KR102671237B1 - Negative-type Photosensitive Resin Composition - Google Patents

Abstract

The present invention is a negative photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the alkali-soluble resin includes a first alkali-soluble resin containing a long-chain aliphatic hydrocarbon group having a trialkoxysilyl group at the terminal. A negative photosensitive resin composition, a photocurable film formed therefrom, and an image display device are provided. The negative photosensitive resin composition according to the present invention maintains litho performance, has good developing adhesion without the addition of a separate adhesion enhancer, has excellent chemical resistance, and does not deteriorate adhesion over time.

Description

Negative-type Photosensitive Resin Composition}

The present invention relates to a negative photosensitive resin composition, and more specifically, to a negative photosensitive resin that maintains litho performance, has good developing adhesion without the addition of a separate adhesion enhancer, has excellent chemical resistance, and does not deteriorate adhesion over time. It relates to a composition, a photocurable film formed using the same, and an image display device including the photocurable film.

In the display field, photosensitive resin compositions are used to form various photocurable films such as photoresist, insulating film, protective film, black matrix, and column spacer.

Pattern formation using photosensitive resin compositions is classified into positive and negative types depending on the solubility of the photosensitive part in the developer. In the case of positive type photoresist, the exposed part is dissolved by the developer, and in the case of negative type photoresist, the exposed part is not dissolved in the developer, but the unexposed part is dissolved to form a pattern. Positive and negative types are used. They differ from each other in terms of binder resin, crosslinking agent, etc.

Recently, the use of touch screens equipped with touch panels has increased explosively, and flexible touch screens have recently received great attention. Accordingly, materials such as various substrates used in touch screens must have flexible characteristics. As a result, the materials that can be used are limited to flexible polymer materials, and the manufacturing process is also required to be performed under milder conditions. there is.

Accordingly, the curing conditions for the photosensitive resin composition also require low-temperature curing instead of the conventional high-temperature curing.

However, during low-temperature curing, unlike high-temperature curing, sufficient curing energy cannot be obtained, so development adhesion may be poor. Even if development adhesion is excellent, adhesion with the lower film may decrease over time, resulting in poor adhesion over time. Chemical resistance to chemical treatments used in the process may be poor.

In order to solve this problem, a method of separately adding an adhesion promoter was proposed [see Korean Patent Publication No. 10-2016-0128218], but in this case, most of the adhesion promoters are cross-linked inside the cured network during curing. There is a problem that a small amount acts between the interface with the lower layer, which is actually necessary while forming. In addition, the adhesion promoter may reduce other physical properties such as litho performance. In particular, when the amount of the adhesion promoter added is increased to increase the amount acting between the interface with the lower film, the litho performance of the photosensitive resin composition deteriorates and preservation. Stability may also deteriorate.

Therefore, there is a need for the development of a negative photosensitive resin composition that maintains litho performance, has good developing adhesion without the addition of a separate adhesion enhancer, has excellent chemical resistance, and does not deteriorate adhesion over time.

Republic of Korea Patent Publication No. 10-2016-0128218

One object of the present invention is to provide a negative photosensitive resin composition that maintains litho performance, has good developing adhesion without the addition of a separate adhesion enhancer, has excellent chemical resistance, and does not deteriorate adhesion over time.

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

Another object of the present invention is to provide an image display device including the photocurable film.

On the other hand, the present invention is a negative photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the alkali-soluble resin comprises a first alkali-soluble resin containing a repeating unit represented by the following formula (1) A negative photosensitive resin composition comprising:

[Formula 1]

In the above equation,

R ¹ is hydrogen or a methyl group,

R ² to R ⁴ are each independently an alkyl group of C ₁ -C ₄ ,

n is an integer from 8 to 20.

In one embodiment of the present invention, the repeating unit represented by Formula 1 may be one in which R ¹ is hydrogen or a methyl group, R ² to R ⁴ are methyl groups, and n is 8.

In one embodiment of the present invention, the first alkali-soluble resin may have a trialkoxysilyl group equivalent of 1.10 × 10 ^-3 mol/g or more.

In one embodiment of the present invention, the first alkali-soluble resin may further include a repeating unit represented by the following formula (3).

[Formula 3]

In the above equation,

R ⁷ is hydrogen or a methyl group,

R ⁸ is an alkylene group of C ₁ -C ₁₀ or an oxyalkylene group of C ₁ -C ₁₀ or does not exist,

p is 0 or 1.

In one embodiment of the present invention, the first alkali-soluble resin may further include a repeating unit represented by the following formula (4).

[Formula 4]

In the above equation,

R ⁹ is hydrogen or a methyl group,

R ¹⁰ is an alkylene group of C ₁ -C ₁₀ or an oxyalkylene group of C ₁ -C ₁₀ or does not exist,

R ¹¹ is hydrogen or an alkyl group of C ₁ -C ₁₀ ,

q is 0 or 1.

In one embodiment of the present invention, the alkali-soluble resin may further include a second alkali-soluble resin containing a repeating unit represented by the following formula (2).

[Formula 2]

In the above equation,

R ⁵ and R ⁶ are each independently hydrogen or a methyl group.

On the other hand, the present invention provides a photocurable film formed from the negative photosensitive resin composition.

In one embodiment of the present invention, the photocurable film may be selected from the group consisting of an array planarization film, a protective film, an insulating film, a photoresist pattern, a black matrix pattern, a column spacer pattern, and a black column spacer pattern.

On the other hand, the present invention provides an image display device including the photocurable film.

The negative photosensitive resin composition according to the present invention maintains litho performance, has good developing adhesion without the addition of a separate adhesion enhancer, has excellent chemical resistance, and does not deteriorate adhesion over time.

Hereinafter, the present invention will be described in more detail.

One embodiment of the present invention is a negative photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a solvent (D), wherein the alkali-soluble resin (A) is a terminal It relates to a negative photosensitive resin composition comprising a first alkali-soluble resin containing a long-chain aliphatic hydrocarbon group having an ettrialkoxysilyl group.

Alkali soluble resin (A)

In one embodiment of the present invention, the alkali-soluble resin is a component that usually has reactivity under the action of light or heat and provides solubility to an alkaline developer used in the development process when forming a pattern.

