KR20170027005A - Photosensitive resin comopsition and cured pattern formed from the same - Google Patents

Abstract

The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition which comprises: a first alkali-soluble resin (A) including a repetitive unit having a specific structure; a second alkali-soluble resin (B); a polymeric compound (C) polymerized by containing a bisphenol A-type epoxy monomer and a bisphenol F-type epoxy monomer, and having the weight average molecular weight of 50,000-60,000; a polymerizable compound (D); a photopolymerization initiator (E); and a solvent (F). According to the present invention, the photosensitive resin composition enables the formation of patterns which exhibit excellent low temperature curing reactivity as well as superior durability such as pencil hardness and chemical resistance.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a photosensitive resin composition and a photocurable pattern formed therefrom.

The present invention relates to a photosensitive resin composition and a photocurable pattern formed therefrom, and more particularly, to a photosensitive resin composition capable of forming a pattern having excellent reactivity and excellent durability even under low-temperature curing conditions.

In the display field, the 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-curable pattern. In order to improve the process yield and improve the physical properties of the application object in this process, a photosensitive resin having a high sensitivity A composition is required.

The pattern formation of the photosensitive resin composition is caused by photolithography, that is, a change in the polarity of the polymer caused by the photoreaction and a crosslinking reaction. Particularly, the change characteristics of the solubility in a solvent such as an aqueous alkali solution after exposure are utilized.

The pattern formation by the photosensitive resin composition is classified into a positive type and a negative type according to the solubility of the photosensitive portion in development. In the positive type photoresist, the exposed portion is dissolved by the developing solution, and the negative type photoresist is a method in which the exposed portion is not dissolved in the developing solution and the unexposed portion is dissolved to form a pattern. In the positive type and negative type, A binder resin, a crosslinking agent, and the like are different from each other.

2. Description of the Related Art Recently, the use of a touch screen equipped with a touch panel has been explosively increased. Recently, a flexible touch screen has received much attention. Accordingly, it is necessary to provide a flexible characteristic for various substrates used for a touch screen, and accordingly, a usable material is also limited by a flexible polymer material, so that the manufacturing process is required to be performed under milder conditions have.

Accordingly, the curing conditions of the photosensitive resin composition also require the necessity of low-temperature curing in the conventional high-temperature curing, and the low-temperature curing has a problem in that the reactivity is lowered and the durability of the formed pattern is deteriorated.

Korean Patent No. 10-1302508 discloses a negative photosensitive resin composition which is excellent in heat resistance and light resistance and can improve sensitivity by including a copolymer polymerized by using a cyclohexenyl acrylate monomer, Conditions do not show required durability.

Korean Patent No. 10-1302508

An object of the present invention is to provide a photosensitive resin composition capable of being cured at a low temperature, excellent in reactivity, and excellent in durability such as hardness and chemical resistance of a formed pattern.

It is another object of the present invention to provide a photosensitive resin composition having an excellent pattern forming ability in a photolithography process.

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

1. A resin composition comprising: a first alkali-soluble resin (A) comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit containing a carboxylic acid group;

A second alkali-soluble resin (B) comprising a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and a repeating unit containing a carboxylic acid group;

(C) polymerized with a bisphenol A type epoxy monomer and a bisphenol F type epoxy monomer and having a weight average molecular weight of 50,000 to 60,000;

Polymerizable compound (D);

A photopolymerization initiator (E); And

A photosensitive resin composition comprising a solvent (F):

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

(Wherein R ₁ , R ₂ , R ₄ , R ₅ and R ₆ are each independently hydrogen or a methyl group, and R ₃ is a straight or branched chain alkyl group or alkenyl group having 1 to 4 carbon atoms).

2. The photosensitive resin composition according to 1 above, wherein the weight average molecular weight of the first alkali-soluble resin (A) is 6,000 to 14,000.

3. The photosensitive resin composition according to 1 above, wherein the second alkali-soluble resin (B) has a weight average molecular weight of 10,000 to 30,000.

4. The photosensitive resin composition according to 1 above, wherein the second alkali-soluble resin (B) contains 60 to 65 mol% of the repeating unit represented by the formula (4) based on 100 mol% of the total repeating units.

5. The photosensitive resin composition according to 1 above, wherein the mixing weight ratio of the first alkali-soluble resin (A) and the second alkali-soluble resin (B) is 50:50 to 90:10.

6. The photosensitive resin composition according to item 1 above, wherein the polymerization molar ratio of the bisphenol A type epoxy monomer and the bisphenol F type epoxy monomer in the polymer compound (C) is 50:50 to 25:75.

7. The photosensitive resin composition according to item 1, wherein curing is possible at a low temperature of 70 to 150 占 폚.

8. A photocurable pattern formed from the photosensitive resin composition of any one of items 1 to 7 above.

9. The photocurable pattern according to the above 8, wherein the photocurable pattern is selected from the group consisting of an array planarizing film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern and a column spacer pattern.

10. An image display device comprising the photocuring pattern of the above 8.

By using an alkali-soluble resin having a specific structure, the photosensitive resin composition of the present invention can exhibit excellent reactivity under low-temperature curing conditions, thereby realizing a pattern with excellent resolution.

The photosensitive resin composition of the present invention can form a pattern having excellent pencil hardness and chemical resistance by using the alkali-soluble resin and a polymer compound having a specific structure in combination.

FIG. 1 schematically shows a definition of a bottom CD size of a pattern according to an embodiment of the present invention.
2 is a photograph of a normal pattern with no residual film in the evaluation of the residual film after development.
Figs. 3 and 4 are photographs of patterns in the case where a residual film is formed after development in the evaluation of residual film after development.
Figures 6 to 8 show pencil hardness evaluation criteria.

