkylaryl sulfonates such as sodium naphthalene sulfonate.

  Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. These surfactants can be used alone or in combination of two or more.

  The concentration of the surfactant in the developer is usually from 0.01 to 10% by mass, preferably from 0.05 to 8% by mass, more preferably from 0.1 to 5% by mass. After the development, the film is washed with water and post-baked at a relatively low temperature of 100 to 150 ° C. for 10 to 60 minutes.

  Hereinafter, preferred embodiments will be described to facilitate understanding of the present invention. However, these embodiments are merely illustrative of the present invention, and do not limit the scope of the appended claims. It will be apparent to those skilled in the art that various changes and modifications can be made to the embodiments within the scope and spirit of the present invention, and such changes and modifications are set forth in the appended claims. It goes without saying that it belongs to

Preparation Example 1. Synthesis of Alkali-Soluble Resin (First Resin (A-1)) A nitrogen atmosphere was introduced at a flow rate of 0.02 L / min into a 1-L flask equipped with a reflux condenser, a dropping funnel, and a stirrer. As below, 200 g of propylene glycol monomethyl ether acetate was charged. After the temperature was raised to 100 ° C., 61.6 g (0.35 mol) of benzyl methacrylate, 22.0 g (0.10 mol) of tricyclo [5.2.1.02,6] decanyl methacrylate, and 47% of methacrylic acid were used. A solution obtained by adding 3.6 g of 2,2′-azobis (2,4-dimethylvaleronitrile) to a mixture containing 0.3 g (0.55 mol) and 150 g of propylene glycol monomethyl ether acetate was added to the flask over 2 hours using a dropping funnel. And stirring was continued at 100 ° C. for another 5 hours.

  Next, the atmosphere in the flask was changed from nitrogen to air, and 42.6 g of glycidyl methacrylate [0.30 mol (55 mol% based on methacrylic acid used in this reaction)] was charged into the flask. A time reaction was performed. As a result, an unsaturated group-containing resin A-1 having a solid content acid value of 104 mgKOH / g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 28,000, and the molecular weight distribution (Mw / Mn) was 3.20.

  At this time, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured using an HLC-8120GPC (manufactured by Tosoh Corporation), and the columns were TSK-GELG4000HXL and TSK-GELG2000HXL in series. The column temperature was 40 ° C., tetrahydrofuran was used as the mobile phase solvent, the flow rate was 1.0 mL / min, the injection volume was 50 μL, the detector was RI, and the concentration of the measurement sample was 0.6% by mass. (Solvent = tetrahydrofuran), and TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation) were used as calibration standard substances.

  The ratio between the obtained weight average molecular weight and number average molecular weight was defined as a molecular weight distribution (Mw / Mn).

Preparation Example 2. Synthesis of alkali-soluble resin (second resin (A-2)) A nitrogen atmosphere was introduced into a 1-L flask equipped with a reflux condenser, a dropping funnel, and a stirrer so that nitrogen was introduced at 0.02 L / min. Then, 150 g of diethylene glycol methyl ethyl ether was charged, stirred, and heated to 70 ° C. Next, 210.2 g (0.95 mol) of a mixture of the following chemical formulas 6-1 and 6-2 (molar ratio: 50:50) and 14.5 g (0.17 mol) of methacrylic acid were added to 150 g of diethylene glycol methyl ethyl ether. A solution was prepared by dissolving.

  After the prepared solution was dropped into a flask using a dropping funnel, 27.9 g (0.11 mol) of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was added to 200 g of diethylene glycol methyl ethyl ether. The dissolved solution was dropped into the flask over another 4 hours using another dropping funnel. After completion of the dropwise addition of the polymerization initiator solution, the temperature was maintained at 70 ° C. for 4 hours, and then cooled to room temperature. Thus, a solution of the copolymer (resin A-2) having a solid content of 41.6% by mass and an acid value of 65 mg-KOH / g (solid content conversion) was obtained.

  The weight average molecular weight (Mw) of the obtained resin A-2 was 8,300, and the molecular weight distribution was 1.85.

Preparation Example 3. Synthesis of Alkali-Soluble Resin (A-3) Nitrogen was introduced into a 1-L flask equipped with a reflux condenser, a dropping funnel, and a stirrer under a nitrogen atmosphere at a flow rate of 0.02 L / min. 200 g of acetate was charged. After raising the temperature to 100 ° C., 47.3 g (0.55 mol) of methacrylic acid, 61.7 g (0.35 mol) of benzyl methacrylate, tricyclo [5.2.1.02,6] decanyl methacrylate 22 A solution obtained by adding 3.6 g of 2,2′-azobis (2,4-dimethylvaleronitrile) to a mixture containing 0.0 g (0.10 mol) and 150 g of propylene glycol monomethyl ether acetate was added from a dropping funnel over 2 hours. After dripping into the flask, stirring was continued at 100 ° C. for further 7 hours. After completion of the reaction, a resin A-3 having an acid value of 134 mgKOH / g of solid content was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 22,700, and the molecular weight distribution (Mw / Mn) was 2.5.

Examples and Comparative Examples Photosensitive resin compositions having compositions and contents (parts by mass) shown in Tables 1 and 2 below were prepared.

