TWI676627B - Photosensitive resin composition, photocurable pattern formed from the same and image display comprising the pattern - Google Patents

Abstract

The present invention provides a photosensitive resin composition, a photocurable pattern formed thereby, and an image display device provided with the photocurable pattern. The present invention relates to a photosensitive resin composition which can be hardened at a low temperature by using a compound containing a specific structure and is excellent in chemical resistance, a photocurable pattern formed thereby, and an image display device provided with the photocurable pattern.

Description

Photosensitive resin composition, photocurable pattern formed thereby, and image display device provided with the photocurable pattern

The present invention relates to a photosensitive resin composition, a photocurable pattern formed thereby, and an image display device provided with the photocurable pattern.

In the field of displays, photosensitive resin compositions are used to form various photo-curable patterns such as photoresist, insulating films, protective films, black matrices, and column spacers. Specifically, the photosensitive resin composition is selectively exposed and developed through a photo-etching step to form a desired photo-hardening pattern. In this process, in order to improve the yield in the step and to improve the physical properties of the application target, a highly sensitive photosensitive resin composition is required.

In recent years, in the LCD manufacturing process, in order to improve productivity, when performing pattern manufacturing, a low-temperature firing step is used to manufacture a more reliable filter than a high-temperature firing step. However, when the conventional photosensitive resin composition is cured at a temperature of 200 ° C or lower, the curing of the resin composition does not proceed sufficiently, the adhesion to the lower substrate decreases, pattern peeling occurs, or the amount of exposure increases to form a thin film. Question points with reduced sensitivity, etc. Therefore, the demand for a low-temperature-curable photosensitive resin composition that can be sufficiently hardened in the low-temperature firing step is increasing.

In addition, it is required that low-temperature hardening is possible, and the photosensitive resin composition is required to be in a severe environment such as an alkali during the step, and chemical resistance is also required to be improved.

Patent Document 1 discloses a photosensitive resin composition including: a monomer containing a block isocyanate group; a monomer having an ethylenically unsaturated double bond and an acid group; and a resin binder containing an ethylenic compound having an ethylene content of 1 or more. A copolymerized monomer of a saturated double bond; a polyfunctional monomer having an ethylenically unsaturated double bond; an initiator; a colorant and a solvent; but no substitution scheme for the aforementioned problems is suggested. Prior technical literature Patent literature

[Patent Document 1] Korean Published Patent No. 2014-0147056

Problems to be solved by the invention

An object of the present invention is to provide a photosensitive resin composition that can be cured at a low temperature and has excellent durability such as chemical resistance for pattern formation.

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

Furthermore, an object of the present invention is to provide an image display device including the aforementioned light-hardened pattern. Technical means to solve problems

1. A photosensitive resin composition comprising the following Chemical Formula 1;

[Chemical 1] [Chemical Formula 1]

(Wherein R ₁ to R ₆ , R ₈ and R ₉ are each independently hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms, R ₇ is hydrogen, and X ^- is an organic acid salt anion.)

2. The photosensitive resin composition according to the item 1, wherein all of R ₁ to R ₉ of the compound of the chemical formula 1 are hydrogen.

3. The photosensitive resin composition according to the item 1, wherein the anion of the compound of the chemical formula 1 is selected from the group consisting of a p-toluenesulfonate anion, a 2-carboxybenzoate anion, and an octanoate anion. Either.

4. The photosensitive resin composition according to the aforementioned item 1, wherein the compound of the chemical formula 1 contains 0.05 to 10 parts by weight based on 100 parts by weight of the entire composition.

5. The photosensitive resin composition according to the item 1, further comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

6. The photosensitive resin composition according to the item 5, wherein the alkali-soluble resin includes an alkali-soluble resin having an epoxy group.

7. The photosensitive resin composition according to the item 5, wherein the alkali-soluble resin includes: a first resin having a repeating unit represented by the following chemical formula 2; and a second resin having a repeating unit represented by the following chemical formula 3 Repeating unit

[Chemical 2] [Chemical Formula 2]

(In the formula, R ₁ , R ₂ and R ₃ are each independently hydrogen or methyl, and R ₄ is derived from (meth) acrylic acid, 2 甲基 (meth) acrylic acid, oxyethyl hexahydrophthalate) Esters (2 ‒ ((Metha) Acryloyloxy) ethyl hexahydro phthalate), 2 ‒ ((Metha) Acryloyloxy) ethyl phthalate), and 2‒ The structure of the monomer selected from the group of ((Metha) Acryloyloxy) ethyl succinate); R ₅ is derived from the following formulas (1) to ( 9) the structure of the monomers selected in the group; R ₆ is a structure derived from a monomer selected from the group consisting of the following formulae (10) to (12); a = 10 to 60 mol%, b = 20 to 50 mol%, and c = 10 to 70 mol%. )

[Formula 3] [Chemical Formula 3]