The alkali-soluble resin includes a first alkali-soluble resin containing a long-chain aliphatic hydrocarbon group having a trialkoxysilyl group at the terminal represented by the following formula (1).

[Formula 1]

In the above equation,

R ¹ is hydrogen or a methyl group,

R ² to R ⁴ are each independently an alkyl group of C ₁ -C ₄ ,

n is an integer from 8 to 20.

The C ₁ -C ₄ alkyl group used herein refers to a straight-chain or branched monovalent hydrocarbon having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, and n-butyl. , i-butyl, t-butyl, etc., but are not limited thereto.

In one embodiment of the present invention, the repeating unit represented by Formula 1 may be one in which R ¹ is hydrogen or a methyl group, R ² to R ⁴ are methyl groups, and n is 8.

In the repeating unit represented by Formula 1, the trialkoxysilyl group is located at the end of the long-chain aliphatic hydrocarbon group and can be arranged outside the cured network, thereby increasing the bond between the trialkoxysilyl group and the interface of the substrate at low temperatures without the addition of a separate adhesion promoter. Improves development adhesion during curing, adhesion over time, and chemical resistance. In addition, there is no need to add an adhesion enhancer to ensure insufficient adhesion during low-temperature curing, so litho performance can be maintained.

The repeating unit represented by Formula 1 may be included in an amount of 30 to 60 mol% based on 100 mol% of the total repeating units constituting the alkali-soluble resin. If the repeating unit represented by Formula 1 is included in an amount of less than 30 mol%, sufficient adhesion may not be achieved due to a lack of trialkoxysilyl groups that can form a bond with the lower membrane, and if the repeating unit represented by Formula 1 is included in an amount exceeding 60 mol%, If included, the physical properties of the cured network of the alkali-soluble resin may change, reducing the reliability of the cured structure.

In one embodiment of the present invention, the first alkali-soluble resin may further include a repeating unit represented by the following formula (3).

[Formula 3]

In the above equation,

R ⁷ is hydrogen or a methyl group,

R ⁸ is an alkylene group of C ₁ -C ₁₀ or an oxyalkylene group of C ₁ -C ₁₀ or does not exist,

p is 0 or 1.

In one embodiment of the present invention, the first alkali-soluble resin may further include a repeating unit represented by the following formula (4).

[Formula 4]

In the above equation,

R ⁹ is hydrogen or a methyl group,

R ¹⁰ is an alkylene group of C ₁ -C ₁₀ or an oxyalkylene group of C ₁ -C ₁₀ or does not exist,

R ¹¹ is hydrogen or an alkyl group of C ₁ -C ₁₀ ,

q is 0 or 1.

The C ₁ -C ₁₀ alkylene group used herein refers to a straight-chain or branched divalent hydrocarbon having 1 to 10 carbon atoms, such as methylene, ethylene, propylene, butylene, pentylene, and hexylene. It includes, but is not limited to, etc.

As used herein, the oxyalkylene group of C ₁ -C ₁₀ refers to a functional group in which at least one chain carbon is replaced with oxygen in a straight-chain or branched divalent hydrocarbon consisting of 1 to 10 carbon atoms, for example, oxyalkylene group. It includes, but is not limited to, methylene, oxyethylene, oxypropylene, oxybutylene, oxypentylene, oxyhexylene, etc.

The C ₁ -C ₁₀ alkyl group used herein refers to a straight-chain or branched monovalent hydrocarbon having 1 to 10 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl. , i-butyl, t-butyl, n-pentyl, n-hexyl, etc., but are not limited thereto.

In one embodiment of the present invention, the repeating unit represented by Formula 3 may be one where R ⁷ is hydrogen or a methyl group, R ⁸ is absent, and p is 1.

In one embodiment of the present invention, the repeating unit represented by Formula 4 is wherein R ⁹ is hydrogen or a methyl group, R ¹⁰ is an alkylene group of C ₁ -C ₁₀ , and R ¹¹ is an alkyl group of C ₁ -C ₁₀ , q may be 1. Specifically, the repeating unit represented by Formula 4 may be one in which R ⁹ is hydrogen or a methyl group, R ¹⁰ is a methylene group, R ¹¹ is an ethyl group, and q is 1.

The repeating unit represented by Formula 3 may be included in an amount of 5 to 50 mol% based on 100 mol% of the total repeating units constituting the alkali-soluble resin. When the repeating unit represented by Formula 3 is included within the mole percent range, the reliability of the heat resistance, chemical resistance, etc. of the cured network obtained from the alkali-soluble resin can be improved.

The repeating unit represented by Formula 4 may be included in an amount of 30 mol% or less based on 100 mol% of the total repeating units constituting the alkali-soluble resin. When the repeating unit represented by Formula 4 is included within the mole percent range, a heat curing reaction may proceed in the baking step to improve chemical resistance.

The first alkali-soluble resin may secure solubility in an alkaline developer by including a repeating unit containing a carboxyl group.

The carboxyl group-containing repeating unit may be introduced by an ethylenically unsaturated monomer having a carboxyl group. Specific examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; Examples include polymer mono(meth)acrylates having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate, and acrylic acid and methacrylic acid are preferred.

The carboxyl group-containing repeating unit may be included in an amount of 5 to 40 mol% based on 100 mol% of the total repeating units constituting the first alkali-soluble resin. When the carboxyl group-containing repeating unit is included within the above mole% range, the desired pattern can be formed cleanly within a set process time without leaving residues in the unexposed area during the process of forming the pattern through the exposure and development steps.

The first alkali-soluble resin may be a block copolymer in which the repeating units represented by Formulas 1, 3, and 4 and the carboxyl group-containing repeating units are respectively repeated regularly, or it may be a random copolymer in which these repeating units are randomly repeated.

In the present invention, the repeating unit or compound represented by a chemical formula includes isomers of the repeating unit or compound, and when there are isomers of the repeating unit or compound represented by each chemical formula, the repeating unit or compound represented by the chemical formula Compounds include their isomers.

In one embodiment of the present invention, the first alkali-soluble resin has a trialkoxysilyl group equivalent of 1.10 × 10 ^-3 mol/g or more, for example, 1.10 × 10 ^-3 mol/g to 2.00 × 10 ^-3 mol/g. It can be something to have. If the trialkoxysilyl group equivalent of the first alkali-soluble resin is less than 1.10 × 10 ^-3 mol/g, development adhesion, adhesion over time, and chemical resistance may be poor.