The present invention relates to a photosensitive resin composition, and more particularly to a photosensitive resin composition comprising a first alkali-soluble resin (A) containing a repeating unit of a specific structure; A second alkali-soluble resin (B); (C) polymerized with a bisphenol A type epoxy monomer and a bisphenol F type epoxy monomer and having a weight average molecular weight of 50,000 to 60,000; Polymerizable compound (D); A photopolymerization initiator (E); And a solvent (F), thereby forming a pattern having excellent low temperature curing reactivity and excellent durability such as pencil hardness and chemical resistance.

Hereinafter, the present invention will be described in detail.

<Photosensitive resin composition>

The photosensitive resin composition of the present invention comprises a first alkali-soluble resin (A), a second alkali-soluble resin (B), a polymer compound (C) polymerized from a bisphenol- And a solvent (F).

In the present invention, each repeating unit represented by the formula includes an isomer of the repeating unit, and when the repeating unit represented by each formula is an isomer, the repeating unit represented by the formula is represented by a Means a chemical formula.

In the present invention, each repeating unit can be freely positioned at any position of the chain within a predetermined mol% range. That is, the parentheses in the formulas representing the polymer or the resin are represented by one block for expressing the mol%, but each repeating unit may be placed in a block or separately as long as it is within the resin.

The first alkali-soluble resin (A)

The alkali-soluble resin is a component which imparts solubility to the alkali developing solution used in the development processing at the time of forming the pattern. In the present invention, by using an alkali-soluble resin having a repeating unit having a specific structure in combination, For example, 70 to 150 DEG C), it is possible to form a pattern with excellent reliability and excellent reliability.

The photosensitive resin composition according to the present invention comprises a first alkali-soluble resin (A) and a second alkali-soluble resin (B) in which the repeating units are different from each other.

The first alkali-soluble resin (A) according to the present invention comprises a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2) and a repeating unit containing a carboxyl group, And performs a function of improving chemical resistance.

[Chemical Formula 1]

(2)

In the formula, R ₁ and R ₂ are each independently hydrogen or a methyl group, and R ₃ is a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms.

In the first alkali-soluble resin (A), the repeating unit containing a carboxyl group has a function of imparting solubility to an alkali developer, and may be one derived from methacrylic acid, 2-vinylacetic acid or the like.

An example of the first alkali-soluble resin (A) according to the present invention may be a structure represented by the following formula (A).

(A)

In the formula, R ₁ , R ₂ and R ₃ are the same substituents as described above, R ₇ is hydrogen or a methyl group, a = 20 to 70 mol%, b = 20 to 60 mol% and c = 5 to 30 mol% .

The weight average molecular weight of the first alkali-soluble resin (A) according to the present invention is not particularly limited, but it is preferably 6,000 to 20,000 from the viewpoint of improving the reactivity and chemical resistance of the photosensitive resin composition at low temperature, 13,000 to 17,000. When the above range is satisfied, CD-Bias of the pattern can be realized in an appropriate range to form a pattern having excellent resolution, and the chemical resistance and pencil hardness can also be improved. On the other hand, when the weight average molecular weight of the first alkali-soluble resin (A) is more than 20,000, the molecular weight becomes excessively large and the compatibility with the other components of the photosensitive resin composition is lowered, The line width of the pattern also increases and the CD-Bias characteristic may be degraded.

The second alkali-soluble resin (B)

The second alkali-soluble resin (B) according to the present invention comprises a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4) and a repeating unit containing a carboxyl group, And improves durability such as chemical resistance.

(3)

[Chemical Formula 4]

In the formulas, R ₄ , R ₅ and R ₆ independently of one another are hydrogen or a methyl group.

In the present invention, since the repeating unit represented by the general formula (3) of the second alkali-soluble resin (B) contains an acryloyloxy 2-hydroxypropyl group, the polymerization reaction with the polymerizable compound in the photopolymerization reaction in the exposure step Thereby forming a hardened network, thereby improving the pattern formability.

In addition, the repeating unit represented by the formula (4) includes an aromatic ring, thereby improving the compatibility between the binder polymer and the monomer containing an unsaturated group, thereby improving the pattern formability and durability.

In the second alkali-soluble resin (B), the repeating unit containing a carboxyl group has a function of imparting solubility to an alkali developer and may be one derived from methacrylic acid, 2-vinylacetic acid, or the like.

The number of moles of each repeating unit of the second alkali-soluble resin (B) is not particularly limited, and the repeating unit represented by the formula (4) may be contained in an amount of 60 to 65 mol% based on 100 mol% of the total repeating units. When it is included in the above-mentioned range, it is preferable that the pencil hardness can be realized while realizing proper developability. On the other hand, when the number of moles of the repeating unit represented by Formula 4 is more than 65 mol%, the reactivity of the curing reaction may be lowered because the other functional groups are relatively decreased, and the hydrophobicity may be somewhat increased, have.

The second alkali-soluble resin (B) according to the present invention may contain only a repeating structure having the above-mentioned formula (3), (4) and a carboxyl group, and may be a structure represented by the following formula (B).

[Chemical Formula B]

In the formula, R ₄ , R ₅ and R ₆ are the same substituents as those described above, and a = 60 to 65 mol%, b = 1 to 10 mol%, c = 5 to 35 mol% and d = 1 to 25 mol%.

The weight average molecular weight of the second alkali-soluble resin (B) according to the present invention is not particularly limited, but is preferably from 10,000 to 30,000, more preferably from 20,000 to 25,000 from the viewpoint of pattern formation and improvement in durability . When the above range is satisfied, a pattern having excellent durability and chemical resistance can be formed, which is preferable. On the other hand, when the weight average molecular weight of the second alkali-soluble resin (B) is less than 10,000, the pencil hardness of the pattern may be lowered.