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or methyl. R ₅ is derived from (meth) acrylic acid, 2‒ (meth) acrylic acid, oxyethyl hexahydro ortho) Phthalate (2) ((Metha) Acryloyloxy) ethyl hexahydro phthalate), 2 ‒ ((meth) acryloyloxy) ethyl phthalate), And 2‒ (meth) acryloxy succinate (2 丁 ((Metha) Acryloyloxy) ethyl succinate) selected from the group of monomer structure; R ₆ series from (meth) acrylic acid Benzyl ester, phenoxyethylene glycol (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, (2'phenyl) phenoxyethoxy (meth) acrylate, 2 ‒Hydroxy‒ (2‒phenyl) phenolpropyl (meth) acrylate, 2‒hydroxy‒ (3‒phenyl) phenoxypropyl (meth) acrylate, tetrahydrofuran methyl (meth) acrylate, (Meth) styrene, vinyltoluene, vinylnaphthalene, N-benzyl cis-butenediimine, methyl (meth) acrylate, ethyl (meth) acrylate, methoxyethylene glycol ( (Meth) acrylate, methoxydiethylene glycol (meth) acrylate Acid ester, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol Structure of monomers selected from the group of alcohol (meth) acrylate and tetrahydrofuran methyl (meth) acrylate; R ₇ is derived from monomers selected from the group including the aforementioned formulae (1) to (9) The structure of R ₈ is a structure derived from a monomer selected from the group consisting of the following formulae (10) to (16); d = 10-30 mol%, e = 10-20 mol%, f = 30-60 mol%, and g = 10-30 mol%. )

8. The photosensitive resin composition according to the item 5, further comprising a polyfunctional thiol group.

9. The photosensitive resin composition according to the aforementioned item 1, which can be cured at 70 to 100 ° C.

10. A light-hardening pattern manufactured from the photosensitive resin composition as described in any one of said items 1-9.

11. The light-hardening pattern according to the item 10, wherein the light-hardening pattern includes an adhesive layer, an array flattening film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a color filter pattern, and black Select from a matrix pattern and a column spacer pattern.

12. A pattern display device including the photocurable pattern according to the item 10 above. Effect of the invention

Since the photosensitive resin composition of the present invention can be cured at a low temperature, it exhibits excellent reactivity.

In addition, the pattern produced from the photosensitive resin composition of the present invention exhibits high durability such as excellent chemical resistance.

The present invention is particularly applicable to a negative photosensitive resin.

Forms used to implement the invention

The present invention relates to a photosensitive resin composition which can be hardened at a low temperature by using a compound containing a specific structure and has excellent chemical resistance, a photocurable pattern formed thereby, and an image display device provided with the photocurable pattern. .

The present invention is explained in detail below.

Photosensitive resin composition The photosensitive resin composition of the present invention includes a compound of the following Chemical Formula 1.

[Chemical 1] [Chemical Formula 1]

In the formula, R ₁ to R ₆ , R ₈ and R ₉ are each independently hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms, R ₇ is hydrogen, and X ^- is an organic acid salt anion.

The hydrogen at the R7 position of the compound of the aforementioned Chemical Formula 1 is acidic and can be easily detached. Therefore, the photosensitive resin composition can be hardened even at a low temperature of 100 ° C or lower. In particular, when the alkali-soluble resin contains an epoxy structure, the epoxy group can be ring-opened by the acidic hydrogen to further improve the degree of hardening at a low temperature.

As an embodiment of the present invention, all of R ₁ to R ₉ of the compound of the aforementioned Chemical Formula 1 may be hydrogen.

The chemical formula of the anionic compound 1 (X ^-) is not easy if combined with hydrogen desorbed from R _7, a high degree of ionization, and without departing from the object of the present invention may be those, which are not particularly restricted species. Specifically, any one may be selected from the group consisting of p-toluenesulfonate anion, 2-carboxybenzoate anion, and octanoate anion.

According to the photosensitive resin composition of the present invention, the content of the compound represented by the aforementioned Chemical Formula 1 is not particularly limited. Specifically, it may contain 0.05 to 5 parts by weight, and more preferably 0.1 to 5 parts with respect to 100 parts by weight of the entire composition. Weight department. If the content of the compound represented by the aforementioned Chemical Formula 1 is within the aforementioned range, the low-temperature curing ability of the photosensitive resin composition is further enhanced.

The photosensitive resin composition of the present invention may further include components known in the art in addition to the compound of Chemical Formula 1. For example, it may further contain an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

Alkali-soluble resin In the present invention, the alkali-soluble resin provides soluble components to the alkali developing solution used in the development processing step during pattern formation, as long as it does not deviate from the object of the present invention, the type thereof can be used without particular limitation.

Specific examples of the acrylic copolymer include a copolymer of a carboxyl group-containing monomer and other monomers copolymerizable with the monomer.

