KR102015054B1 - Negative-type photosensitive resin comopsition - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, more specifically, an alkali-soluble first resin comprising a repeating unit having a specific structure; Alkali-soluble second resin comprising a repeating unit having a specific structure; Polymerizable compounds; Photopolymerization initiator; And a solvent, the present invention relates to a negative photosensitive resin composition capable of forming a pattern having excellent pattern formation capability in a photolithography process and having excellent mechanical properties, durability, and adhesion to a lower substrate.

Description

Negative photosensitive resin composition {NEGATIVE-TYPE PHOTOSENSITIVE RESIN COMOPSITION}

The present invention relates to a negative photosensitive resin composition, and more particularly, to a negative photosensitive resin composition capable of forming a pattern having excellent pattern forming ability and excellent durability.

In the field of display, the photosensitive resin composition is used to form various photocuring patterns such as photoresist, insulating film, protective film, black matrix, column spacer and the like. Specifically, the photosensitive resin composition is selectively exposed and developed by a photolithography process to form a desired photocuring pattern. In this process, the photosensitive resin having high sensitivity is used to improve the yield of the process and to improve the physical properties of the application target. A composition is required.

The pattern formation of the photosensitive resin composition is based on photolithography, that is, the polarity change and crosslinking reaction of the polymer caused by the photoreaction. In particular, the change characteristic of solubility to solvents, such as aqueous alkali solution after exposure, is used.

Pattern formation by the photosensitive resin composition is classified into a positive type and a negative type according to the solubility to the development of the photosensitive part. The positive type photoresist is a method in which the exposed part is dissolved by the developer, and the negative type photoresist is a method in which the exposed part is not dissolved in the developer and the unexposed part is dissolved to form a pattern, and the positive type and the negative type are used. Binder resins, crosslinking agents, etc. are mutually different.

Recently, the use of a touch screen with a touch panel has exploded, and recently, a flexible touch screen has attracted much attention. Accordingly, the flexible characteristics of materials such as various substrates used in the touch screen should be provided. Accordingly, the materials that can be used are also limited to the flexible polymer materials, and the manufacturing process is also required to be performed under milder conditions. have.

Accordingly, the curing conditions of the photosensitive resin composition also require the need for low temperature curing in conventional high temperature curing, but low temperature curing has a problem of lowering reactivity and lowering durability of the formed pattern.

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 using a cyclohexenyl acrylate monomer. The conditions do not exhibit the required durability.

Korean Patent Registration No. 10-1302508

An object of the present invention is to provide a negative photosensitive resin composition which is excellent in mechanical properties of the formed pattern and excellent in durability, such as chemical resistance and peeling resistance.

Moreover, an object of this invention is to provide the negative photosensitive resin composition which has the outstanding pattern formation ability in a photolithography process.

Moreover, an object of this invention is to provide the negative photosensitive resin composition excellent in image development adhesiveness with respect to the lower substrate of the formed pattern.

Moreover, an object of this invention is to provide the photocuring pattern formed from the said photosensitive resin composition.

1. Alkali-soluble first resin containing a repeating unit represented by following formula (1);

An alkali-soluble second resin including a repeating unit represented by Formula 2 below;

Polymerizable compounds;

Photopolymerization initiator; And

A negative photosensitive resin composition comprising a solvent:

[Formula 1]

(Wherein R ₁ , R _{2 ,} R ₃ and R ₄ are each independently hydrogen or a methyl group,

R ₅ is a structure derived from a monomer represented by the following formula (1), R ₉ is hydrogen or a methyl group,

R ₆ is a structure derived from a monomer selected from the group consisting of the following formulas (2) to (4),

R ₇ is a structure derived from a monomer selected from the group consisting of the following formulas (5) to (7), X ₁ is an alkylene group having 1 to 12 carbon atoms, X ₂ is an alkyl group having 1 to 6 carbon atoms,

R ₈ is a group consisting of (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2- (meth) acryloyloxyethyl succinate Is a structure derived from a monomer selected from

a = 5 to 50 mol%, b = 20 to 60 mol%, c = 10 to 50 mol%, d = 5 to 30 mol%)

 [Formula 2]

(Wherein R ₁₀ , R _11, and R ₁₂ are each independently hydrogen or a methyl group,

R ₁₃ is a structure derived from a monomer represented by the following formula (8), R ₁₆ is hydrogen or a methyl group,

R ₁₄ is a group consisting of (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2- (meth) acryloyloxyethyl succinate Is a structure derived from a monomer selected from

또는

이고, R₁₇ 및 R₁₈은 서로 독립적으로 탄소수 1 내지 6의 알킬기 또는 탄소수 3 내지 6의 시클로알킬기이며, "*"는 결합손을 나타내고,R ₁₅ is

or

R ₁₇ and R ₁₈ are each independently an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, and “*” represents a bond;

e = 20 to 70 mol%, f = 10 to 50 mol%, g = 10 to 50 mol%).