In one embodiment of the present invention, the alkali-soluble resin may further include an acrylate-based resin containing a repeating unit derived from an unsaturated acrylate monomer as a second alkali-soluble resin.

The second alkali-soluble resin may include a repeating unit containing a (meth)acrylate group at the end to improve photocurability. For example, the second alkali-soluble resin may include a repeating unit represented by the following formula (2).

[Formula 2]

In the above equation,

R ⁵ and R ⁶ are each independently hydrogen or a methyl group.

The repeating unit represented by Formula 2 may be included in an amount of 10 to 50 mol% based on 100 mol% of the total repeating units constituting the second alkali-soluble resin. When the repeating unit represented by Formula 2 is included within the mole% range, sufficient curing density is secured even when a low-temperature process is applied to promote photocuring in the exposure step and heat curing at a relatively low temperature, thereby ensuring heat resistance and chemical resistance. The reliability of the hardened structure can be improved.

By including the second alkali-soluble resin, the photocurability of the negative photosensitive resin composition according to the present invention can be improved. Additionally, the repeating unit includes a hydroxyl group, so adhesion to the substrate and developability can be further improved.

The second alkali-soluble resin may further include a carboxyl group-containing repeating unit to further improve developability and adhesion to the substrate. The carboxyl group-containing repeating unit may be introduced by an ethylenically unsaturated monomer having a carboxyl group. As the ethylenically unsaturated monomer having a carboxyl group, the same ones as those exemplified in the first alkali-soluble resin can be used.

The carboxyl group-containing repeating unit may be included in an amount of 10 to 30 mol% based on 100 mol% of the total repeating units constituting the second alkali-soluble resin. When the carboxyl group-containing repeating unit is contained within the above mole% range, the solubility of the alkali-soluble resin in the developer is adequate, so that only the unexposed portion can be dissolved without deteriorating adhesion in the development process without leaving any residue.

The second alkali-soluble resin may further include an aromatic ring-containing repeating unit as an additional repeating unit to improve reliability such as heat resistance and chemical resistance.

The aromatic ring-containing repeating units include, for example, vinyltoluene, p-isopropenyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, and o-vinylbenzylmethyl ether. , can be derived from aromatic vinyl compounds such as m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether. there is.

In addition to the repeating units described above, the second alkali-soluble resin may further include repeating units formed of other monomers known in the art.

The monomer forming the repeating unit that can be further added as described above is not particularly limited as long as it is a monomer used in the relevant field. For example, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenyl. N-substituted maleimide compounds such as maleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, and N-p-methoxyphenylmaleimide; Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-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)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. unsaturated oxetane compounds; Unsaturated oxirane compounds such as methylglycidyl (meth)acrylate; (meth)acrylate substituted with a cycloalkane or dicycloalkane ring having 4 to 16 carbon atoms; Unsaturated alicyclic compounds such as norbornene may be included, but are not limited thereto. These can be used alone or in combination of two or more types.

For example, the second alkali-soluble resin may include a structure represented by Structural Formula 1 below.

[Structural Formula 1]

In the above formula, R ⁵ and R ⁶ are as defined above, and R ¹² to R ¹⁵ are each independently hydrogen or a methyl group. a, b, c and d represent the molar ratio of each unit, and a may be 15 to 65 mol%, b may be 1 to 15 mol%, c may be 10 to 40 mol%, and d may be 15 to 65 mol%.

In the present invention, each repeating unit shown in Structural Formula 1 should not be construed as limited as shown in each structural formula, and the sub-repeating unit in parentheses may be freely located at any position in the chain within a set mole% range. That is, each parenthesis in Structural Formula 1 is expressed as one block to express mole%, but each sub-repeating unit can be located as a block or separately within the corresponding resin without limitation.

The acid value of the alkali-soluble resin is preferably in the range of 20 to 200 (KOH mg/g), for example, 50 to 100 (KOH mg/g). If the acid value is within the above range, excellent developability and stability over time can be achieved.

In addition, the weight average molecular weight in terms of polystyrene (hereinafter simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; using tetrahydrofuran as an elution solvent) is 3,000 to 100,000, preferably 5,000 to 50,000. Alkali-soluble resins are preferred. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film rate is high, the solubility of non-exposed parts in the developer is excellent, and resolution tends to be improved, which is preferable.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the alkali-soluble resin is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. A molecular weight distribution of 1.5 to 6.0 is preferable because developability is excellent.

The alkali-soluble resin may be included in an amount of 10 to 90% by weight, preferably 30 to 70% by weight, based on 100% by weight of the total solid content in the negative photosensitive resin composition. When the alkali-soluble resin is included in the above range, the solubility in the developing solution is sufficient to improve developability, and a photocurable film with excellent mechanical properties can be formed.

photopolymerizability Compound (B)

In one embodiment of the present invention, the photopolymerizable compound (B) increases the crosslinking density during the manufacturing process and serves to strengthen the mechanical properties of the photocurable film.

The photopolymerizable compound is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and includes a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, or a trifunctional or more multifunctional photopolymerizable compound.

Specific examples of the monofunctional photopolymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Examples include vinylpyrrolidone, and commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku), or Viscot 158 (Osaka Yukigagaku High School).

Specific examples of the bifunctional photopolymerizable compound include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate. ester, bis(acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate. Commercially available products include Aronix M-210, M-1100, and M-1200 (Toagosei). ), KAYARAD HDDA (Nippon Kayaku), Biscot 260 (Osaka Yuki Kagaku High School), AH-600, AT-600 or UA-306H (Kyoeisha Kagaku).

Specific examples of the trifunctional or more multifunctional photopolymerizable compound include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, and propoxylated trimethylolpropane tri(meth)acrylate. , pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol Hexa(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, etc. Commercially available products include NK ESTER ATM-4E (new Nakamura), NK ESTER A-DPH-12E (Shin Nakamura), A-9570 (Shin Nakamura), Aronics M-309, M-520 (Toagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kaya) Ku), etc.

The photopolymerizable compounds exemplified above can be used alone or in combination of two or more types.