Specific examples of the carboxyl group-containing monomer include unsaturated monocarboxylic acids, and unsaturated polycarboxylic acids such as unsaturated dicarboxylic acids having 1 or more carboxyl groups in molecules such as unsaturated dicarboxylic acids and unsaturated tricarboxylic acids. Wait.

These carboxyl group-containing monomers can be used individually or in combination of two or more kinds.

Specific examples of other monomers that can be copolymerized with the carboxyl group-containing monomer include: aromatic vinyl compounds; unsaturated carboxylic acid esters; unsaturated carboxylic acid amino alkyl esters; unsaturated carboxylic acid glycidol Base esters; vinyl carboxylic acid esters; unsaturated ethers; vinyl cyanide compounds; unsaturated amidines; unsaturated amidines; aliphatic conjugated diene; polystyrene, polyacrylic acid Methyl ester, polymethyl methacrylate, poly n-butyl acrylate, poly n-butyl methacrylate, and polysiloxane polymer molecular chain ends, with a mono-acryl group or mono-methacryl group Body class, etc.

These monomers can be used individually or in combination of two or more.

The content of the carboxyl-containing monomer unit of the alkali-soluble resin is generally 10 to 50% by mass, more preferably 15 to 40% by mass, and even more preferably 25 to 40% by mass. When the content of the carboxyl group-containing monomer unit is 10 to 50% by mass, the solubility in the developing solution is good, and the pattern tends to be formed correctly during development, so it is more suitable.

Examples of the acrylic copolymer include a (meth) acrylic acid / (meth) acrylic acid copolymer, a (meth) acrylic acid / (meth) acrylic acid benzyl ester copolymer, and a (meth) acrylic acid / 2 hydroxy group. Ethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / (meth) ) Methyl acrylate / poly (meth) acrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate poly (meth) acrylate macromonomer copolymer, (meth) Acrylic acid / 2 hydroxy ethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2 hydroxy ethyl (meth) acrylate / (methyl) ) Benzyl acrylate / poly (meth) acrylic acid macromonomer copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenyl cis butylene diimide copolymer, (Meth) acrylic acid / succinic acid mono (2‒acrylic acid) / styrene / (meth) acrylic acid benzyl ester / N‒phenylcis butylene diimide copolymer, (meth) acrylic acid / butyl Diacid mono (2‒propylene 醯 oxyethyl) / benzene Ene / (meth) acrylic acid ester / N-phenyl cis butene difluorene imine copolymer, (meth) acrylic acid / benzyl (meth) acrylate / N phenyl cis butylene diimide / Styrene / glycerol mono (meth) acrylate copolymer and the like. Here, (meth) acrylate means acrylate or methacrylate.

Among them, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, and (meth) acrylic acid / (meth) acrylic acid are particularly suitable. Methyl ester copolymer, (meth) acrylic acid / methyl (meth) acrylate / styrene copolymer.

The aforementioned alkali-soluble resin may preferably contain an alkali-soluble resin having an epoxy group.

As one embodiment of the aforementioned alkali-soluble resin having an epoxy group, the alkali-soluble resin of the present invention may include: a first resin having a repeating unit represented by the following chemical formula 2; and a second resin having the following chemical formula Repeating unit shown in 3.

[Chemical 2] [Chemical Formula 2]

In the formula, R ₁ , R _2, and R ₃ are each independently hydrogen or methyl, and R ₄ is derived from (meth) acrylic acid, 2 甲基 (meth) acryl 醯 oxyethyl hexahydrophthalic acid Esters (2 ‒ ((Metha) Acryloyloxy) ethyl hexahydro phthalate), 2 ‒ ((Metha) Acryloyloxy) ethyl phthalate), 2 ‒ ((Metha) Acryloyloxy) ethyl phthalate), and 2‒ ( The structure of monomers selected from the group consisting of (meth) acryloyloxy ethyl succinate; (R ₅₎ is derived from the following formulae (1) to (9) The structure of the monomer selected in the group of); R ₆ is a structure derived from a monomer selected from the group consisting of the following formulae (10) to (12); a = 10 to 60 mol%, b = 20 to 50 mol%, and c = 10 to 70 mol%.

[Chemical 3] [Chemical Formula 3]

In the formula, R1, R2, R3, and R4 are each independently hydrogen or methyl, and R ₅ is derived from (meth) acrylic acid, 2‒ (meth) acryl 醯 oxyethyl hexahydrophthalate. (2 ‒ ((Metha) Acryloyloxy) ethyl hexahydro phthalate), 2 ‒ ((Metha) Acryloyloxy) ethyl phthalate), and 2 ‒ ((Metha) Acryloyloxy) ethyl phthalate), and The structure of the monomers selected from the group of (meth) acryloyloxy ethyl succinate; R ₆ is derived from the group consisting of benzyl (meth) acrylate, phenoxy Ethylene 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, tetrahydrofuran methyl (meth) acrylate, (meth) benzene Ethylene, vinyl toluene, vinyl naphthalene, N-benzyl cis-butene diimide, 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 ( Structures of monomers selected from the group consisting of meth) acrylates and tetrahydrofuran methyl (meth) acrylate; R ₇ is a structure derived from monomers selected from the group consisting of the aforementioned formulae (1) to (9) ; R ₈ is a structure derived from a monomer selected from the group consisting of the following formulae (10) to (16); d = 10-30 mol%, e = 10-20 mol%, f = 30-60 mol%, and g = 10-30 mol%.