The first alkali-soluble resin (A) and the second alkali-soluble resin (B) according to the present invention may further comprise, independently of each other, a repeating unit formed from other monomers known in the art, It may be formed only as a repeating unit.

In the synthesis of the alkali-soluble resin, the monomer forming the repeating unit which can be further added is not particularly limited, and examples thereof include monocarboxylic acids such as crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid, and anhydrides thereof; mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate; Vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, m- vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinyl Aromatic vinyl compounds such as benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide; Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate; Alicyclic (meth) acrylates such as cyclopentyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate and 2-dicyclopentanyloxyethyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds; Unsaturated oxirane compounds such as methyl glycidyl (meth) acrylate; A (meth) acrylate substituted with a cycloalkane or a dicycloalkane ring having 4 to 16 carbon atoms; And the like. These may be used alone or in combination of two or more.

It is preferable that the acid value of the first alkali-soluble resin (A) and the second alkali-soluble resin (B) are independently in the range of 20 to 200 (KOH mg / g). When the acid value is in the above range, excellent developability and long-term stability can be obtained.

The mixing weight ratio of the first alkali-soluble resin (A) and the second alkali-soluble resin (B) according to the present invention is not particularly limited, but is, for example, 50:50 to 90:10, To 85:15. It is preferred that the content of the first alkali-soluble resin (A) is higher than that of the second alkali-soluble resin (B) in order to ensure low-temperature curability, but the content of the first alkali- If it exceeds 9 times the weight of the soluble resin (B), durability such as chemical resistance may be lowered.

In the present invention, the content of the alkali-soluble resin in which the first alkali-soluble resin (A) and the second alkali-soluble resin (B) are combined is not particularly limited. For example, the total amount of the photosensitive resin composition 10 to 90 parts by weight, preferably 25 to 70 parts by weight. When it is contained within the above-mentioned range, solubility in a developing solution is sufficient, and the developing property is excellent, and a photocurable pattern having excellent mechanical properties can be formed.

Bisphenol-based  The polymer compound (C)

By containing the bisphenol-based polymer (C) having a specific molecular weight, the photosensitive resin composition of the present invention can improve the pencil hardness and chemical resistance of the coating film after curing.

The polymer compound (C) according to the present invention is a compound thermally polymerized by ring-opening reaction of an epoxy compound including a bisphenol A type epoxy monomer and a bisphenol F type epoxy monomer and having a weight average molecular weight of 50,000 to 60,000. The polymer compound (C) includes a relatively large molecular weight and a rigid aromatic ring structure repeatedly so as to improve the pencil hardness after curing of the photosensitive resin composition and exhibit strong hydrophobicity, so that the chemical resistance can also be improved.

On the other hand, when a bisphenol A-type epoxy monomer and a bisphenol F-type epoxy monomer are included as a polymerizable compound in a photosensitive resin composition, it is difficult to form a curing network between the epoxy monomers. As a result, Is difficult to implement. That is, only when the two epoxy monomers are synthesized with a high molecular weight compound having a weight average molecular weight of 50,000 to 60,000, the mechanical properties of the cured product can be secured.

The polymer compound (C) according to the present invention is a compound having a weight average molecular weight of 50,000 to 60,000 as described above. When the molecular weight of the polymer compound (C) is less than 50,000, mechanical reliability may be deteriorated. , There is a problem that the hydrophobicity is excessively increased, a residual film around the pattern is formed at the time of pattern formation, whitening occurs on the surface, and the CD-Bias characteristic of the pattern is deteriorated. Also, the developability may be reduced, and compatibility with other components may be lowered.

In the polymer compound (C) according to the present invention, the polymerization molar ratio of the bisphenol A-type epoxy monomer to the bisphenol F-type epoxy monomer is not particularly limited. However, since the bisphenol A type epoxy monomer contains a methyl group in the molecule, the bisphenol A type epoxy monomer is relatively more hydrophobic than the bisphenol F type epoxy monomer. Accordingly, when the bisphenol A type epoxy monomer is polymerized by using an excess amount of the bisphenol A type epoxy monomer, The CD-Bias characteristic of the pattern may be deteriorated, such as the occurrence of a residual film around the photosensitive drum and the formation of whiteness on the surface thereof. In this case, the speed with respect to the developer in the developing process is lowered and the compatibility with other components of the photosensitive resin composition is lowered there is a problem.

From this point of view, it is preferable to polymerize bisphenol F type epoxy monomers in an excess amount rather than bisphenol A type epoxy monomers. For example, bisphenol A type epoxy monomers and bisphenol F type epoxy monomers are used in an amount of 50:50 to 25:75 It is preferable that they are polymerized in a molar ratio.

An example of the polymer compound (C) according to the present invention may be a structure represented by the following formula (C).

&Lt; RTI ID = 0.0 &

In the above formula, the number of moles (a, b) of the repeating unit can be appropriately selected within a range that satisfies the above-mentioned weight-average molecular weight and molar ratio.

The content of the polymer compound (C) according to the present invention is not particularly limited, but may be in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the photosensitive resin composition based on the solid content. When added in a small amount in the above-mentioned range, the pencil hardness and chemical resistance of the coating film after curing can be improved, and when contained in the above range, compatibility with other components and developability of pattern are not lowered.

Polymerizable  Compound (D)

The polymerizable compound (D) used in the photosensitive resin composition of the present invention increases the crosslinking density during the production process and can enhance the mechanical properties of the photocuring pattern.

The polymerizable compound (D) can be used in the art without any particular limitation, and examples thereof include monofunctional monomers, bifunctional monomers and other multifunctional monomers, and the kind thereof is not particularly limited, For example.

Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money and so on. 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) Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, and the like. Of these, multifunctional monomers having two or more functional groups are preferably used.