The content of the photopolymerizable compound is not particularly limited, but for example, it is preferably contained in 5 to 60% by weight, and 10 to 50% by weight based on 100% by weight of the total solid content in the negative photosensitive resin composition. It is more desirable. When the photopolymerizable compound is included in the above content range, excellent durability can be achieved and developability can be improved.

light curing initiator (C)

In one embodiment of the present invention, the photopolymerization initiator (C) can be used without particular restrictions as long as it can polymerize the photopolymerizable compound (B). In particular, the photopolymerization initiator (C) is acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, biimidazole-based compounds, oxime-based compounds and It is preferable to use at least one compound selected from the group consisting of thioxanthone-based compounds.

Specific examples of the acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2-hydroxy Roxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1 -one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc.

Examples of the benzophenone-based compounds include benzophenone, 0-benzoylmethylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra ( tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

Specific examples of the triazine-based compounds 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-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2- yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl )-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc.

Specific examples of the biimidazole-based compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole Dazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl)-4 , 4',5,5'-tetraphenyl-1,2'-biimidazole or a biimidazole compound in which the phenyl group at the 4,4',5,5' position is substituted by a carboalkoxy group, etc. there is. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4' ,5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole are preferred. It is used.

Specific examples of the oxime-based compounds include o-ethoxycarbonyl-α-oxymino-1-phenylpropan-1-one, 1,2-octanedione, -1-(4-phenylthio)phenyl, -2- (o-benzoyloxime), ethanone, -1-(9-ethyl)-6-(2-methylbenzoyl)carbazol-3-yl, 1-(o-acetyloxime), etc., and commercially available products include CGI-124 (Ciba Geigi), CGI-224 (Ciba Geigi), Igacure OXE-01 (BASF), Igacure OXE-02 (BASF), N-1919 (Adeka), NCI-831 ( Adekasa), etc.

Examples of the thioxanthone-based compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. There is.

The photopolymerization initiator may be included in an amount of 0.1 to 40 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin and the photopolymerizable compound. When the photopolymerization initiator is included within the above range, the negative photosensitive resin composition becomes highly sensitive and the exposure time is shortened, thereby improving productivity and maintaining high resolution.

Solvent (D)

In one embodiment of the present invention, the solvent (D) is not particularly limited, and any solvent commonly used in the technical field may be used without limitation.

Specific examples of the solvent 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 methyl ethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve 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; 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; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic esters, such as γ-butyrolactone, etc. are mentioned.

In terms of applicability and drying properties, organic solvents having a boiling point of 100°C to 200°C are preferred among the above solvents, alkylene glycol alkyl ether acetates, ketones, and esters are more preferred, and propylene glycol monomethyl ether acetate and propylene glycol are more preferred. Monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate are more preferable. These solvents can be used individually or in mixture of two or more types.

The solvent may be included in an amount of 40 to 95% by weight, preferably 45 to 85% by weight, based on 100% by weight of the total negative photosensitive resin composition. When the solvent content satisfies the above range, the applicability tends to be good when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes called a die coater), or inkjet. It is desirable because it exists.

Additive (E)

In addition to the above components, the negative photosensitive resin composition according to an embodiment of the present invention contains photopolymerization initiation aids, other polymer compounds, curing agents, surfactants, adhesion promoters, and antioxidants as needed by those skilled in the art, within the range that does not impair the purpose of the present invention. , additives such as ultraviolet absorbers and anti-agglomerates can be used together.

The photopolymerization initiation aid can improve productivity by further increasing the sensitivity of the negative photosensitive resin composition of the present invention.

As the photopolymerization initiation aid, for example, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and organic sulfur compounds having a thiol group may be preferably used.

Specifically, the amine compounds include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethyl. 2-ethylhexyl aminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone), 4,4'-bis(di Aromatic amine compounds such as ethylamino)benzophenone can be used, and it is especially preferable to use aromatic amine compounds.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, and dimethoxyphenylthioacetic acid. Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

Specific examples of the organic sulfur compounds having the thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris(3-mercaptobutyloxyethyl). -1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercapto) butyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. You can.

When the photopolymerization initiation aid is further used, the photopolymerization initiation aid may be included in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin and the photopolymerizable compound. When the amount of the photopolymerization initiation aid used is within the above range, the sensitivity of the negative photosensitive resin composition can be further increased, and the productivity of the photocurable film formed using the composition can be improved.

Specific examples of the other polymer compounds include thermosetting resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. I can hear it.

The curing agent is used to improve deep hardening and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

Specific examples of the epoxy compound in the curing agent include bisphenol A-based epoxy resin, hydrogenated bisphenol A-based epoxy resin, bisphenol F-based epoxy resin, hydrogenated bisphenol F-based epoxy resin, novolak-type epoxy resin, other aromatic epoxy resins, and cycloaliphatic epoxy. Resin, glycidyl ester-based resin, glycidylamine-based resin, or brominated derivatives of these epoxy resins, aliphatic, alicyclic, or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxide, isoprene (Co)polymer epoxide, glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, etc. are mentioned.

Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The curing agents exemplified above can be used individually or in combination of two or more types.

The curing agent may be used in combination with a curing auxiliary compound that can cause ring-opening polymerization of the epoxy group of an epoxy compound and the oxetane skeleton of an oxetane compound. The curing auxiliary compounds include, for example, polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, and acid generators. The above polyhydric carboxylic acid anhydride can be used as a commercially available epoxy resin curing agent. Specific examples of the above epoxy resin hardener include brand name (Adeka Hadona EH-700) (manufactured by Adeka Kogyo Co., Ltd.), brand name (Rika Siddo HH) (manufactured by Shin Nippon Ewha Co., Ltd.), brand name (MH-700) (manufactured by Shin Nippon Ewha Co., Ltd.) (manufactured by Japan Ewha Co., Ltd.), etc.

The surfactant can be used to further improve the film formation of the photosensitive resin composition, and a fluorine-based surfactant or a silicone-based surfactant can be preferably used.