In the present invention, each repeating unit shown in Chemical Formula 2 and Chemical Formula 3 must not be interpreted as being limited to that shown in Chemical Formula 2 or Chemical Formula 3. The child repeating units in parentheses can be freely located at any position in the chain within the set Mohr% range . That is, each parenthesis of Chemical Formula 2 and Chemical Formula 3 is expressed as one block in order to express mole%. However, if each sub-repeating unit is in the resin, it can be located without restriction, and can be separated as a block or separately. Both.

Preferable examples of the compound of Chemical Formula 2 of the present invention include compounds of the following Chemical Formula 2-1.

[Chemical 2-1] [Chemical Formula 2-1]

In the formula, R ₁ , R _2, and R ₃ are each independently hydrogen or methyl, a = 10 to 60 mol%, b = 20 to 50 mol%, and c = 10 to 70 mol%.

Preferable examples of the compound of Chemical Formula 3 of the present invention include the following compounds of Chemical Formula 3-1.

[Chem. 3-1] [Chemical Formula 3-1]

In the formula, R ₁ , R ₂ , R _3, and R ₄ are each independently hydrogen or methyl, d = 10-30 mol%, e = 10-20 mol%, f = 30-60 mol%, and g = 10-30 mol%.

The first resin of the present invention functions to improve the chemical resistance and reactivity of the photosensitive resin composition. From this viewpoint, the weight average molecular weight of the first resin is preferably 6,000 to 12,000. When it is in the aforementioned molecular weight range, the most excellent reactivity and chemical resistance can be exhibited.

The second resin of the present invention has a function of improving the durability of the photosensitive resin composition, such as pattern formation properties and heat resistance. From this viewpoint, the weight average molecular weight of the second resin is preferably 20,000 to 30,000. When it is in the aforementioned molecular weight range, the most excellent pattern-forming property, heat resistance, and the like can be exhibited.

The mixing weight ratio of the first resin and the second resin of the present invention may be 50:50 to 90:10, and more preferably 70 to 30 to 80:20. When the content of the first resin is less than that of the second resin, the low-temperature curability is reduced, and residues after development occur. When the content of the first resin exceeds 9 times the weight of the second resin, the pattern formability is reduced.

The first resin and the second resin of the present invention may include, in addition to each other, repeating units of Chemical Formula 2 and Chemical Formula 3 alone, and may further include repeating units formed of other monomers known in the art, or only repeating units of Chemical Formula 2. Can be formed.

The polystyrene-equivalent weight average molecular weight of the alkali-soluble resin is generally 5,000 to 50,000, preferably 8,000 to 40,000, more preferably 10,000 to 35,000, and most preferably 10,000 to 30,000. If the molecular weight of the alkali-soluble resin is 5,000 to 50,000, the hardness of the guide film is increased, and the residual film ratio is also increased. The unexposed portion has good solubility for the developer, and the resolution tends to increase, so it is more suitable.

The acid value of the alkali-soluble resin is generally 50 to 150, preferably 60 to 140, more preferably 80 to 135, and most preferably 80 to 130. If the acid value is 50 to 150, the solubility in the developing solution is improved, and the non-exposure property is easy to dissolve and the sensitivity is increased. During development, the pattern of the exposed portion remains and the residual film rate tends to increase, so it is more suitable. Here, the acid value refers to a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and is generally determined by titration with an aqueous potassium hydroxide solution.

The content of the alkali-soluble resin is not particularly limited. Specifically, it may contain 10 to 90 parts by weight, and more preferably 25 to 80 parts by weight based on 100 parts by weight of the entire photosensitive resin composition of the present invention. When the content is included as described above, since the developer has sufficient solubility in the developing solution, development residues are unlikely to occur on the substrate of the non-pixel portion, and during development, it is difficult to reduce the film of the pixel portion of the exposed portion, so the non-pixel portion falls off. Sex tends to be good. In addition, a photo-hardening pattern having excellent mechanical properties can be formed, which is preferable.

Photopolymerizable compound The polymerizable compound used in the photosensitive resin composition of the present invention can increase the bridging density in the manufacturing step and strengthen the mechanical properties of the photocurable pattern.

The photopolymerizable compound can be used in the field without particular limitation, such as a monofunctional monomer, a difunctional monomer, and other polyfunctional monomers. The type is not particularly limited, and the following compounds are exemplified.