The content of the polymerizable compound (D) is not particularly limited, but may be, for example, 10 to 90 parts by weight, preferably 30 to 80 parts by weight, based on 100 parts by weight of the alkali-soluble resin based on the solid content in the photosensitive resin composition Lt; / RTI &gt; When the polymerizable compound (D) is contained in the above-mentioned content range, it can have excellent durability and improve the developability of the composition.

Light curing Initiator (E)

The type of the photopolymerization initiator (E) according to the present invention is not particularly limited as long as it can polymerize the polymerizable compound (D), and examples thereof include acetophenone compounds, benzophenone compounds, At least one compound selected from the group consisting of a basic compound, a non-imidazole-based compound, a thioxanthone-based compound, and an oxime ester-based compound can be used, and an oxime ester-based compound is preferably used.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane -1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Specific examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4 Bis (trichloromethyl) -6- [2- (5-methylfuran-1-yl) Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- L-methylethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Specific examples of the imidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4 ', 5,5' position is substituted by a carboalkoxy group , Preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis , 4 ', 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole .

Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- propanedioxanthone And the like.

Specific examples of the oxime ester compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, 1,2-octanedione, (O-benzoyloxime), 1- (9-ethyl) -6- (2-methylbenzoyl- Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (Adeca), NCI-831 (Ciba Geigy), CGI- Adeca).

The photopolymerization initiator (E) may further include a photopolymerization initiator to improve the sensitivity of the photosensitive resin composition of the present invention. Since the photosensitive resin composition according to the present invention contains a photopolymerization initiator, the sensitivity can be further increased and the productivity can be improved.

Examples of the photopolymerization initiator 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; aliphatic amines such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, 2-ethylhexyl dimethylbenzoate, 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.

Concrete examples of the carboxylic acid compound include aromatic heteroacetic acid compounds. Phenylthioacetic acid, methylphenylthioacetic acid, methylphenylthioacetic acid, methylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic 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-mercaptobutyloxy Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), and the like can be used. .

The content of the photopolymerization initiator (E) is not particularly limited, but may be in the range of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the photosensitive resin composition based on the solid content . When the above range is satisfied, the sensitivity of the photosensitive resin composition is increased and the exposure time is shortened. Thus, the productivity is improved, the resolution can be maintained, and the strength of the formed pixel portion and the smoothness on the surface of the pixel portion can be improved. good.

Solvent (F)

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

Specific examples of the solvent (F) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate and 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, and methoxypentyl acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether and propylene glycol ethyl propyl ether; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol and butoxybutyl alcohol; Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate and butoxybutyl acetate; Butanediol monoalkyl ether propionates such as methoxy butyl propionate, ethoxy butyl propionate, propoxy butyl propionate and butoxy butyl propionate; Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol methyl ethyl 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; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Examples of the solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, methylhydroxyacetate, , Hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, Methyl methoxyacetate, methyl methoxyacetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propoxypropylacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, butyl Methoxypropionate, ethyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, , Propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, Ethoxypropionate, propyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, Propoxy propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionic acid ethyl, 3-propoxypropionate, Esters such as ropil, 3-butoxy-propionic acid butyl; Cyclic ethers such as tetrahydrofuran and pyran; and cyclic esters such as? -butyrolactone. The solvents exemplified herein may be used alone or in combination of two or more.

The solvent may be selected from esters such as alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate And more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, 3-methoxypropionic acid Methyl and the like can be used.

The content of the solvent (F) may be in the range of 40 to 95 parts by weight, preferably 45 to 85 parts by weight based on 100 parts by weight of the total amount of the photosensitive resin composition. When the above-mentioned range is satisfied, it is preferable because the coating property is improved when applied by a spin coater, a slit & spin coater, a slit coater (sometimes called a die coater, a curtain flow coater), an ink jet or the like.

Additive (G)

The photosensitive resin composition according to the present invention may further contain additives known in the art as needed. Examples of such additives include fillers, other polymer compounds, curing agents, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, coagulation inhibitors and chain transfer agents. These additives may be used singly or in combination.

< Photocuring  Pattern and image display device>

An object of the present invention is to provide an image display device including the photo-curable pattern made of the photosensitive resin composition and the photo-curable pattern.

The photocurable pattern prepared from the photosensitive resin composition is excellent in low temperature curability and excellent in chemical resistance and pencil hardness. As a result, it can be used for various patterns such as an adhesive layer, an array flattening film, a protective film, an insulating film pattern, and the like in an image display apparatus, and can be used as a photoresist, a black matrix, a column spacer pattern, a black column spacer pattern, However, it is not limited to this, and is particularly suitable for an insulating film pattern.

The image display device having the light curing pattern or using the pattern during the manufacturing process may include a liquid crystal display device, an OLED, a flexible display, and the like. However, the present invention is not limited thereto, Can be exemplified.

The photo-curing pattern can be produced by applying the above-described photosensitive resin composition of the present invention onto a substrate and forming a photo-curable pattern (after the development step if necessary).

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

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

(One) Manufacturing example  A-1

A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with nitrogen at 0.02 L / min to make a nitrogen atmosphere. 150 g of diethylene glycol methyl ethyl ether was added and heated to 70 캜 with stirring. Subsequently, 132.2 g (0.60 mol) of a mixture of the following formulas (6) and (7) (molar ratio of 50:50), 55.3 g (0.30 mol) of 3-ethyl-3-oxetanyl methacrylate and 8.6 g 0.10 mol) was dissolved in 100 g of diethylene glycol methyl ethyl ether.