2. In the above 1, wherein the formula 1 in the first resin, a = 10 to 30 mol%, b = 40 to 60 mol%, c = 20 to 40 mol%, d = 5 to 20 mol%, negative photosensitive resin composition.

3. In the above 1, wherein in the second resin Formula 2 is e = 50 to 60 mol%, f = 10 to 30 mol%, g = 20 to 40 mol%, negative photosensitive resin composition.

4. In the above 1, wherein the mixed weight ratio of the first resin and the second resin is 10:90 to 90:10, the negative photosensitive resin composition.

5. The above 1, wherein the mixed weight ratio of the first resin and the second resin is 50:50 to 80:20, the negative photosensitive resin composition.

6. according to the above 1, the weight average molecular weight of the first resin is 5,000 to 20,000, the negative photosensitive resin composition.

7. In the above 1, the weight average molecular weight of the second resin is 10,000 to 30,000, the negative photosensitive resin composition.

8. according to the above 1, further comprising a polyfunctional thiol compound represented by the following formula (3), the negative photosensitive resin composition:

[Formula 3]

(Wherein Z ₁ is a methylene group or a linear or branched alkylene group or alkylmethylene group having 2 to 10 carbon atoms, Y is a single bond, -CO-, -O-CO- or -NHCO-, n is An integer of 3 to 10, X is an n-valent hydrocarbon group having 2 to 70 carbon atoms which may have one or a plurality of ether bonds, or n is 3 and X is a trivalent group represented by the following general formula (4):

[Formula 4]

(Wherein Z ₂ , Z ₃ and Z ₄ are each independently a methylene group or an alkylene group having 2 to 6 carbon atoms, and “*” represents a bond).

9. The photocurable pattern is formed of the negative photosensitive resin composition of any one of the above 1 to 8.

10. The photocuring pattern of 9 above, wherein the photocuring pattern is selected from the group consisting of an array planarization film pattern, a protection film pattern, an insulation film pattern, a photoresist pattern, a black matrix pattern, and a column spacer pattern.

11. The image display device including the photocuring pattern of the above nine.

The pattern produced from the photosensitive resin composition of the present invention not only has excellent mechanical properties such as elastic recovery rate but also shows high durability such as excellent chemical resistance and peeling resistance.

Moreover, the photosensitive resin composition of this invention shows the outstanding pattern formation ability in the photolithography process.

Moreover, the pattern manufactured from the photosensitive resin composition of this invention is excellent in image development adhesiveness with respect to a lower board | substrate.

Figure 1 schematically shows the definition of the Bottom CD size of the pattern according to an embodiment of the present invention.
2 to 7 are pattern photographs of 5B, 4B, 3B, 2B, 1B, and 0B in order in chemical resistance evaluation.

The present invention is an alkali-soluble first resin comprising a repeating unit represented by the formula (1); An alkali-soluble second resin including a repeating unit represented by Formula 2; Polymerizable compounds; Photopolymerization initiator; And a solvent, the present invention relates to a negative photosensitive resin composition capable of forming a pattern having excellent pattern formation capability in a photolithography process and having excellent mechanical properties, durability, and adhesion to a lower substrate.

In the present specification, the monomers, repeating units, and compounds represented by the above formula include monomers, repeating units, and isomers of the compounds, and when the monomers, repeating units, and compounds represented by each formula have isomers, Monomers, repeating units, compounds represented by the formula means a representative formula including the isomers.

Hereinafter, the present invention will be described in detail.

<Photosensitive resin composition>

The photosensitive resin composition of this invention contains alkali-soluble resin, a polymerizable monomer compound, a photoinitiator, and a solvent.

Alkali soluble resin

Alkali-soluble 1st resin used for this invention is a component which gives solubility, mechanical property, and durability with respect to the alkaline developing solution used at the image development process at the time of forming a pattern, Comprising: It contains the repeating unit represented by following General formula (1). It contains a 1st resin.

[Formula 1]

(Wherein R ₁ , R _{2 ,} R ₃ and R ₄ are each independently hydrogen or a methyl group,

R ₅ is a structure derived from a monomer represented by the following formula (1), R ₉ is hydrogen or a methyl group,

R ₆ is a structure derived from a monomer selected from the group consisting of the following formulas (2) to (4),

R ₇ is a structure derived from a monomer selected from the group consisting of the following formulas (5) to (7), X ₁ is an alkylene group having 1 to 12 carbon atoms, X ₂ is an alkyl group having 1 to 6 carbon atoms,

R ₈ is a group consisting of (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2- (meth) acryloyloxyethyl succinate Is a structure derived from a monomer selected from

a = 5 to 50 mol%, b = 20 to 60 mol%, c = 10 to 50 mol%, d = 5 to 30 mol%)

The photosensitive resin composition of the present invention further includes an alkali-soluble second resin represented by the following Chemical Formula 2 in addition to the alkali-soluble first resin, thereby further improving pattern forming ability, mechanical properties, durability, and adhesion to a lower substrate.