Specific examples of the monofunctional monomer include carbyl nonylphenyl acrylate, propyl 2-hydroxy-3-phenoxyacrylate, carbitol 2-ethylhexyl acrylate, ethyl 2-hydroxyacrylate, and N- Vinyl benzalkanone and the like. Specific examples of the difunctional monomer include 1,6-hexamethylene di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethyl Glycol di (meth) acrylate, bis (acryloxyethyl) ether of bisphenol A, 3-methylpentanediol (meth) acrylate, and the like. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated (ethoxylated) trimethylolpropane tri (meth) acrylate, and propoxylated ( (Propoxy) trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated (ethyl Oxidation) dipentaerythritol hexa (meth) acrylate, propoxylated (propoxylated) dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Among them, it is particularly preferable to use a difunctional or more polyfunctional monomer.

The content of the polymerizable compound is not particularly limited. For example, based on the solid content in the photosensitive resin composition, it is preferably in the range of 10 to 90 parts by mass, and more preferably in the range of 30 to 80 parts by mass based on 100 parts by weight of the alkali-soluble resin. To use. If the content of the polymerizable compound is within the aforementioned range, it can have excellent durability and can improve the developability of the composition.

Photopolymerization initiator The type of the photopolymerization initiator of the present invention is not particularly limited as long as it can polymerize the aforementioned polymerizable compound, and examples thereof include acetophenone-based compounds, benzophenone-based compounds, and triazines. As the at least one compound selected from the group consisting of a series compound, a biimidazole compound, a thioxanthone compound, and an oxime ester compound, a biimidazole compound or an oxime ester compound is preferably used.

In addition, the photopolymerization initiator may further include a photopolymerization initiator in order to improve the sensitivity of the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention contains a photopolymerization initiation aid to further increase sensitivity and improve productivity.

Examples of the photopolymerization starting aid include one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group.

The content of the photopolymerization initiator is not particularly limited. For example, based on the solid content, it may contain 0.1 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the entire photosensitive resin composition. If it falls within the aforementioned range, the photosensitive resin composition will be highly sensitive and the exposure time will be shortened. Therefore, productivity will be improved, high resolution can be maintained, and the strength of the formed pixel portion and the smoothness of the pixelized surface are good, which is suitable.

Solvent If the solvent is generally used in the field, any solvent can be used without limitation.

Specific examples of the solvent include ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, ethylene glycol alkyl ether acetates, alkylene glycol alkyl ether acetates, and propylene glycol monoalkyl ethers. , Propylene glycol dialkyl ethers, propylene glycol alkyl ether propionates, butanediol monoalkyl ethers, butanediol monoalkyl ether acetates, butanediol monoalkyl ether propionates, dipropylene glycol dialkyl ethers , Aromatic hydrocarbons, ketones, alcohols, esters, and cyclic esters. The solvents exemplified herein may be used alone or in combination of two or more. From the standpoint of coatability and drying properties, the aforementioned solvents are preferably alkylene glycol alkyl ether acetates, diethylene glycol dialkyl ethers, alkylene glycol alkyl ether acetates, ketones, butane. Glycol alkyl ether acetates, butanediol monoalkyl ethers, and esters, and further preferably propylene glycol monomethyl ether acetate, diethylene glycol methyl ether, propylene glycol monoethyl ether acetate, cyclohexanone, Methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The content of the aforementioned solvent is not particularly limited. Specifically, it may contain 40 to 95 parts by weight, and more preferably 45 to 85 parts by weight, based on 100 parts by weight of the entire photosensitive resin composition. If the above range is met, spin coaters, slit and spin coaters, slit coaters (also sometimes referred to as die coaters, curtain coaters), inkjet coaters, etc. When the coating device is applied, the applicability is improved, so it is suitable.

Additives The photosensitive resin composition of the present invention may further include fillers, other polymer compounds, hardeners, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, agglutination preventers, chain transfer agents, etc. as required. additive.

The content of the aforementioned additives is not particularly limited. Specifically, it may contain 0.1 to 15 parts by weight, and more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the entire photosensitive resin composition.

Photocurable pattern and image display device An object of the present invention is to provide a photocurable pattern produced from the photosensitive resin composition and an image display device including the photocurable pattern.

The photocurable pattern produced from the photosensitive resin composition is excellent in low-temperature curability and excellent in chemical resistance and the like. Therefore, it can be used in various patterns of image display devices, such as adhesive layers, array planarization films, protective films, and insulating film patterns. It can also be used in photoresist, black matrix, column spacers, etc., but it is not limited to This is particularly suitable as a photoresist pattern.

Examples of the image display device having such a light-hardened pattern or using the aforementioned pattern in the manufacturing process include a liquid crystal display device, an OLED, and a flexible display. However, the image display device is not limited to these devices, and the applicable field is exemplified. All image display devices known in the art.

The light-hardening pattern can be produced by coating the photosensitive resin composition of the present invention (after exposing and exposing steps as necessary) on the substrate to form a light-hardening pattern.