[Chemical Formula 6]

(7)

The resulting 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 Was added dropwise to the flask over 4 hours using a separate dropping funnel. After the dropwise addition of the polymerization initiator solution was completed, the solution was maintained at 70 DEG C for 4 hours and then cooled to room temperature to obtain a copolymer having a solid content of 35.9% by mass and an acid value of 62 mg-KOH / g (in terms of solid content) (Resin A-1) represented by the following formula (1) was obtained. The weight average molecular weight Mw was 7,900 and the molecular weight distribution was 1.8.

(A-1)

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured by using HLC-8120GPC (manufactured by TOSOH CORPORATION), and the columns were TSK-GELG4000HXL and TSK-GELG2000HXL connected in series , The column temperature was 40 占 폚, the mobile phase solvent was tetrahydrofuran, the flow rate was 1.0 ml / min, the injection amount was 50 占, and the detector RI was used. The concentration of the test sample was 0.6 mass% (solvent = tetrahydrofuran) TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500 and A-500 (manufactured by TOSOH CORPORATION) were used.

The ratio of the weight average molecular weight to the number average molecular weight obtained above was defined as a molecular weight distribution (Mw / Mn).

(2) Manufacturing example  A-2

A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with nitrogen at 0.02 L / min to make a nitrogen atmosphere. 150 g of diethylene glycol methyl ethyl ether was added and heated to 70 캜 with stirring. Subsequently, 132.2 g (0.60 mol) of the mixture of the above-mentioned formulas (6) and (7) (molar ratio of 50:50), 55.3 g (0.30 mol) of 3-ethyl-3-oxetanyl methacrylate and 8.6 g mol) was dissolved in 150 g of diethylene glycol methyl ethyl ether to prepare a solution.

The resulting 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 Was added dropwise to the flask over 6 hours using a separate dropping funnel. After completion of the dropwise addition of the polymerization initiator solution, the mixture was maintained at 70 캜 for 10 hours, and then cooled to room temperature to obtain a copolymer (resin A-1) having a solid content of 35.6% by mass and an acid value of 63 mg-KOH / 2). A-2 had a weight average molecular weight Mw of 12,800 and a molecular weight distribution of 2.2.

(3) Manufacturing example  A-3

A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with nitrogen at 0.02 L / min to make a nitrogen atmosphere. 150 g of diethylene glycol methyl ethyl ether was added and heated to 70 캜 with stirring. Subsequently, 132.2 g (0.60 mol) of a mixture of the following structural formula 6 and 7 (molar ratio 50:50), 55.3 g (0.30 mol) of 3-ethyl-3-oxetanyl methacrylate and 8.6 g mol) was dissolved in 150 g of diethylene glycol methyl ethyl ether to prepare a solution.

The resulting 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 Was added dropwise to the flask over 8 hours using a separate dropping funnel. After the completion of the dropwise addition of the polymerization initiator solution, the mixture was maintained at 70 캜 for 18 hours and then cooled to room temperature to obtain a copolymer (resin A-3) having a solid content of 35.3% by mass and an acid value of 63 mg-KOH / 3). A-3 had a weight average molecular weight Mw of 25,600 and a molecular weight distribution of 2.5.

(4) Manufacturing example  A-4

198.2 g (0.90 mol) of a mixture (molar ratio of 50:50) and 8.6 g (0.10 mol) of methacrylic acid were added under the same conditions as in Preparation Example A-1, , A solids content of 41.6% by mass, and an acid value of 59 mg-KOH / g (in terms of solid content) (resin A-4).

The resin A-4 thus obtained had a weight average molecular weight Mw of 7,790 and a molecular weight distribution of 1.9.

(A-4)

Manufacturing example  2. Synthesis of second alkali-soluble resin (B)

(One) Manufacturing example  B-1

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was introduced at 0.02 L / min to make a nitrogen atmosphere, and 200 g of propylene glycol monomethyl ether acetate was introduced. After elevating the temperature to 100 캜, 21.6 g Azobis (2,4-dimethylvaleronitrile) 3.0 (trade name, manufactured by Toagosei Co., Ltd.), 4.7 g (0.05 mol) of norbornene, 76.8 g (0.65 mol) of vinyltoluene and 150 g of propylene glycol monomethyl ether acetate g was added dropwise to the flask over a period of 6 hours from the dropping funnel, and stirring was further continued at 100 ° C for 12 hours.

Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 28.4 g (0.20 mol) of glycidyl methacrylate (67 mol% based on the acrylic acid used in the present reaction) was charged into the flask, and the reaction was continued at 110 DEG C for 8 hours , And an unsaturated group-containing resin (B-1) having a solid acid value of 53 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 23,400 and the molecular weight distribution (Mw / Mn) was 2.5.

(B-1)

(2) Manufacturing example  B-2

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 200 g of propylene glycol monomethyl ether acetate was introduced. After raising the temperature to 100 캜, 24.5 g Azobis (2,4-dimethylvaleronitrile) 3.0 (2.9 g) was added to a mixture containing 4.7 g (0.05 mol) of norbornene, 72.1 g (0.61 mol) of vinyltoluene and 150 g of propylene glycol monomethyl ether acetate g was added dropwise to the flask over a period of 6 hours from the dropping funnel, and stirring was further continued at 100 ° C for 12 hours.

Subsequently, 28.4 g (0.20 mol (relative to acrylic acid used in this reaction) of 59 mol%) of glycidyl methacrylate was charged into the flask, and the reaction was continued at 110 DEG C for 6 hours , And an unsaturated group-containing resin B-2 having a solid acid value of 71 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 25,700 and the molecular weight distribution (Mw / Mn) was 2.7.

(3) Manufacturing example  B-3

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was introduced at 0.02 L / min to make a nitrogen atmosphere, and 200 g of propylene glycol monomethyl ether acetate was introduced. After elevating the temperature to 100 캜, 28.8 g Azobis (2,4-dimethylvaleronitrile) 3.0 (0.07 mol) was added to a mixture containing 4.7 g (0.05 mol) of norbornene, 65.0 g (0.55 mol) of vinyltoluene and 150 g of propylene glycol monomethyl ether acetate g was added dropwise to the flask over a period of 2 hours from the dropping funnel, and stirring was further continued at 100 ° C for 5 hours.