A-1: Resin of Preparation Example 1 A-2: Resin of Preparation Example 2 A-3: Resin of Preparation Example B-1: Dipentaerythritol hexaacrylate (KAYARAD DPHA: manufactured by Nippon Kayaku Co., Ltd.)
C-1: 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole (B-CIM: manufactured by Hodogaya Chemical Industry Co., Ltd.)
C-2: 2,2'-bis (o-methoxyphenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole (HABI-107: manufactured by Tronly)
C-3: Biimidazole compound represented by Formula 7 C-4: Oxime ester compound represented by Formula 8 C-5: Oxime ester compound represented by Formula 9 D-1: Compound represented by Formula 10 D -2: Compound represented by Chemical Formula 11 D-3: Compound represented by Chemical Formula 12 D-4: Compound represented by Chemical Formula 13 D-5: Compound represented by Chemical Formula 14 E-1: Propylene glycol monomethyl ether acetate: Diethylene glycol Methyl ethyl ether (6: 4 volume ratio)
F-1: Compound represented by Chemical Formula 15 G-1 (Antioxidant): 4,4′-butylidenebis [6-tert-butyl-3-methylphenol] (BBM-S: manufactured by Sumitomo Seimitsu Chemical)

Test Method A 2-inch square glass substrate (Eagle 2000, manufactured by Corning) was sequentially washed with a neutral detergent, water, and alcohol, and then dried. After spin-coating each of the photosensitive resin compositions prepared in Examples and Comparative Examples on this glass substrate, prebaking was performed at 90 ° C. for 125 seconds using a hot plate. After cooling the prebaked substrate at room temperature, the distance between the prebaked substrate and the photomask made of quartz glass was set to 150 μm, and an exposure amount of 60 mJ / cm ² (based on 365 nm) using an exposure machine (UX-1100SM; manufactured by Ushio Corporation). ). At this time, a photomask in which the next pattern was formed on the same plane was used.

  The pattern has an octagonal opening (hole pattern) which is an octagonal pattern of 14 μm, the interval between them is 100 μm, and 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide after light irradiation. %, Was immersed in an aqueous developer containing 25% at 25 ° C. for 60 seconds, developed, and washed with water. Thereafter, post-baking was performed in an oven at 100 ° C. for 1 hour. The patterns thus obtained were evaluated for physical properties as follows, and the results are shown in Table 3 below.

(1) Measurement of pattern top / bottom width ratio (T / B ratio)
The obtained dot pattern is observed with a three-dimensional shape measuring device (SIS-2000 system; manufactured by SNU Precision), and a portion at 5% of the entire height from the bottom of the pattern is a bottom CD (a), and the entire height is from the bottom. Is defined as the top CD (b), the length of (b) is divided by the length of (a), and the value multiplied by 100 (= b / a × 100) is defined as T / B. Defined as ratio.

(2) Pattern CD-Bias
The pattern size at the film thickness of 3.0 μm obtained above was measured using a three-dimensional shape measuring device (SIS-2000 system; manufactured by SNU Precision), and the difference from the mask size was determined by CD-Bias as follows. Is calculated. CD-Bias is better the closer to 0, (+) means that the size of the pattern is larger than the mask, and (-) means that the size of the pattern is smaller than the mask.
CD-Bias = (formed pattern size) − (mask size used in formation)

(3) Adhesion Measurement The development adhesion is a measure of the degree to which a pattern generated using a half-tone mask (Half-tone Mask) having a transmittance of 25% is adhered to a substrate. is there. The actual size of the pattern (line) when 100% of the pattern formed with a film thickness of 3 μm remains without dropping by a photomask having 1000 dot patterns with a diameter of 5 to 20 μm and 1 μm intervals. Width) was measured using a three-dimensional shape measuring instrument SIS-2000 manufactured by SNU Precision. The value of the pattern line width was defined as a value of the bottom CD at a position 5% of the entire height from the bottom surface of the pattern. The smaller the minimum pattern size that remains without missing, the better the development adhesion.

(4) Evaluation of Residual Film Ratio After applying the resin compositions of Examples and Comparative Examples to a substrate and performing spin coating, respectively, prebaking was performed at 90 ° C. for 125 seconds using a hot plate. After cooling the substrate subjected to the prebaking at ambient temperature, exposure machine; was irradiated with light on the entire surface of the coated film (UX-1100SM Ushio (Ltd.)) exposure of 60 mJ / cm ² by using a (365 nm reference) .

  After the light irradiation, the film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 60 seconds, developed, and washed with water. Thereafter, post-baking was performed at 230 ° C. for 30 minutes in an oven.

  At this time, the film thickness after the exposure and the film thickness after the completion of the post-baking step were measured, and the ratio of the undeveloped film was measured using the following equation.

  The higher the residual film ratio, the better the performance.