The silicone-based surfactants are, for example, commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, SH8400 from Dow Corning Toray Silicone, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, and TSF-4460 from GE Toshiba Silicone. , TSF-4452, etc. Examples of the fluorine-based surfactant include commercially available products such as Megapeace F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink Chemicals. The surfactants exemplified above can be used individually or in combination of two or more types.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 3-gly Sidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltri Methoxysilane, 8-methacryloxyoctyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate propyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, etc. The adhesion promoters exemplified above can be used individually or in combination of two or more.

Specific examples of the antioxidant include 4,4'-butylidene bis[6-tert-butyl-3-methylphenol], 2,2'-thiobis(4-methyl-6-t-butylphenol), 2 , 6-di-t-butyl-4-methylphenol, etc. are mentioned.

Specific examples of the ultraviolet absorber include 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, etc.

Specific examples of the anti-agglomeration agent include sodium polyacrylate.

One embodiment of the present invention relates to a photocurable film formed using the negative photosensitive resin composition described above.

The photocurable film may be used as an array planarization film, a protective film, an insulating film, etc., and may also be used as a photoresist pattern, a black matrix pattern, a column spacer pattern, a black column spacer pattern, etc., but is not limited thereto, and is particularly used as an insulating film or It is very suitable as a photoresist pattern.

The photocurable film according to one embodiment of the present invention can be manufactured by applying the above-described negative photosensitive resin composition on a substrate and exposing it to light. If necessary, development can be further performed and patterned.

First, the negative photosensitive resin composition of the present invention is applied to a substrate and then heated and dried to remove volatile components such as solvents to obtain a smooth coating film.

Application methods include, for example, inkjet printing, spin coating, flexible coating, roll coating, slit and spin coating, or slit coating.

After application, it is heated and dried (pre-bake) or dried under reduced pressure and then heated to volatilize volatile components such as solvents. At this time, the heating temperature is a relatively low temperature of 70 to 150°C. The coating film thickness after heat drying is usually about 1 to 8 μm.

The coating film obtained in this way is irradiated with ultraviolet rays. In the case of patterning, ultraviolet rays are irradiated through a mask to form the desired pattern. At this time, it is desirable to use a device such as a mask aligner or stepper so that parallel light is uniformly irradiated to the entire exposure area and the mask and the substrate are accurately aligned. When ultraviolet rays are irradiated, curing occurs in the area irradiated with ultraviolet rays.

As the ultraviolet rays, g-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm), etc. can be used. The irradiation amount of ultraviolet rays can be appropriately selected depending on needs.

In the case of patterning, a process of developing the cured coating film by contacting it with a developing solution to dissolve the unexposed portion may be further performed.

The development method may be any of a liquid addition method, a dipping method, or a spray method. Additionally, the substrate may be tilted at an arbitrary angle during development.

After development, it is washed with water and post-baked at a relatively low temperature of 70 to 100°C for 10 to 60 minutes.

One embodiment of the present invention relates to an image display device including the photocurable film described above. The image display device may include, but is not limited to, a liquid crystal display, OLED, and flexible display, and may include all applicable image display devices known in the art.

Hereinafter, the present invention will be described in more detail through examples, comparative examples, and experimental examples. These examples, comparative examples, and experimental examples are only for illustrating the present invention, and it is obvious to those skilled in the art that the scope of the present invention is not limited thereto.

Manufacturing example 1: Preparation of first alkali-soluble resin (A-1)

300 g of methylethyl diethylene glycol was added to a 1 L flask purged with nitrogen, followed by a mixture of the following formulas (a) and (b) (molar ratio: 50:50), 61.7 g (0.28 mol), (3-ethyl-3-oxetanyl) 27.6 g (0.15 mol) of methyl methacrylate and 49.1 g (0.57 mol) of methacrylic acid were added and dissolved by heating to 80°C. A solution of 12.7 g (0.05 mol) of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 100 g of methyl ethyl diethylene glycol was added to the flask over 3 hours using a separate dropping funnel. Then, it was heated to 80°C and stirred for 6 hours.

[Formula a]

[Formula b]

Next, the atmosphere in the flask was changed from nitrogen to air, and 91.9 g [0.30 mol (53 mol% relative to methacrylic acid used in this reaction)] of 8-glycidoxyoctyltrimethoxysilane] was added into the flask and incubated at 100°C. The reaction was continued for 6 hours, and the first alkali-soluble resin (A-1) with a solid acid value of 76 mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 14,500, and the molecular weight distribution (Mw/Mn) was 2.1.

Manufacturing example 2: Preparation of first alkali-soluble resin (A-2)

A mixture of formula a and formula b (molar ratio 50:50) 37.4 g (0.17 mol), (3-ethyl-3-oxetanyl)methyl methacrylate 27.6 g (0.15 mol), and 58.5 g (0.15 mol) methacrylic acid ( Preparation Example 1 and The same procedure was performed to obtain a first alkali-soluble resin (A-2) with a solid content of 34.4% by mass and an acid value of 70 mg-KOH/g (converted to solid content). The weight average molecular weight in terms of polystyrene measured by GPC was 7,400, and the molecular weight distribution was 1.98.

Manufacturing example 3: Preparation of first alkali-soluble resin (A-3)

A mixture of formula a and formula b (molar ratio 50:50) 15.4 g (0.07 mol), (3-ethyl-3-oxetanyl)methyl methacrylate 25.8 g (0.14 mol), and 68.0 g methacrylic acid ( Preparation Example 1 and The same procedure was performed to obtain the first alkali-soluble resin (A-3) with a solid content of 34.4 mass% and an acid value of 72 mg-KOH/g (converted to solid content). The weight average molecular weight in terms of polystyrene measured by GPC was 7,400, and the molecular weight distribution was 1.98.

Manufacturing example 4: Preparation of first alkali-soluble resin (A-4)

After reacting 70.5 g (0.32 mol) of the mixture of Formula a and Formula b (molar ratio 50:50) and 49.1 g (0.68 mol) of methacrylic acid, 122.6 g of 8-glycidoxyoctyltrimethoxysilane [0.40 mol (59 mol% relative to methacrylic acid used in this reaction)] was carried out in the same manner as Preparation Example 1, except that the reaction was carried out to produce a first alkali-soluble resin (A-4) having a solid acid value of 71 mgKOH/g. ) was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 14,500, and the molecular weight distribution (Mw/Mn) was 2.1.