[Formula 2]

(Wherein R ₁₀ , R _11, and R ₁₂ are each independently hydrogen or a methyl group,

R ₁₃ is a structure derived from a monomer represented by the following formula (8), R ₁₆ is hydrogen or a methyl group,

R ₁₄ is a group consisting of (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2- (meth) acryloyloxyethyl succinate Is a structure derived from a monomer selected from

또는

이고, R₁₇ 및 R₁₈은 서로 독립적으로 탄소수 1 내지 6의 알킬기 또는 탄소수 3 내지 6의 시클로알킬기이며, "*"는 결합손을 나타내고,R ₁₅ is

or

R ₁₇ and R ₁₈ are each independently an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, and “*” represents a bond;

e = 20 to 70 mol%, f = 10 to 50 mol%, g = 10 to 50 mol%).

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

In the present invention, each repeating unit represented by the formulas (1) and (2) should not be construed as limited to those represented by the formulas (1) and (2), and the sub-repeat units in parentheses may be freely positioned at any position in the chain within a defined mole% range. Can be located. That is, the parentheses of the formulas (1) and (2) are represented by one block to express mol%, but each sub-repeat unit may be positioned in blocks or separately, without limitation, in the resin.

Preferred examples of the compound of formula 1 according to the present invention include a compound of formula 1-1.

[Formula 1-1]

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or a methyl group, a = 5 to 50 mol%, b = 20 to 60 mol%, c = 10 to 50 mol%, d = 5 to 30 mol% being).

In addition, preferred examples of the compound of formula 2 according to the present invention include a compound of formula 2-1 or a formula 2-2.

[Formula 2-1]

 [Formula 2-2]

(Wherein R ₁₀ , R _11, and R ₁₂ are each independently hydrogen or a methyl group, e = 20 to 70 mol%, f = 10 to 50 mol%, g = 10 to 50 mol%).

The first resin according to the present invention serves to improve the mechanical properties and chemical resistance of the photosensitive resin composition, in this aspect, the weight average molecular weight of the first resin is preferably 5,000 to 20,000. It can exhibit the best mechanical properties and chemical resistance in the molecular weight range.

In the aspect of maximizing the effect of improving the mechanical properties, the formula (1) in the first resin is preferably a = 10 to 30 mol%, b = 40 to 60 mol%, c = 20 to 40 mol%, d = 5 to 20 mol%.

The second resin according to the present invention functions to improve durability, such as pattern formation, mechanical properties, chemical resistance, and the like of the photosensitive resin composition.

In the aspect of maximizing the effect of improving the mechanical properties, the formula (2) in the second resin is preferably e = 50 to 60 mol%, f = 10 to 30 mol%, g = 20 to 40 mol%.

In addition, the weight average molecular weight of the second resin according to the present invention is preferably 10,000 to 30,000. It can exhibit the best mechanical properties and chemical resistance in the molecular weight range.

Specifically, the photosensitive resin composition of the present invention includes a first resin and a second resin containing an aromatic ring derived from styrene or vinyl toluene in a repeating unit, and by using an alkali-soluble resin containing the aromatic ring, a conventional ester Compared to using a resin having a functional group having a bond, it is also resistant to hydrolysis of acids and bases, and can realize excellent mechanical properties and durability while maintaining excellent resolution of the prepared pattern.

The mixing weight ratio of the first resin and the second resin according to the present invention is 10:90 to 90:10, preferably 50:50 to 80:20. It can exhibit the most excellent pattern formation, mechanical properties and chemical resistance in the above range.

In addition to the repeating unit represented by Formula 1, the first resin according to the present invention may further include a repeating unit formed of another monomer known in the art, and may be formed only of the repeating unit represented by Formula 1.

Monomers that form a repeating unit that may be further added to Formula 1 are not particularly limited, but are monocarboxylic acids; Dicarboxylic acids and their anhydrides; Mono (meth) acrylates of polymers; Aromatic vinyl compounds; N-substituted maleimide compounds; Alkyl (meth) acrylates; Aryl (meth) acrylates; Unsaturated oxetane compound; Unsaturated oxirane compounds; (Meth) acrylate substituted with cycloalkane or dicycloalkane ring; Etc. can be mentioned. These can be used individually or in mixture of 2 or more types.

In addition to the repeating unit represented by Formula 2, the second resin according to the present invention may further include a repeating unit formed of other monomers known in the art, if necessary, and may be formed only of the repeating unit represented by Formula 2.

The monomer forming a repeating unit which may be further added to the formula (2) is not particularly limited, but may further include, for example, a monomer represented by the following formula (5) (repeating unit h).

[Formula 5]

(In Formula 5, n is 0 or 1, H ₁ and H ₂ are each independently an aliphatic or aromatic hydrocarbon containing or not including a hydrogen, a hetero atom having 1 to 12 carbon atoms, H ₃ , H ₄ , H ₅ and H ₆ are each independently a hydrogen, an aliphatic or aromatic hydrocarbon containing or without a hetero atom having 1 to 30 carbon atoms, and two selected from H ₃ , H ₄ , H ₅ , and H ₆ are linked to each other. Ring or unlinked branches).