In the following, preferred embodiments are suggested in order to help understand the present invention, but these embodiments are only for exemplifying the present invention, and do not limit the scope of the attached patent application. It is obvious to the industry that it is within the scope of the present invention. Within the scope of technical and technical ideas, various changes and amendments are applied to the embodiments, and such changes and amendments naturally belong to the scope of the attached patent application.

Example 1. Synthesis of alkali-soluble resin (first resin) in the manufacture with a reflux condenser, dropping funnel and a stirrer within the 1L flask, diethylene glycol methyl ethyl placed 300g (4.05 mole), stirring and Heat to 70 ° C. Next, 300 g (1.36 mol) of a mixture of the following Chemical Formulas 8 and 9 (molar ratio 50:50), 150 g (1.06 mol) of glycidyl methacrylate, and 50 g (1.7 mol) of methacrylic acid, It was dissolved in 140 g (0.94 mole) of methyl ethyl diethylene glycol and prepared into a solution.

[Chemical 8] [Chemical Formula 8]

[Chemical 9] [Chemical Formula 9]

The prepared solution was dropped into a flask held at 70 ° C. using a dropping funnel over 4 hours. In addition, 30 g (0.12 mol) of a polymerization initiator 2,2 ′ azobis (2,4 dimethyl valeronitrile) was dissolved in 225 g (1.5 mol) of methyl ethyl diethylene glycol. The solution was dropped into the flask over 4 hours using another dropping funnel. After the dropping of the solution of the polymerization initiator was completed, it was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a copolymer having a solid content of 36.7 mass% and an acid value of 59 mg-KOH / g (in terms of solid content) (No. 1 Resin).

The weight average molecular weight Mw of the obtained first resin was 8,200, and the molecular weight distribution was 1.85.

At this time, the measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the aforementioned dispersing resin is performed using an HLC-8120GPC (manufactured by TOSOH Co., Ltd.) device, and the column system is a series of TSK-GELG4000HXL and TSK-GELG2000HXL For connection use, the column temperature is 40 ° C, the transfer phase solvent is tetrahydrofuran, the flow rate is 1.0mL / min, the injection volume is 50mL, the detector uses RI, and the measurement sample concentration is 0.6mass% (solvent = tetrahydrofuran). The calibration standard The substance used was TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (made by TOSOH Co., Ltd.).

The ratio of the weight-average molecular weight and the number-average molecular weight obtained above is referred to as a molecular weight distribution (Mw / Mn).

Example 2. Synthesis of alkali-soluble resin (second resin) in addition to the monomers for producing the styrene 30g (0.29 mole), methacrylic acid 45g (0.5 mole), glycidyl methacrylate 135g (0.95 mole), A solid material was obtained in the same manner as in Production Example 1 except that 2 g (octahydrofluorene 4,7 g bridge, 1H g, indene g, 5 gyl), methyl gland 2 g, ethyl acrylate, and 65 g (0.3 mol) were used. A solution of a copolymer (second resin) of 32.4 mass% and an acid value of 31 mg-KOH / g (in terms of solid content).

The weight average molecular weight Mw of the obtained second resin was 28,000, and the molecular weight distribution was 3.20.

Example 1 consists of 12.8 parts by weight of alkali-soluble resin 1 synthesized in Production Example 1, 27.0 parts by weight of alkali-soluble resin 2 synthesized in Production Example 2, and dipentaerythritol hexaacrylate (KAYARAD DPHA, Japan) as a photopolymerizable compound. (Made by Chemical Pharmaceutical Co., Ltd.) 9.7 parts by weight, oxime ester compound OXE-01 as a photopolymerization initiator 0.7 parts by weight, 2,2'-bis (2-chlorobenzene) -4,4 ', 5,5 0.2 parts by weight of '-tetraphenylpyrene 1, 2' and biimidazole, and (2,4,6, trioxo, 1,3,5, triazine, 1,3,5,3) of polyfunctional thiol groups Tris (ethane‒2,1-diyl) tris (3‒butyric acid thiol ((2,4,6‒trioxo‒1,3,5‒triazinane‒1,3,5‒triyl) tris ( ethane‒2,1‒diyl) tris (3‒mercaptobutanoate)) 7.3 parts by weight, and SH-8400 0.1 parts by weight of the additive. For the purpose of improving the hardening degree, U-CAT SA506 (2,3,4,6, 7,8,9,10‒octahydropyrimido [1,2‒a] aqepin‒1‒ium (2,3,4,6,7,8,9,10‒octahydropyrimido [1,2‒a] aqepin ‒1‒ium) and p-toluenesulfonate salts, manufactured by San Apro) 0.2 parts by weight, the mixing ratio of diethylene glycol methyl ether: propylene glycol monomethyl ether acetate ( Ratio) 4: 6 of the solvent, so that the whole became 100 parts by weight, was stirred for 3 hours to prepare a photosensitive resin composition.

Example 2 except that U-CAT SA810 (2-carboxy anions benzoate, San Apro Ltd.)., Are used in the same manner as in Example, for producing a photosensitive resin composition.