Subsequently, 28.4 g (0.20 mol (relative to acrylic acid used in this reaction) of 50 mol%) of glycidyl methacrylate was charged into the flask, and the reaction was continued at 110 DEG C for 6 hours To obtain an unsaturated group-containing resin B-3 having a solid acid value of 94 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 27,500 and the molecular weight distribution (Mw / Mn) was 3.1.

(4) Manufacturing example  B-4

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 200 g of propylene glycol monomethyl ether acetate was introduced. After raising the temperature to 100 캜, 24.5 g Azobis (2,4-dimethylvaleronitrile) 3.6 (4.7 g, 0.05 mole), norbornene 72.1 g (0.61 moles) of vinyltoluene and 150 g of propylene glycol monomethyl ether acetate g was added dropwise to the flask over a period of 2 hours from the dropping funnel, and stirring was further continued at 100 ° C for 5 hours.

Subsequently, 28.4 g (0.20 mol (relative to acrylic acid used in this reaction) of 59 mol%) of glycidyl methacrylate was charged into the flask, and the reaction was continued at 110 DEG C for 6 hours , And an unsaturated group-containing resin B-4 having a solid acid value of 70 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 14,300 and the molecular weight distribution (Mw / Mn) was 2.2.

(5) Manufacturing example  B-5

200 g of propylene glycol monomethyl ether acetate was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer at a flow rate of 0.02 L / min to obtain a nitrogen atmosphere. After raising the temperature to 100 캜, 18.0 g Azobis (2,4-dimethylvaleronitrile) 3.6 (0.07 mol) was added to a mixture containing 4.7 g (0.05 mol) of norbornene, 82.7 g (0.70 mol) of vinyltoluene and 150 g of propylene glycol monomethyl ether acetate g was added dropwise to the flask over 2 hours from the dropping funnel and stirring was further continued at 100 ° C for 6 hours to obtain an unsaturated group-containing resin B-5 having an acid value of 138 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 18,400 and the molecular weight distribution (Mw / Mn) was 2.4.

Example  And Comparative Example

A photosensitive resin composition having the composition and the content (parts by weight) shown in the following Tables 1 and 2 was prepared.

division
(Parts by weight) Example One 2 3 4 5 6 7 8 9 10 11 12 13 A A-1 8.47 8.47 8.47 - - - - - - - - - - A-2 - - - 8.47 8.47 8.47 10.59 8.85 6.36 8.13 8.47 8.47 - A-3 - - - - - - - - - - - - 8.47 A-4 - - - - - - - - - - - - - B B-1 4.24 - 4.24 4.24 - 4.24 2.12 4.42 6.36 4.07 - - 4.24 B-2 - 4.24 - - 4.24 - - - - - - - - B-3 - - - - - - - - - - 4.24 - - B-4 - - - - - - - - - - - 4.24 - B-5 - - - - - - - - - - - - - C C-1 - - 2.12 - - 2.12 - - - - - - - C-2 2.12 2.12 - 2.12 2.12 - 2.12 1.11 2.12 3.05 2.12 2.12 2.12 C-3 - - - - - - - - - - - - - C-4 - - - - - - - - - - - - - C-5 - - - - - - - - - - - - - D B-1 8.47 8.47 8.47 8.47 8.47 8.47 8.47 8.85 8.47 8.13 8.47 8.47 8.47 E E-1 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.22 0.21 0.20 0.21 0.21 0.21 E-2 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.66 0.64 0.61 0.64 0.64 0.64 E-3 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.66 0.64 0.61 0.64 0.64 0.64 G G-1 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.22 0.21 0.21 0.21 0.21 0.21 F F-1 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 F-2 45.0 45.0 45.0 45.0 45.0 45.0 45.0 45.0 45.0 45.0 45.0 45.0 45.0

division
(Parts by weight) Comparative Example One 2 3 4 5 6 7 8 A A-1 - - - - - - - - A-2 12.71 - 9.26 8.47 - 8.47 8.47 8.47 A-3 - - - - - - - - A-4 - - - - 8.47 - - - B B-1 - 12.71 4.63 4.24 4.24 4.24 4.24 - B-2 - - - - - - - - B-3 - - - - - - - - B-4 - - - - - - - - B-5 - - - - - - - 4.24 C C-1 - - - - - - - - C-2 2.12 2.12 - - 2.12 - - - C-3 - - - 2.12 - - - - C-4 - - - - - 2.12 - - C-5 - - - - - - 2.12 - D B-1 8.47 8.47 9.26 8.47 8.47 8.47 8.47 8.47 E E-1 0.21 0.21 0.23 0.21 0.21 0.21 0.21 0.21 E-2 0.64 0.64 0.69 0.64 0.64 0.64 0.64 0.64 E-3 0.64 0.64 0.69 0.64 0.64 0.64 0.64 0.64 G G-1 0.21 0.21 0.23 0.21 0.21 0.21 0.21 0.21 F F-1 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 F-2 45.00 45.00 45.00 45.00 45.00 45.00 45.00 45.00

The first alkali-soluble resin (A)

A-1 to A-4: An alkali-soluble resin prepared according to Production Example 1

The second alkali-soluble resin (B)

B-1 to B-5: The alkali-soluble resin prepared according to Production Example 2

The polymer compound (C) - Example

C-1: Polymer (Bispenol A type: Bispenol F type = 50: 50 (jER4250, manufactured by Mitsubishi Chemical Corporation) having a structure of formula 5 (Mw = 59,000)

[Chemical Formula 5]