The hetero atom may be present in the main skeleton or in a branch, and may exist in the form of a carbonyl group, an ether group, an alcohol group, an amine group, a heterocycle, and the like, and is not limited.

For example, Formula 5 may be selected from the group consisting of the following formula (repeat unit h).

Another example of the monomer forming a repeating unit which may be further added to the formula (2) may include a structure derived from a monomer represented by the following formulas (12) to (18) (repeating unit i).

(Wherein I ₁ is Hydrogen or methyl group.

The second resin according to the present invention may be formed only of the repeating units represented by the above (e), (f) and (g), in addition to the repeating units represented by the above (e), (f) and (g). It may further include a repeating unit represented by (h) or (i). Further, in addition to the repeating unit represented by (h) or (i), it may further include a repeating unit formed of other monomers known in the art.

The alkali-soluble resin according to the present invention preferably has an acid value in the range of 20 to 200 (KOHmg / g). If the acid value is in the above range, it may have excellent developability and stability over time.

Although the total content of alkali-soluble resin is not specifically limited, For example, with respect to 100 weight part of total photosensitive resin compositions based on solid content, it may be included as 10-90 weight part, Preferably it is 25-70 weight part. When included in the above range, the solubility in a developing solution is sufficient, so that the developability is excellent, and the photocuring pattern having excellent mechanical properties can be formed.

Polymerizable  compound

The polymerizable compound used in the photosensitive resin composition of the present invention may increase the crosslinking density during the manufacturing process, and may enhance the mechanical properties of the photocured pattern.

The polymerizable compound may be used without particular limitation as used in the art, for example, a monofunctional monomer, a bifunctional monomer, and other multifunctional monomers, and the kind thereof is not particularly limited, but the following compounds may be exemplified. have.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrroli Money, etc. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol tree. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. Of these, bifunctional or higher polyfunctional monomers are preferably used.

Although the content of the said polymeric compound is not specifically limited, For example, it uses in the range of 10-90 weight part, Preferably it is 30-80 weight part with respect to 100 weight part of alkali-soluble resin based on solid content in the photosensitive resin composition. do. When the polymerizable compound (B) is included in the above content range, it may have excellent durability, and developability of the composition may be improved.

Photopolymerization Initiator

As long as the photoinitiator which can superpose | polymerize the said polymeric compound, the photoinitiator can be used without a restriction | limiting in particular, For example, an acetophenone type compound, a benzophenone type compound, a triazine type compound, a biimida At least one compound selected from the group consisting of a sol compound, a thioxanthone compound and an oxime ester compound can be used, and preferably an oxime ester compound is used.

In addition, the photopolymerization initiator may further include a photopolymerization initiation aid to improve the sensitivity of the photosensitive resin composition of the present invention. Since the photosensitive resin composition which concerns on this invention contains a photoinitiation start adjuvant, a sensitivity can become high and productivity can be improved.

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

Although the content of the photoinitiator is not particularly limited, for example, it may be included in 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight based on 100 parts by weight of the total photosensitive resin composition based on solids. When the above range is satisfied, the photosensitive resin composition may be highly sensitive to shorten the exposure time, thereby improving productivity and maintaining high resolution, and the strength of the formed pixel portion and smoothness on the surface of the pixel portion may be improved. good.

menstruum

The solvent can be used without any limitation as long as it is conventionally used in the art.

Specific examples of the solvent include ethylene glycol monoalkyl ethers; Diethylene glycol dialkyl ethers; Ethylene glycol alkyl ether acetates; Alkylene glycol alkyl ether acetates; Propylene glycol monoalkyl ethers; Propylene glycol dialkyl ethers; Propylene glycol alkyl ether propionates; Butyl diol monoalkyl ethers; Butanediol monoalkyl ether acetates; Butanediol monoalkyl ether propionate; Dipropylene glycol dimethyl ether and dipropylene glycol dialkyl ethers; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones; Alcohols; Esters; Cyclic ethers such as tetrahydrofuran and pyran; Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned. The solvent illustrated here can be used individually or in mixture of 2 or more types, respectively.

The solvent may be included in the photosensitive resin composition in an amount of 40 to 95 parts by weight, preferably 45 to 85 parts by weight, based on 100 parts by weight of the total. When the said range is satisfied, since applicability | paintability becomes favorable when apply | coating with coating apparatuses, such as a spin coater, a slit & spin coater, a slit coater (it may also be called a die coater, a curtain flow coater), and inkjet, it is preferable.

additive

The photosensitive resin composition according to the present invention may further include additives such as a polyfunctional thiol compound, a filler, another polymer compound, a curing agent, a leveling agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent, a chain transfer agent, and the like, if necessary. .

Among the additives, the polyfunctional thiol compound may have a function of improving crosslinking density, improving durability of the photocuring pattern and adhesion to the substrate, and preventing yellowing at high temperature.