Manufacturing example 5: Preparation of first alkali-soluble resin (A-5)

A mixture of formula a and formula b (molar ratio 50:50) 99.1 g (0.45 mol), 40.5 g (0.22 mol) (3-ethyl-3-oxetanyl)methyl methacrylate, and 28.4 g (0.22 mol) methacrylic acid ( Preparation Example 1 and The same procedure was performed to obtain a first alkali-soluble resin (A-5) having a solid acid value of 76 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 14,500, and the molecular weight distribution (Mw/Mn) was 2.1.

Manufacturing example 6: Preparation of first alkali-soluble resin (A-6)

300 g of methylethyl diethylene glycol was added to a 1 L flask purged with nitrogen, followed by 50.7 g (0.23 mol) of a mixture of Formula a and Formula b (molar ratio 50:50), (3-ethyl-3-oxetanyl)methyl 27.6 g (0.15 mol) of methacrylate, 99.3 g (0.40 mol) of 3-methacryloxypropyltrimethoxysilane, and 18.9 g (0.22 mol) of methacrylic acid were added and dissolved by heating to 80°C. A solution of 12.7 g (0.05 mol) of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 100 g of methyl ethyl diethylene glycol was added to the flask over 3 hours using a separate dropping funnel. Then, the reaction was carried out while heating to 80°C and stirring for 6 hours to obtain the first alkali-soluble resin (A-6) with a solid content of 34.4 mass% and an acid value of 71 mg-KOH/g (converted to solid content). The weight average molecular weight in terms of polystyrene measured by GPC was 7,400, and the molecular weight distribution was 1.98.

Manufacturing example 7: Preparation of first alkali-soluble resin (A-7)

A mixture of formula a and formula b (molar ratio 50:50) 44.1 g (0.20 mol), (3-ethyl-3-oxetanyl)methyl methacrylate 27.6 g (0.15 mol), and 60.0 g methacrylic acid. Preparation Example 1 above, except that after reacting (0.65 mol), 94.5 g of 3-glycidoxypropyltrimethoxysilane [0.40 mol (62 mol% based on methacrylic acid used in this reaction)] was reacted. By performing the same procedure as above, a first alkali-soluble resin (A-7) having a solid acid value of 72 mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 14,500, and the molecular weight distribution (Mw/Mn) was 2.1.

Manufacturing example 8: Preparation of first alkali-soluble resin (A-8)

300 g of methylethyl diethylene glycol was added to a 1L flask purged with nitrogen, followed by 132.2 g (0.60 mol) of a mixture of Formula a and Formula b (molar ratio 50:50), (3-ethyl-3-oxetanyl)methyl 55.3 g (0.30 mol) of methacrylate and 8.6 g (0.10 mol) of methacrylic acid were added and dissolved by heating to 80°C. A solution of 12.7 g (0.05 mol) of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 100 g of methyl ethyl diethylene glycol was added to the flask over 3 hours using a separate dropping funnel. Afterwards, the reaction was carried out while heating to 80°C and stirring for 6 hours to obtain the first alkali-soluble resin (A-8) with a solid content of 37.2 mass% and an acid value of 58 mg-KOH/g (converted to solid content). The weight average molecular weight in terms of polystyrene measured by GPC was 8,500, and the molecular weight distribution (Mw/Mn) was 1.75.

Manufacturing example 9: Preparation of second alkali-soluble resin (A-9)

Put 300 g of propylene glycol monomethyl ether acetate in a 1 L flask purged with nitrogen, add 24.5 g (0.34 mol) of acrylic acid, 4.7 g (0.05 mol) of norbornene, and 72.1 g (0.61 mol) of vinyl toluene, then heat to 100°C. After heating and dissolving, a solution of 12.7 g (0.05 mol) of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 100 g of propylene glycol monomethyl ether acetate was added to 3 mL using a separate dropping funnel. After being added into the flask over time, it was heated to 100°C and stirred for 5 hours.

Next, 28.4 g [0.20 mol (59 mol% relative to the acrylic acid used in this reaction)] of glycidyl methacrylate was added into the flask, and the reaction was continued at 100°C for 6 hours to obtain a solid content of 31.5 mass% and an acid value of 76 mg-KOH. /g (solid content conversion) of the second alkali-soluble resin (A-9) was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 19,500, and the molecular weight distribution (Mw/Mn) was 2.30.

Example 1 to 4 and Comparative example 1 to 7: Negative type Preparation of photosensitive resin composition

A negative photosensitive resin composition was prepared by mixing each component in the composition shown in Table 1 below (unit: weight %).

Example Comparative example One 2 3 4 One 2 3 4 5 6 7 First alkali soluble resin A-1 6.70 - - - - - - - - - - A-2 - 6.70 - - - - - - - - - A-3 - - 6.70 - - - - - - - - A-4 - - - 6.70 - - - - - - - A-5 - - - - - - 6.70 - - - - A-6 - - - - - - - 6.70 - - - A-7 - - - - - - - - 6.70 - - A-8 - - - - - 6.70 - - - 6.13 6.13 Secondary alkali soluble resin (A-9) 1.68 1.68 1.68 1.68 8.38 1.68 1.68 1.68 1.68 1.53 1.53 Photopolymerizable compound (B-1) 8.38 8.38 8.38 8.38 8.38 8.38 8.38 8.38 8.38 7.67 7.67 photopolymerization initiator C-1 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.46 0.46 C-2 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.31 0.31 C-3 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 additive
(E) E-1 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.06 0.06 E-2 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.23 0.23 E-3 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 E-4 - - - - - - - - - 1.53 - E-5 - - - - - - - - - - 1.53 solvent
(D) D-1 24.60 24.60 24.60 24.60 24.60 24.60 24.60 24.60 24.60 24.60 24.60 D-2 57.39 57.39 57.39 57.39 57.39 57.39 57.39 57.39 57.39 57.39 57.39

A-1: Alkali-soluble resin of Preparation Example 1 (trialkoxysilyl group equivalent weight 1.30 × 10 ^-3 mol/g)

A-2: Alkali-soluble resin of Preparation Example 2 (trialkoxysilyl group equivalent weight 1.63 × 10 ^-3 mol/g)

A-3: Alkali-soluble resin of Preparation Example 3 (trialkoxysilyl group equivalent weight 1.91 × 10 ^-3 mol/g)