C-2: 화학식 5의 구조를 가지는 고분자(Bispenol A형:Bispenol F형=25:75(jER®4275, ㈜ 미쓰비시화학 제조))(Mw=60,000)

C-2: Polymer (Bispenol A type: Bispenol F type = 25: 75 (jER4275, manufactured by Mitsubishi Chemical Corporation) having a structure of formula 5 (Mw = 60,000)

C-3: Polymer polymerized only with Bispenol A type (jER®1256, Mitsubishi Chemical Corporation) (Mw = 51000)

C-4: Bispenol A bifunctional epoxy compound (Fw = 340.41) represented by the formula (6)

[Chemical Formula 6]

C-5: Bispenol F-type bifunctional epoxy compound (Fw = 312.36) represented by the formula (7)

(7)

Polymerizable  Compound (D)

D-1: dipentaerythritol hexaacrylate (KAYARAD DPHA: manufactured by Nippon Yakuza Co., Ltd.)

Light curing Initiator (E)

E-1: 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole (B-CIM manufactured by Hodogaya Chemical Co.,

E-2: Oxime ester compound

E-3: Multifunctional Thiol compound

Additive (G)

G-1: 4,4'-butylidenebis [6-tert-butyl-3-methylphenol] (BBM-S, manufactured by Sumitomo Fine Chemical)

Solvent (F)

F-1: Diethylene glycol methyl ethyl ether

F-2: Propylene glycol monomethyl ether acetate

Test Methods

A glass substrate (Eagle 2000; Corning) having an aspect ratio of 2 inches was sequentially washed with a neutral detergent, water and alcohol, and then dried. The photosensitive resin compositions prepared in the above Examples and Comparative Examples were respectively spin-coated on this glass substrate and then pre-baked at 80 DEG C for 120 seconds using a hot plate. The prebaked substrate was cooled to room temperature and light was irradiated at an exposure dose of 40 mJ / cm 2 (based on 365 nm) using an exposure apparatus (UX-1100SM; Ushio Co., Ltd.) with an interval of 150 μm from the quartz glass photomask Respectively. At this time, the photomask used was a photomask in which the following pattern was formed on the same plane.

After the light irradiation, the coating film was immersed in an aqueous 2.38% tetraammonium hydroxide solution at 25 캜 for 60 seconds, developed, washed with water and dried, and then transferred to a clean oven , Post-baking was performed at 130 캜 for 60 minutes. The obtained pattern height was 1.5 占 퐉. The pattern thus obtained was evaluated for physical properties as described below, and the results are shown in Tables 3 and 4 below.

(1) Bottom CD size measurement of pattern

The obtained rectangular Dot pattern was observed with a three-dimensional shape measuring device (SIS-2000 system; manufactured by SNU Precision), and a point 5% of the total height from the bottom surface of the rectangular pattern was defined as Bottom CD, The mean value of the measured values was defined as the CD line width of the pattern. The results are shown in Tables 3 and 4 below.

(2) Pattern of CD-Bias

The pattern size at the film thickness of 3.0 mu m obtained above was measured using a three-dimensional shape measuring apparatus (SIS-2000 system; manufactured by SNU Precision), and the difference from the mask size was calculated by CD-bias as follows. The results are shown in Tables 3 and 4 below.

CD-bias is better the closer to 0, (+) means that the pattern is larger in size than the mask and (-) is smaller in size than the mask.

(3) After development Azure  Whether or not

The Dot pattern obtained above was measured with a scanning electron microscope (Hitachi, S-4700) to confirm whether there was a film residue around the pattern. The results are shown in Tables 3 and 4 below.

The remainder of the Contact Dot pattern defined here means a residue in which the line width is reduced by blocking the bottom portion while remaining like a residual film in the dot. 2 is a photograph of a normal pattern without a residual film, and FIGS. 3 and 4 are photographs of a residual film after development.

(4) Check whether whitening occurs

The resist coating film coated on the glass substrate under the above conditions was exposed and developed, dried, and visually checked for the state of the coating film before the post-baking, thereby confirming whether whitening occurred. The results are shown in Tables 3 and 4 .

The coating film free from whitening maintains the colorless transparent initial state, but when whitening occurs, the surface becomes finer and becomes white. Fig. 5 is a photograph of a case where whitening occurs.

(5) Chemical resistance evaluation

The prepared resist solution was applied to a glass substrate (Eagle 2000; Corning), spin-coated, and pre-baked at 90 DEG C for 125 seconds using a hot plate. After the prebaked substrate was cooled to room temperature. Light was irradiated onto the entire surface of the coating film with an exposure amount of 40 mJ / cm 2 (365 nm standard) using an exposure machine (UX-1100SM; Ushio Co., Ltd.). After the light irradiation, the coating film was immersed in a 2.38% aqueous solution of tetraammonium hydroxide at 25 DEG C for 60 seconds, developed, washed with water and dried, and post-baked at 130 DEG C for 60 minutes using a clean oven. The coated film was immersed in HNO3 and HCl aqueous solution (70% nitric acid (80%) + concentrated hydrochloric acid (20%)) and treated for 45 minutes / 2 minutes. The coated film was cut with a cutter according to ASTM D- After the tape was cut, the tape was attached to the surface and then peeled off. The results are shown in Tables 3 and 4 below.

It is judged that the degree of peeling of the coating film in Cutting / Tape test after the chemical solution treatment is defined as 0B to 5B according to the standard test method, and 5B has the best performance.