The polyfunctional thiol compound is not particularly limited as long as it is a compound that can be used in the photosensitive resin composition, a trifunctional or higher functional thiol compound is preferable, and more preferably a tetrafunctional or higher functional thiol compound is preferable. For example, the thiol compound according to the present invention may be represented by the following Chemical Formula 3.

[Formula 3]

(Wherein Z ₁ is a methylene group or a linear or branched alkylene group or alkylmethylene group having 2 to 10 carbon atoms, Y is a single bond, -CO-, -O-CO- or -NHCO-, n is An integer of 3 to 10, X is an n-valent hydrocarbon group having 2 to 70 carbon atoms which may have one or a plurality of ether bonds, or n is 3 and X is a trivalent group represented by the following general formula (4):

[Formula 4]

(Wherein Z ₂ , Z ₃ and Z ₄ are each independently a methylene group or an alkylene group having 2 to 6 carbon atoms, and “*” represents a bond).

n is preferably 4 or more, or an integer of 4 to 10, and more preferably 4, 6 or 8.

As n when 3 is 3, the trivalent group represented by following General formula (6-1) is mentioned, for example,

As X when n is 4, 6, or 8, the 4, 6, or 8-valent group represented by following formula (6-2) etc. are mentioned as a preferable thing, respectively.

[Formula 6-1]

(Wherein "*" represents a bonding hand),

[Formula 6-2]

(Wherein m is an integer of 0 to 2 and "*" represents a bond).

< Photocuring  Pattern and Image Display Device>

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

The photocuring pattern made of the photosensitive resin composition has excellent mechanical properties, durability, and adhesion to a lower substrate. Accordingly, the image display device may be used as various patterns, for example, an adhesive layer, an array planarization film, a protective film, an insulating film pattern, or the like, and may be used as a photoresist, a black matrix, a column spacer pattern, and the like. In particular, it is very suitable as a photoresist pattern.

An image display device having such a photocuring pattern or using the pattern during a manufacturing process may include a liquid crystal display device, an OLED, a flexible display, and the like, but is not limited thereto. All image display devices known in the art may be applied. Can be illustrated.

A photocuring pattern can be manufactured by apply | coating the photosensitive resin composition of this invention mentioned above on a base material, and forming a photocuring pattern (after roughening a development process and / or a heating (drying) process as needed).

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.

Production Example  1. Synthesis of alkali-soluble resin (first resin (A-1))

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 150 g of diethylene glycol methylethyl ether was added and heated to 70 ° C while stirring. Next, 88.1 g (0.40 mol) of a mixture of the following Chemical Formulas 7 and 8 ((molar ratio: 50:50), 23.6 g (0.20 mol) of vinyl toluene, 55.3 g (0.30) of 3-ethyl-3-oxetanyl methacrylate) mol) and 7.2 g (0.10 mol) of acrylic acid were dissolved in 100 g of diethylene glycol methylethyl ether.

 [Formula 7]

[Formula 8]

The prepared solution was added dropwise to the flask using a dropping funnel, and then 27.9 g (0.11 mol) of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 200 g of diethylene glycol methylethyl ether. The solution dissolved in was dropped into the flask over 4 hours using a separate dropping funnel. After the dropwise addition of the solution of the polymerization initiator was completed, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature, and the repeating unit of the following formula (9) having a solid content of 30.7 mass% and an acid value of 79 mg-KOH / g (solid content conversion) The solution of the copolymer (resin A-1) represented by was obtained, the weight average molecular weight Mw was 8,400, molecular weight distribution was 1.75.

[Formula 9]

In this case, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured by using an HLC-8120GPC (manufactured by Tosoh Corporation) apparatus, and the column was used by serially connecting TSK-GELG4000HXL and TSK-GELG2000HXL. The column temperature was 40 ° C, the mobile phase solvent was tetrahydrofuran, the flow rate was 1.0 ml / min, the injection amount was 50 µl, and the detector RI was used. The measurement sample concentration was 0.6 mass% (solvent = tetrahydrofuran), a calibration standard. The material used was TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation).

The ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).

Production Example  2. Synthesis of alkali-soluble resin (first resin (A-2))

Under the same conditions as in Preparation Example 1, a mixture of the formulas (7) and (8) ((molar ratio: 50:50) 103.1 g (0.50 mol), vinyl toluene 11.8 g (0.10 mol), 2-((3-ethyloxetane- 3-yl) methoxy) ethyl methacrylate 68.4 g (0.30 mol) and 7.2 g (0.10 mol) acrylic acid were added to the mixture to obtain a solid content of 30.5 mass% and an acid value of 68 mg-KOH / g. The copolymer (resin A-2) represented by the repeating unit was obtained The weight average molecular weight of polystyrene conversion measured by GPC was 8250, and the molecular weight distribution (Mw / Mn) was 1.8.