(5) Evaluation of Mechanical Properties (Total Displacement and Recovery Rate) In the cured films of the examples and comparative examples obtained above, a pattern having a bottom line width of 14 μm was formed by a dynamic ultra-micro hardness tester (HM-2000; Using Helmut Fischer GmbH + Co.KG), the total displacement (μm) and elastic displacement (μm) were measured under the following measurement conditions, and the recovery rate (%) was determined as follows using the measured values. Calculated. It was determined that the smaller the total displacement and the larger the recovery rate, the better.
Recovery rate (%) = [elastic displacement (μm)] / [total displacement (μm)] × 100

The measurement conditions are as follows.
Test mode: Load-Unload test Test force: 50.0mN
Load speed: 4.41 mN / sec
Maintenance time: 5 sec
Indenter: Four-sided pyramid indenter (50 μm in diameter)

  Referring to Table 3, in the examples using the photosensitive resin composition according to the present invention, the T / B ratio value of the pattern is excellent, the adhesion to the substrate is improved, and the developability is good. Was confirmed.

  In addition, in the case of the example using the photosensitive resin composition according to the present invention, the deviation was shown to be small at 1-2 μm in CD-Bias, and it was confirmed that the CD-Bias could be controlled and the mechanical properties were excellent. Was.

  However, in the case of the comparative example not using the compound of the present invention, it was confirmed that no pattern was formed or the T / B ratio value of the pattern was lowered, and the adhesion to the substrate was significantly poor.

  In addition, in the case of the comparative example not using the compound of the present invention, the CD-Bias showed a large deviation from a negative value to 4.2, and it was confirmed that the mechanical properties were inferior.

Claims (11)

An alkali-soluble resin (A) containing a first resin having a repeating unit represented by the following chemical formula 1 and a second resin having a repeating unit represented by the following chemical formula 2, a polymerizable compound (B), and biimidazole A photosensitive resin composition comprising a system initiator (C1), an oxime ester-based initiator (C2), an ultraviolet absorber (D) represented by the following chemical formula 3, and a solvent (E).
[In the formula, n is an integer of 1 or more, R ₁ is hydrogen or a methyl group, and R ₂ is hydrogen or an alkyl group having 1 to 6 carbon atoms. ]
[Wherein, m is an integer of 1 or more, and R ₃ is hydrogen or a methyl group. ]
Wherein R ₁₄ and R ₁₅ are each independently an alkoxy group having 1 to 5 carbon atoms. ]   The photosensitive resin composition according to claim 1, wherein a mixing weight ratio of the first resin and the second resin is 20:80 to 80:20.   3. The photosensitive resin composition according to claim 1, wherein the first resin has a weight average molecular weight of 10,000 to 30,000. 4.   The photosensitive resin composition according to any one of claims 1 to 3, wherein the second resin has a weight average molecular weight of 2,000 to 20,000. The photosensitive resin composition according to claim 1, wherein the first resin has a repeating unit represented by the following chemical formula 1-1.
[In the formula, the repeating unit a is benzyl (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, (2-phenyl) phenoxyethoxy (meth) acrylate, 2-hydroxy- (2-phenyl ) Phenolpropyl (meth) acrylate, 2-hydroxy- (3-phenyl) phenoxypropyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, styrene, α-methylstyrene , vinyltoluene, vinylnaphthalene, N-benzylmaleimide, methyl (Meth) acrylate, ethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (Meth) acrylate, methoxytetraethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and a monomer selected from the group consisting of tetrahydrofuryl (meth) acrylate Structure
The repeating unit b has a structure derived from a monomer selected from the group consisting of the following formulas (1) to (7); R ₅ is hydrogen or a methyl group;
The repeating unit c is composed of (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, and 2- (meth) A) a structure derived from a monomer selected from the group consisting of acryloyloxyethyl succinate;
R ₇ is hydrogen or a methyl group,
R ₁₁ is hydrogen or an alkyl group having 1 to 6 carbon atoms,
a = 20-60 mol%, b = 5-30 mol%, c = 10-50 mol%, d = 5-30 mol%. ] The photosensitive resin composition according to claim 1, wherein the second resin has a repeating unit represented by the following chemical formula 2-1.
[ Wherein , the repeating unit e is a structure derived from a monomer represented by the following formula (8), R ₁₂ is hydrogen or a methyl group,
The repeating unit f is composed of (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, and 2- (meth) A) a structure derived from a monomer selected from the group consisting of acryloyloxyethyl succinate;
e = 50-95 mol% and f = 5-50 mol%. ] The photosensitive resin composition according to any one of claims 1 to 6, wherein the biimidazole-based initiator (C1) is represented by the following Chemical Formula 4.
[In the formula, L _{3 to} L ₂₀ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom. ] The photosensitive resin composition according to any one of claims 1 to 7, wherein the oxime ester-based initiator (C2) is a compound represented by the following Chemical Formula 5.
[Wherein, L ₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, L ₂ is hydrogen, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and L ₃ is hydrogen, an alkyl group having 1 to 6 carbon atoms, an aryl group, or _-SC 6 _{H 5} having 6 to 12 carbon atoms. ]   A photocurable pattern formed from the photosensitive resin composition according to claim 1.   The light curing pattern according to claim 9, wherein the light curing pattern is selected from the group consisting of an array flattening film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, and a column spacer pattern.   An image display device comprising the photocurable pattern according to claim 9.