<Evaluation criteria for chemical resistance>

5B peeling 0%> 4B peeling less than 5%> 3B peeling 5 to 15%> 2B peeling 15 to 35%> 1B peeling 35 to 65%> 0B peeling 65% or more

(6) Evaluation of pencil hardness

The surface hardness of the cured film obtained by using the substrate manufacturing method was measured. The surface hardness was measured by contacting a Mitsubishi pencil with a pencil hardness tester (Pencil Hardness Tester) and placing a weight of 500 g on the substrate. The surface hardness was measured at a rate of 50 mm / sec The surface hardness was measured by scratching the surface and observing the surface. The measurement standard was evaluated based on the case where no abrasion, peeling, tearing or scratching of the surface was observed at a level corresponding to the pencil hardness, and the results are shown in Tables 3 and 4 below.

&Lt; Criteria for evaluating the strength of pencil hardness &

6B <5B <4B <3B <2B <HB <H <2H <3H <4H <5H <6H <7H <8H <9H (SOFTER -> HARDER)

In general, when the pencil hardness was measured, the marks and the abrasion occurred on the area where the pencil passed, but the hardness was remarkably low as summarized in the comparative example, so that the coating film may be peeled off completely, . The results of this study are as follows.

In the case of ◯, only the pressing and abrasion occurs. In the case of △, the part where the pencil passes is peeled off. In the case of ×, the area where the pencil passes is peeled off.

Figs. 6 to 8 show the pencil hardness evaluation results according to the criteria of O, DELTA, and x.

division Example One 2 3 4 5 6 7 8 9 10 11 12 13 Bottom size (탆) 32.9 32.1 33.5 33.2 33.0 34.3 34.8 32.7 34.7 35.5 32.9 34.6 35.1 CD-Bias (占 퐉) 2.9 2.1 3.5 3.2 3.0 4.3 4.8 2.7 4.7 5.5 2.9 4.6 5.1 Film residue around pattern none none none none none none none none none Occur none none Occur The phenomenon none none none none none none none none none none none none none Chemical resistance 5B 5B 5B 5B 5B 5B 5B 5B 5B 5B 5B 5B 5B Pencil hardness Hardness 3H 3H 4H 4H 3H 4H 3H 3H 3H 4H 2H 3H 4H Tearing ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

division Comparative Example One 2 3 4 5 6 7 8 Bottom size (탆) 36.9 29.3 30.4 42.4 33.9 37.4 34.5 pattern
Exfoliation CD-Bias (占 퐉) 6.9 -0.7 0.4 12.4 3.9 7.4 4.5 Film residue around pattern none none none Occur none Occur Occur The phenomenon none none none Occur none none none Occur Chemical resistance 3B 0B 5B 5B 0B 4B 4B 0B Pencil hardness Hardness 2H 2H 2B 3H 2B HB 2B 2B Tearing △ X △ ○ X △ X ○

Referring to Tables 3 and 4, the CD-bias value of the pattern prepared using the photosensitive resin composition of the present invention was close to zero and the residual film was not generated after development, It was confirmed that pattern formation was excellent. Further, it was confirmed that the pattern produced by using the photosensitive resin composition according to the present invention did not cause development whitening, and was excellent in chemical resistance and durability.

On the other hand, in the case of Example 10 in which the polymeric compound (C) of the present invention was added in a slight excess, the components having high hydrophobicity and high molecular weight were increased, .

In the case of Example 11 in which the number of moles of the repeating unit containing an aromatic ring represented by the general formula (4) of the second alkali-soluble resin was rather small, the functional group component contributing to the mechanical performance was decreased. As a result, In Example 13, in which the molecular weight of the first alkali-soluble resin was rather large, the residue around the pattern was generated as compared with other examples due to the decrease in development due to the increase in the molecular weight of the entire composition, -Bias is slightly decreased.

However, in the case of the pattern prepared using the comparative example other than the photosensitive resin composition of the present invention, it can be confirmed that the CD-bias value greatly deviates from 0 or the residual film is generated after development, and the pattern formation is not excellent. And it was confirmed that the pencil hardness and chemical resistance were lower than those of the examples.

Claims (10)

A first alkali-soluble resin (A) comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit containing a carboxylic acid group;
A second alkali-soluble resin (B) comprising a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and a repeating unit containing a carboxylic acid group;
(C) polymerized with a bisphenol A type epoxy monomer and a bisphenol F type epoxy monomer and having a weight average molecular weight of 50,000 to 60,000;
Polymerizable compound (D);
A photopolymerization initiator (E); And
A photosensitive resin composition comprising a solvent (F):
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

(Wherein R ₁ , R ₂ , R ₄ , R ₅ and R ₆ are each independently hydrogen or a methyl group, and R ₃ is a straight or branched chain alkyl group or alkenyl group having 1 to 4 carbon atoms).
The photosensitive resin composition according to claim 1, wherein the first alkali-soluble resin (A) has a weight average molecular weight of 6,000 to 20,000.
The photosensitive resin composition according to claim 1, wherein the second alkali-soluble resin (B) has a weight average molecular weight of 10,000 to 30,000.
The photosensitive resin composition according to claim 1, wherein the second alkali-soluble resin (B) contains 60 to 65 mol% of the repeating unit represented by the formula (4) based on 100 mol% of the total repeating units.
The photosensitive resin composition according to claim 1, wherein a mixing weight ratio of the first alkali-soluble resin (A) and the second alkali-soluble resin (B) is 50:50 to 90:10.
The photosensitive resin composition according to claim 1, wherein the polymerization molar ratio of the bisphenol A-type epoxy monomer to the bisphenol F-type epoxy monomer in the polymer compound (C) is 50:50 to 25:75.
The photosensitive resin composition according to claim 1, which is capable of curing at a low temperature of 70 to 150 ° C.
A photocurable pattern formed from the photosensitive resin composition according to any one of claims 1 to 7.
9. The photocurable pattern according to claim 8, wherein the photocurable pattern is selected from the group consisting of an array planarizing 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 apparatus comprising the photocurable pattern of claim 8.

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