[Formula 10]

Production Example  3. Synthesis of Alkali Soluble Resin (A-3)

Under the same conditions as in Preparation Example 1, 132.2 g (0.60 mol) of the mixture of Formulas 7 and 8 ((molar ratio is 50:50), 55.3 g (0.30 mol) of 3-ethyl-3-oxetanyl methacrylate) Synthesis was performed by adding 8.6 g (0.10 mol) of methacrylic acid to obtain a copolymer (resin A-3) represented by a repeating unit of the following Formula 11 having a solids content of 36.5 mass% and an acid value of 62 mg-KOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 8,200, and molecular weight distribution (Mw / Mn) was 1.82.

[Formula 11]

Production Example  4. Synthesis of Alkali Soluble Resin (A-4)

Under the same conditions as in Preparation Example 1, 176.2 g (0.80 mol) of the mixture of Formulas 7 and 8 ((molar ratio is 50:50), 11.8 g (0.10 mol) of vinyl toluene, and 7.2 g (0.10 mol) of acrylic acid) were added thereto. The synthesis was carried out to obtain a copolymer (resin A-4) represented by a repeating unit represented by the following formula 12 having a solid content of 35.9% by mass and an acid value of 55 mg-KOH / g: The weight average molecular weight in terms of polystyrene measured by GPC was 8,070 and a molecular weight distribution (Mw / Mn) was 1.93.

[Formula 12]

Production Example  5. Synthesis of Alkali Soluble Resin (A-5)

Under the same conditions as in Preparation Example 1, 198.2 g (0.90 mol) of the mixture of Formulas 7 and 8 ((molar ratio is 50:50) and 8.6 g (0.10 mol) of methacrylic acid were added to the mixture to obtain 41.2 mass of solids). %, An acid value of 65 mgKOH / g, a copolymer (resin A-5) represented by the repeating unit of formula 13. The weight average molecular weight of polystyrene conversion measured by GPC was 8,200, and the molecular weight distribution (Mw / Mn) was 1.78.

[Formula 13]

Production Example  6. Synthesis of alkali-soluble resin (second resin (A-6))

Into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, 200 g of propylene glycol monomethyl ether acetate was introduced, and the temperature was raised to 100 ° C., followed by 29.4 g of maleic anhydride ( 0.30 mol), 67.7 g (0.65 mol) of styrene, and 11.0 g (0.05 mol) of tricyclo [5.2.1.0 ^2,6 ] decanyl acrylate are added, followed by stirring.

Subsequently, a solution in which 3.6 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 150 g of propylene glycol monomethyl ether acetate was added dropwise to the flask over 2 hours from the dropping funnel. Stirring was continued for another 5 hours.

To the reaction mixture, 37.7 g of hydroxyethyl methacrylate [0.29 mol (94 mol% of the maleic anhydride used in this reaction)] was added to the flask, and the reaction was continued at 110 DEG C for 6 hours, and the solid content was 32.4 mass. The copolymer (resin A-6) represented by the repeating unit of formula (14) having a% and a solid acid value of 147 mg-KOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 11,400, and molecular weight distribution (Mw / Mn) was 2.1.

[Formula 14]

Production Example  7. Synthesis of alkali-soluble resin (second resin (A-7))

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 a nitrogen atmosphere, 200 g of propylene glycol monomethyl ether acetate was introduced, and the temperature was raised to 100 ° C., followed by 25.2 g of acrylic acid (0.35 mol). ), 4.7 g (0.05 mole) norbornene, 70.9 g (0.60 mole) vinyltoluene and 150 g propylene glycol monomethylether acetate were added. Then, a solution obtained by dissolving 3.6 g of 2,2'-azobis (2,4-dimethylvaleronitrile) in 150 g of propylene glycol monomethyl ether acetate was added dropwise to the flask over 2 hours from a dropping lot, followed by 5 hours at 100 ° C. Further stirring was continued.

Subsequently, the atmosphere in the flask was changed from nitrogen to air, 28.4 g of glycidyl methacrylate [0.20 mol (57 mol% of acrylic acid used in the reaction)] was added to the flask, and the reaction was continued at 110 ° C. for 6 hours. And the copolymer (resin A-7) represented by the repeating unit of following formula (15) whose solid content acid value is 70 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 14,500, and molecular weight distribution (Mw / Mn) was 2.3.

[Formula 15]

Production Example  8. Synthesis of alkali-soluble resin (second resin (A-8))

Under the same conditions as in Preparation Example 7, in a mixture containing 32.4 g (0.45 mole) acrylic acid, 59.1 g (0.50 mole) vinyltoluene, 7.7 g (0.05 mole) cyclohexyl acrylate, and 350 g propylene glycol monomethylether acetate 2, A solution of 3.6 g of 2'-azobis (2,4-dimethylvaleronitrile) dissolved in 150 g of propylene glycol monomethyl ether acetate was added dropwise to the flask over 2 hours from the dropping lot, and the stirring was continued at 100 DEG C for 5 hours. Thereafter, 42.6 g [0.30 mol (67 mol% of acrylic acid used in this reaction)] of glycidyl methacrylate was added to the flask and the reaction was continued at 110 DEG C for 6 hours, where the solid acid value was 78 mgKOH / g. To obtain a copolymer (resin A-8) represented by a repeating unit of the formula (16). The weight average molecular weight of polystyrene conversion measured by GPC was 15,400, and molecular weight distribution (Mw / Mn) was 2.6.