Example 3 except that U-CAT SA102 (octanoic acid salt anion, San Apro Ltd.)., Are used in the same manner as in Example 1, producing the photosensitive resin composition.

Example 4 except for containing a U-CAT SA506 8 parts by weight, 34.2 parts by weight of solvent, are used in the same manner as in Example 1, producing the photosensitive resin composition.

Example 5 except for containing SA506 12 weight portions, 30.2 parts by weight of the solvent U-CAT, 1 are used in the same manner as in Example, for producing the photosensitive resin composition.

Except that U-CAT SA506 was not included in Comparative Example 1 , a photosensitive resin composition was produced in the same manner as in Example 1.

Comparative Example 2 except that U-CAT SA506 was substituted with 1,8-diazabicyclo [5,4,0] undec-7-ene (1,8-diazabicyclo [5,4,0] undec‒7‒ene) In the same manner as in Example 1, a photosensitive resin composition was produced.

In Comparative Example 3 , a photosensitive resin composition was produced in the same manner as in Example 1 except that U-CAT 5002 (manufactured by San Apro) was used instead of U-CAT SA506.

Comparative Example 4 except for 1‒methyl‒2,3,4,6,7,8,9,10‒ octahydropyrimido [1,2‒a] aqepin‒1‒ium (2,3,4,6 , 7,8,9,10‒octahydropyrimido [1,2‒a] aqepin‒1‒ium) and salts of p‒toluenesulfonate were manufactured by the same method as in Example 1. Photosensitive resin composition.

Test method A 2 inch by 2 inch glass substrate (EAGLE 2000, manufactured by Corning) was sequentially washed with a neutral detergent, water, and ethanol, and then dried. The photosensitive resin compositions produced in the foregoing Examples and Comparative Examples were spin-coated on the glass substrate, and then prebaked at 90 ° C. for 125 seconds using a hot plate. After cooling the pre-baked substrate to 25 ° C., the distance from the reticle made of quartz glass was set to 150 mm, and an exposure machine (UX-1100SM, manufactured by Ushio Co., Ltd.) was used at an exposure of 60 mJ / cm ² (365 nm standard ) Irradiate light. Here, the photomask is a photomask formed on the same plane with the next pattern.

Regular square openings (Hole patterns) with a 30mm square pattern, spaced at a distance of 100mm from each other, after light irradiation, an aqueous developer containing 0.12% non-ionic surfactant and 0.04% potassium hydroxide , The aforementioned guide film was immersed at 25 ° C. for 60 seconds, developed, washed in water in an oven, and then baked at 80 ° C. for 1 hour. For the pattern thus obtained, the following physical properties were evaluated, and the results are shown in Table 1 below.

(1) Heat-resisting residual film rate ( evaluation of low-temperature hardening performance ) After the pattern-developed cured product is heated at 80 ° C for 1 hour and finally cured, it is further heated at 230 ° C for 30 minutes, and the film caused by additional heating is observed. Degree of contraction.

Under low-temperature hardening conditions, materials with excellent hardening properties are considered to be materials with small shrinkage of the film after additional heating and a high heat-resistance residual film rate after additional heating. It is judged that the low-temperature hardening performance is better.

(2) Evaluation of acid resistance The conductive film manufactured by the aforementioned method was immersed in HNO ₃ and HCl aqueous solution at 45 ° C for 2 minutes. After that, the surface cut by the cutter is affixed with an adhesive tape, and the degree of peeling of the guide film when peeled off is confirmed according to standard test conditions (ASTM D-3359-08) to evaluate the acid resistance.

<Evaluation criteria> 5B: 0% peeling 4B: More than 0% peeling, less than 5% 3B: More than 5% peeling, less than 15% 2B: More than 15% peeling, less than 35% 1B: More than 35% peeling, less than 65% 0B : 65% or more

(3) Alkali solubility evaluation On the substrate, each of the manufactured components was spin-coated, and then pre-baked at 80 ° C for 120 seconds using a hot plate. After cooling the pre-baked substrate to 25 ° C., immerse it in a 0.04% KOH-based aqueous solution, and observe the dissolution process of the guide film for 90 seconds. The alkali solubility was evaluated according to the following criteria.

<Evaluation Criteria> 5B: Dissolved after 40 seconds elapsed 4B: Dissolved after 40 seconds elapsed and less than 60 seconds 3B: Dissolved after 60 seconds elapsed and less than 80 seconds 2B: Elapsed 80 seconds or more and less than 100 seconds Post-dissolution 1B: Dissolution 0B after 100 seconds or more: peeling

(4) Evaluation of peel resistance The guide film produced by the aforementioned method was immersed in SAM-19 (DONGWOO FINE-CHEM stripper) for 2 minutes. Thereafter, the degree of occurrence of peeling was evaluated in accordance with standard test conditions (ASTM D-3359-08), and the resistance to peeling liquid was evaluated.