A-4: Alkali-soluble resin of Preparation Example 4 (trialkoxysilyl group equivalent weight 1.59 × 10 ^-3 mol/g)

A-5: Alkali-soluble resin of Preparation Example 5 (trialkoxysilyl group equivalent weight 0.50 × 10 ^-3 mol/g)

A-6: Alkali-soluble resin of Preparation Example 6 (trialkoxysilyl group equivalent weight 2.03 × 10 ^-3 mol/g)

A-7: Alkali-soluble resin of Preparation Example 7 (trialkoxysilyl group equivalent weight 1.80 × 10 ^-3 mol/g)

A-8: Alkali-soluble resin of Preparation Example 8 (without trialkoxysilyl group)

A-9: Alkali-soluble resin of Preparation Example 9

B-1: Dipentaerythritol penta(meth)acrylate (A-9570, manufactured by Shinnakamura Co., Ltd.)

C-1: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (B-CIM: manufactured by Hodogaya Chemical Industry Co., Ltd.)

C-2: Compound represented by the following formula 5:

C-3: Oxime ester-based compound represented by the following formula (6)

[Formula 5] [Formula 6]

E-1: 4,4'-butylidene bis[6-tert-butyl-3-methylphenol] (BBM-S: manufactured by Sumitomo Fine Chemicals)

E-2: Pentaerythritol tetrakis (3-mercaptopropionate) (PEMP: manufactured by SC Chemicals Co., Ltd.)

E-3: SH8400 (manufactured by GE Toshiba-Toray)

E-4: 8-methacryloxyoctyltrimethoxysilane (KBM-5803: manufactured by Shin-Etsu)

E-5: 8-glycidoxyoctyltrimethoxysilane (KBM-4803: manufactured by Shin-Etsu)

D-1: Diethylene glycol methyl ethyl ether

D-2: Propylene glycol monomethyl ether acetate

Experiment example One

The litho performance, development adhesion, adhesion over time, and chemical resistance of the negative photosensitive resin compositions prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 2 below.

(One) Riso Performance

A 2-inch by 2-inch glass substrate (Eagle 2000; manufactured by Corning) was sequentially washed with neutral detergent, water, and alcohol and then dried. The negative photosensitive resin compositions prepared in Examples and Comparative Examples were spin-coated on this glass substrate and then prebaked at 90°C for 125 seconds using a hot plate. The prebaked substrate was cooled to room temperature and then irradiated with light at an exposure dose of 60 mJ/cm2 (based on 365 nm) using an exposure machine (MA6 from MICOSUSS) with a gap of 50 μm between the quartz glass photomask and the prebaked substrate. At this time, a photomask was used that had a square pattern with a side of 10 ㎛ and the patterns with mutual spacing of 100 ㎛ formed on the same plane. After light irradiation, the film was developed by immersing it in a 2.38% tetraammonium hydroxide aqueous solution at 25°C for 60 seconds, washed and dried, and then post-baked at 90°C for 120 minutes using a clean oven. The obtained pattern height was 2.0 μm.

① Pattern bottom CD size

The hole pattern obtained above was observed with a three-dimensional shape measuring device (SIS-2000 system; manufactured by SNU Precision), and a point that was 5% of the total height from the bottom surface of the hole pattern was defined as the Bottom CD, and measured in the horizontal direction. The average value of the measured values in the vertical direction was defined as the line width of the pattern (unit: ㎛).

② CD-bias of the pattern

The difference between the bottom line width value of the hole pattern obtained above and the mask size was calculated using CD-bias (unit: ㎛). CD-bias is better as it approaches 0. (-) means that the bottom CD value of the hole pattern is smaller than the mask size, and (+) means that the bottom CD value of the hole pattern is larger than the mask size. .

③ Phenomenon remnants

The hole pattern obtained above was observed with a scanning electron microscope (Hitachi, S-4700) to check whether any residual film remained after development, and evaluated according to the following evaluation criteria. At this time, the residual film refers to a residual film that remains within the hole pattern and blocks the bottom, thereby reducing the line width.

<Evaluation criteria>

○: No residual film

△: Slight residual film occurs

×: The residual film is very severe.

(2) Development adhesion

The negative photosensitive resin compositions prepared in the above Examples and Comparative Examples were spin-coated on a 2-inch by 2-inch glass substrate on which silicon nitride was deposited to a thickness of 1200 Å, and then coated at 70°C using a hot plate. Prebaked for 90 seconds. The prebaked substrate was cooled to room temperature and then irradiated with light at an exposure dose of 30 mJ/cm2 (based on 365 nm) using an exposure machine (MA6 from MICOSUSS) with a gap of 50 μm between the quartz glass photomask and the prebaked substrate. At this time, a photomask in which 1000 dot patterns (octagons) with line widths (sizes) ranging from 5㎛ to 20㎛ and spaced at 100㎛ were formed on the same plane was used.

After light irradiation, the film is developed by immersing it in a 2.38% tetraammonium hydroxide aqueous solution at 25°C for 90 seconds, and after washing with water and drying, the pattern formed with a pattern height of 3 ㎛ by a photomask remains 100% without any defects. The actual size of the pattern was measured using SNU Precision's SIS-2000, a three-dimensional shape measuring device, to measure the line width. The value of the pattern line width was defined as the value of Bottom CD, which is 5% of the total height from the bottom of the pattern. It was determined that the smaller the minimum pattern size remaining without defects, the better the developing adhesion.

(3) Adhesion over time

After the negative photosensitive resin compositions prepared in the examples and comparative examples were left at room temperature for 72 hours, a pattern was formed in the same manner as the development adhesion evaluation method, and adhesion over time was evaluated in the same manner.

(4) Chemical resistance

The negative photosensitive resin compositions prepared in the examples and comparative examples were spin-coated on a 2-inch by 2-inch glass substrate on which silicon nitride was deposited to a thickness of 1200 Å, and then applied at 90°C for 125 seconds using a hot plate. Heated. After cooling the prebaked substrate to room temperature. Light was irradiated to the entire surface of the coating film at an exposure dose of 60 mJ/cm2 (based on 365 nm) using an exposure machine (MA6, manufactured by MICOSUSS). After light irradiation, the film was developed by immersing it in a 2.38% tetraammonium hydroxide aqueous solution at 25°C for 60 seconds, washed with water, dried in an oven, and then post-baked at 90°C for 120 minutes using a clean oven.

The produced film was immersed in positive resist stripper (prepared by dissolving 60 g of 2-amino-1-propanol in 60 g of N-methyl-2-pyrrolidone and 80 g of diethylene glycol methylbutyl ether) and heated to 45°C for 2 hours. After treatment for a few minutes, the coating was cut with a cutter according to ASTM D-3359-08 standard test conditions, and then adhesion was confirmed by attaching and removing tape to the surface. The degree of peeling of the coating film was measured in a cutting/tape test after treatment with the stripping solution, and chemical resistance was evaluated according to the following evaluation criteria based on a standard test method.

<Evaluation criteria>

5B: 0% peeling

4B: Delamination greater than 0% but less than 5%

3B: Delamination 5% or more but less than 15%

2B: Delamination 15% or more but less than 35%

1B: Delamination 35% or more but less than 65%

0B: Delamination 65% or more

division Example Comparative example One 2 3 4 One 2 3 4 5 6 7 Riso performance CD size 8.7 8.2 6.9 7.1 11.2 6.3 7.0 7.3 7.5 7.9 8.1 CD-Bias -1.3 -1.8 -3.1 -2.9 +1.2 -3.7 -3.0 -2.7 -2.5 -2.1 -1.9 phenomenon ○ ○ △ ○ ○ ○ ○ ○ ○ × × Development adhesion 18㎛
OK 16㎛
OK 14㎛
OK 14㎛
OK 20㎛
peeling 20㎛
peeling 20㎛
peeling 19㎛
OK 17㎛
OK 14㎛
OK 15㎛
OK Adhesion over time 18㎛
OK 16㎛
OK 14㎛
OK 14㎛
OK 20㎛
peeling 20㎛
peeling 20㎛
peeling 20㎛
peeling 20㎛
peeling 20㎛
peeling 20㎛
peeling chemical resistance 5B 5B 4B 5B 0B 2B 2B 4B 4B 1B 1B

As shown in Table 2, the negative photosensitive resin compositions of Examples 1 to 4 according to the present invention maintain litho performance, have good developing adhesion without the addition of a separate adhesion enhancer, have excellent chemical resistance, and have excellent chemical resistance over time. It was confirmed that there was no decrease in adhesion.

On the other hand, Comparative Example 1 containing only the second alkali-soluble resin and not the first alkali-soluble resin, Comparative Example 2 containing the first alkali-soluble resin not containing a trialkoxysilyl group, and the equivalent weight of the trialkoxysilyl group is 1.10 × In the negative photosensitive resin composition of Comparative Example 3 containing less than 10 ^-3 mol/g of the first alkali-soluble resin, peeling occurred even at 20㎛, the maximum line width of the photomask used, and development adhesion and adhesion over time were greatly reduced, and chemical resistance was significantly reduced. It was also confirmed that it was defective.

In addition, the negative photosensitive resin compositions of Comparative Examples 4 and 5 containing the first alkali-soluble resin with n of less than 8 showed good development adhesion but poor adhesion over time. This appears to be because the hydrocarbon group to which the trialkoxysilyl group is bonded is short, forming a cured network, and the trialkoxysilyl group gets caught up inside the cured network and is not arranged at the interface with the necessary lower film.

In addition, the negative photosensitive resin compositions of Comparative Examples 6 and 7, which contain a first alkali-soluble resin without a trialkoxysilyl group instead of the first alkali-soluble resin containing a repeating unit represented by Formula 1 and a separate adhesion promoter. It was confirmed that, although the development adhesion was good, not only was the adhesion over time poor, but also a development residual film was generated and chemical resistance was poor.

As the specific parts of the present invention have been described in detail above, it is clear to those skilled in the art that these specific techniques are merely preferred embodiments and do not limit the scope of the present invention. do. Anyone skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above contents.

Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (9)

A negative photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
A negative photosensitive resin composition wherein the alkali-soluble resin includes a first alkali-soluble resin containing a repeating unit represented by the following formula (1):
[Formula 1]

In the above equation,
R ¹ is hydrogen or a methyl group,
R ² to R ⁴ are each independently an alkyl group of C ₁ -C ₄ ,
n is an integer from 8 to 20. The negative photosensitive resin composition according to claim 1, wherein in Formula 1, R ¹ is hydrogen or a methyl group, R ² to R ⁴ are methyl groups, and n is 8. The negative photosensitive resin composition according to claim 1, wherein the first alkali-soluble resin has a trialkoxysilyl group equivalent of 1.10 × 10 ^-3 mol/g or more. The negative photosensitive resin composition according to claim 1, wherein the first alkali-soluble resin further comprises a repeating unit represented by the following formula (3):
[Formula 3]

In the above equation,
R ⁷ is hydrogen or a methyl group,
R ⁸ is an alkylene group of C ₁ -C ₁₀ or an oxyalkylene group of C ₁ -C ₁₀ or does not exist,
p is 0 or 1. The negative photosensitive resin composition according to claim 1, wherein the first alkali-soluble resin further comprises a repeating unit represented by the following formula (4):
[Formula 4]

In the above equation,
R ⁹ is hydrogen or a methyl group,
R ¹⁰ is an alkylene group of C ₁ -C ₁₀ or an oxyalkylene group of C ₁ -C ₁₀ or does not exist,
R ¹¹ is hydrogen or an alkyl group of C ₁ -C ₁₀ ,
q is 0 or 1. The negative photosensitive resin composition of claim 1, wherein the alkali-soluble resin further comprises a second alkali-soluble resin comprising a repeating unit represented by the following formula (2):
[Formula 2]

In the above equation,
R ⁵ and R ⁶ are each independently hydrogen or a methyl group. A photocurable film formed from the negative photosensitive resin composition of any one of claims 1 to 6. The photocurable film of claim 7, wherein the photocurable film is selected from the group consisting of an array planarization film, a protective film, an insulating film, a photoresist pattern, a black matrix pattern, a column spacer pattern, and a black column spacer pattern. An image display device comprising the photocurable film of claim 7.