<Evaluation criteria> 5B: Not peeled 4B: More than 0%, less than 5% 3B: More than 5%, less than 15% 2B: More than 15%, less than 35% 1B: More than 35%, less than 65% 0B: 65% or more

(5) Evaluation of storage stability After the manufactured composition was stored in a 23 ° C incubator for 48 hours, the temperature of the viscometer (TVE-33L, manufactured by Toki-SanGyo) was adjusted to 25 ° C, and the composition was dropped using a micro pipette. After 1.2 mL, the change in viscosity was observed, and the following evaluation criteria were used.

<Evaluation criteria> ○: No change over 2cp ×: Change over 2cp

[Table 1]

From the foregoing Table 1, it can be seen that the examples included in the scope of the present invention have higher heat resistance and residual film ratio, so they have better low-temperature hardening performance, and have higher acid resistance and resistance to peeling liquid, so they have chemical resistance. Better. In addition, in the evaluation of alkali solubility, since the faster the dissolution, the better the alkali solubility is evaluated, it is confirmed that the present invention is applicable to a negative photosensitive resin (especially a negative photoresist).

Claims (10)

A photosensitive resin composition comprising the following chemical formula 1 and an alkali-soluble resin; (Wherein R ₁ to R ₆ , R ₈ and R ₉ are each independently hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms, R ₇ is hydrogen, and X ^- is an organic acid salt anion;) The alkali-soluble resin includes: a first resin having a repeating unit represented by the following chemical formula 2; and a second resin having a repeating unit represented by the following chemical formula 3; (Wherein R ₁ , R ₂ and R ₃ are independently hydrogen or methyl, and R ₄ is derived from (meth) acrylic acid, 2- (meth) acryloxyethylhexahydrophthalate (2-((Metha) Acryloyloxy) ethyl hexahydrophthalate), 2-((Metha) Acryloyloxy) ethyl phthalate), and 2-((Metha) Acryloyloxy) ethyl phthalate), and 2- ( The structure of the monomers selected from the group of 2-((Metha) Acryloyloxy) ethyl succinate); R ₅ is derived from the following formulae (1) ~ (9 The structure of the monomer selected in the group of); R ₆ is a structure derived from a monomer selected from the group consisting of the following formulae (10) to (12); a = 10 ~ 60mol%, b = 20 ~ 50mol%, c = 10 ~ 70mol%;) _{(Wherein, R 1, R 2, R} 3 and R ₄ are independently hydrogen or methyl, R ₅ include lines derived from a (meth) acrylic acid, 2- (meth) oxyethyl hexahydrophthalic Bing Xixi Phthalate (2-((Metha) Acryloyloxy) ethyl hexahydrophthalate), 2- (meth) acryloyloxy) ethyl phthalate, and The structure of the monomers selected from the group of 2-((Metha) Acryloyloxy) ethyl succinate; R ₆ is derived from benzyl (meth) acrylate Ester, 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, tetrahydrofuran methyl (meth) acrylate, ( (Meth) styrene, vinyltoluene, vinylnaphthalene, N-benzylcis-butenediimine, methyl (meth) acrylate, ethyl (meth) acrylate, methoxyethylene glycol Base) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (Meth) acrylate, methoxytetraethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and ( Structure of monomers selected from the group of tetrahydrofuran methyl methacrylate; R ₇ is a structure derived from monomers selected from the group including the aforementioned formulae (1) to (9); R ₈ is a structure derived from a monomer selected from the group consisting of the following formulae (10) to (16); d = 10 ~ 30mol%, e = 10 ~ 20mol%, f = 30 ~ 60mol%, g = 10 ~ 30mol%). For example, the photosensitive resin composition of the first scope of the patent application, wherein all of R ₁ to R _{9 of the} aforementioned chemical formula 1 compound are hydrogen. For example, the photosensitive resin composition of the first patent application range, wherein the anion of the aforementioned chemical formula 1 is any one selected from the group consisting of p-toluenesulfonate anion, 2-carboxybenzoate anion, and octanoate anion. One. For example, the photosensitive resin composition of the first scope of the application for a patent, wherein the compound of the aforementioned chemical formula 1 is contained in an amount of 0.05 to 10 parts by weight relative to 100 parts by weight of the entire composition. For example, the photosensitive resin composition of the first patent application scope further includes a photopolymerizable compound, a photopolymerization initiator, and a solvent. For example, the photosensitive resin composition according to claim 5 of the application, further comprising a polyfunctional thiol group. For example, the photosensitive resin composition of the first patent application scope can be hardened at 70 ~ 100 ° C. A light-hardening pattern is manufactured from a photosensitive resin composition as claimed in any one of claims 1 to 7. For example, the light hardening pattern of the eighth patent application range, wherein the light hardening pattern includes an adhesive layer, an array flattening film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a color filter pattern, and a black matrix. Pattern and column spacer pattern. A pattern display device includes a light-hardened pattern as described in item 8 of the patent application.