[Formula 16]

Production Example  9. Synthesis of Alkali Soluble Resin (A-9)

Under the same conditions as in Production Example 7, 47.3 g (0.55 mol) of methacrylic acid, 35.0 g (0.35 mol) of methyl methacrylate, 22.0 g (0.10 mol) of tricyclo [5.2.1.0 ^2,6 ] decanyl methacrylate Was dissolved in 350 g of propylene glycol monomethyl ether acetate, and then a solution of 3.6 g of 2,2'-azobis (2,4-dimethylvaleronitrile) in 150 g of propylene glycol monomethyl ether acetate was added dropwise from the lot. It was added dropwise to the flask over.

 Thereafter, stirring was further continued at 100 DEG C for 5 hours, and 42.6 g [0.30 mol (55 mol% of the acrylic acid used in the reaction)] glycidyl methacrylate was added to the flask and reacted at 110 DEG C for 6 hours. Then, the copolymer (resin A-9) represented by the repeating unit of following formula (17) whose solid acid value is 103 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 28,400, and molecular weight distribution (Mw / Mn) was 2.2.

[Formula 17]

Production Example  10. Synthesis of Alkali Soluble Resin (A-10)

Under the same conditions as in Production Example 7, 47.3 g (0.55 mol) of methacrylic acid, 61.6 g (0.35 mol) of benzyl methacrylate, 22.0 g (0.10 mol) of tricyclo [5.2.1.0 ^2,6 ] decanyl methacrylate Was dissolved in 350 g of propylene glycol monomethyl ether acetate, and then a solution of 3.6 g of 2,2'-azobis (2,4-dimethylvaleronitrile) in 150 g of propylene glycol monomethyl ether acetate was added dropwise from the lot. It was added dropwise to the flask over.

 Thereafter, 42.6 g [0.30 mol (55 mol% of the acrylic acid used in the reaction)] glycidyl methacrylate was added to the flask and the reaction was continued at 110 DEG C for 6 hours, where the solid acid value was 109 mgKOH / g. To obtain a copolymer (resin A-10) represented by a repeating unit of the formula (18). The weight average molecular weight of polystyrene conversion measured by GPC was 30,400, and molecular weight distribution (Mw / Mn) was 2.4.

[Formula 18]

Example  And Comparative example

The negative photosensitive resin composition which has the composition and content (weight part) of following Table 1 and Table 2 was prepared.

division
(Parts by weight) Example One 2 3 4 5 6 7 8 Alkali solubility
Suzy
(A) A-1 8.6 8.6 8.6 6.9 10.4 13.8 3.5 - A-2 - - - - - - - 8.6 A-3 - - - - - - - - A-4 - - - - - - - - A-5 - - - - - - - - A-6 8.6 - - - - - - - A-7 - 8.6 - 10.4 6.9 3.5 13.8 8.6 A-8 - - 8.6 - - - - - A-9 - - - - - - - - A-10 - - - - - - - - Polymerizable compound
(B) B-1 17.3 17.3 17.3 17.2 17.2 17.2 17.2 17.3 Photopolymerization initiator
(C) C-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 C-2 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 menstruum
(D) D-1 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 D-2 37.0 37.0 37.0 37.0 37.0 37.0 37.0 37.0 additive
(E) E-1 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 E-2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

division
(Parts by weight) Comparative example One 2 3 4 5 6 7 Suzy
(A) A-1 17.3 - - - - 8.6 8.6 A-2 - - - - - - - A-3 - - 8.6 - - - - A-4 - - - 8.6 - - - A-5 - - - - 8.6 - - A-6 - - - - - - - A-7 - 17.3 8.6 8.6 8.6 - - A-8 - - - - - - - A-9 - - - - - 8.6 - A-10 - - - - - - 8.6 Polymerizable
compound
(B) B-1 17.2 17.2 17.3 17.3 17.3 17.3 17.3 Photopolymerization
Initiator
(C) C-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 C-2 1.5 1.5 1.5 1.5 1.5 1.5 1.5 menstruum
(D) D-1 25.0 25.0 25.0 25.0 25.0 25.0 25.0 D-2 37.0 37.0 37.0 37.0 37.0 37.0 37.0 additive
(E) E-1 1.0 1.0 1.0 1.0 1.0 1.0 1.0 E-2 0.5 0.5 0.5 0.5 0.5 0.5 0.5

A-1: Resin of Preparation Example 1, A-2: Resin of Preparation Example 2

A-3: Resin of Preparation Example 3, A-4: Resin of Preparation Example 4

A-5: Resin of Preparation Example 5, A-6: Resin of Preparation Example 6

A-7: Resin of Preparation Example 7, A-8: Resin of Preparation Example 8

A-9: Resin of Preparation Example 9, A-10: Resin of Preparation Example 10

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

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

C-2:

D-1: diethylene glycol methylethyl ether

D-2: Propylene Glycol Monomethyl Ether Acetate

E-1:

E-2: 4,4'-butylidene bis [6-tert-butyl-3-methylphenol] (BBM-S: Sumitomo Fine Chemical Co., Ltd.) as an antioxidant

Test Methods

The glass substrate (Eagle 2000; manufactured by Corning Corporation) having a length and width of 2 inches was washed sequentially with a neutral detergent, water, and alcohol, and dried. Each of the photosensitive resin compositions prepared in Examples and Comparative Examples was spin coated on the glass substrate, and then prebaked at 90 ° C. for 125 seconds using a hot plate. After cooling the prebaked substrate to room temperature, the distance from the quartz glass photomask was set to 200 μm and light was emitted at an exposure amount (365 nm standard) of 80 mJ / cm 2 using an exposure machine (UX-1100SM; manufactured by Ushio Corporation). Investigate. In this case, a photomask in which the next pattern was formed on the same plane was used.

The coating film was immersed at 25 ° C. for 60 seconds in an aqueous developing solution having a square opening having a diameter of 12 μm, having a mutual interval of 100 μm, and containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide after light irradiation. After washing with water, post-baking was performed at 140 ° C. for 30 minutes. The obtained pattern height was 3.0 micrometers.

 The physical properties of the coating film thus obtained were evaluated as follows, and the results are shown in Table 3 below.

(1) Bottom CD size measurement of pattern

The Dot pattern obtained above was observed with a three-dimensional shape measuring device (SIS-2000 system; manufactured by SNU Precision), and as shown in FIG. The average value of the measured values in the horizontal direction and the vertical direction was defined as the line width of the pattern.

(2) CD-Bias of the pattern

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 as CD-bias as follows. The closer CD-bias is to 0, the better. (+) Means that the bottom CD value of the hole pattern is smaller than the mask and (-) means the hole size is larger than the mask.

CD-bias = (formed pattern size)-(mask size used for formation)

(3) Development adhesiveness measurement

Development adhesiveness is a measure of how closely a pattern generated by using a half-tone mask having a 25% transmittance adheres to a substrate. SNU Precision's three-dimensional shape measuring device measures the actual size of the pattern when 100% of the pattern formed with a film thickness of 3 μm is left without missing by a photomask having 1000 dot patterns each having a thickness of 1 μm from 20 μm to 20 μm. Line width was measured using SIS-2000.

The value of the pattern line width was defined as the value of Bottom CD at the point of 5% of the total height from the bottom surface of the pattern. The smaller the minimum pattern size remaining without missing, the better the development adhesion.

(4) chemical resistance evaluation

The prepared resist solution was applied to a glass substrate, spin coated, and then prebaked at 90 ° C. for 125 seconds using a hot plate. After cooling the prebaked substrate to room temperature. Using the exposure machine (UX-1100SM; Ushio Corporation make), the light was irradiated to the whole surface of the coating film by the exposure amount (365 nm reference | standard) of 60 mJ / cm <2>. After light irradiation, the coating film was developed by immersing at 25 ° C for 60 seconds in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, and the film thickness was measured after washing with water. Subsequently, baking was performed for 30 minutes, heating at 140 degreeC in oven.

The coating film obtained above was immersed in HNO ₃ and HCl aqueous solution (70% nitric acid (80%) + concentrated hydrochloric acid (20%)) and treated for 45 minutes / 2 minutes, and then Adhesiveness was confirmed by attaching a tape to the cut surface and peeling it off. In the Cutting / Tape test after chemical treatment, the degree of peeling of the coating film is defined as 0B to 5B based on the standard test method, and 5B is determined to have the best performance (5B peeling 0%, 4B peeling less than 5%). , 3B peeling 5-15%, 2B peeling 15-35%, 1B peeling 35-65%, 0B 65% or more). 2-7 are pattern photographs in the case of 5B, 4B, 3B, 2B, 1B, and 0B in order.

(5) Mechanical property evaluation (total displacement and recovery rate)

Each of the photosensitive resin compositions prepared in Examples and Comparative Examples was spin coated on a glass substrate having a length of 2 inches (Eagle 2000; manufactured by Corning) and then prebaked at 90 ° C. for 125 seconds using a hot plate. After cooling the prebaked substrate to room temperature, the distance from the quartz glass photomask was set to 200 μm and light was emitted at an exposure amount (365 nm standard) of 80 mJ / cm 2 using an exposure machine (UX-1100SM; manufactured by Ushio Corporation). Investigate. In this case, a photomask in which the next pattern was formed on the same plane was used.

The coating film was immersed at 25 ° C. for 60 seconds in an aqueous developing solution having a square opening having a diameter of 12 μm, having a mutual interval of 100 μm, and containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide after light irradiation. After washing with water, post-baking was performed at 235 ° C. for 15 minutes in an oven. The obtained pattern height was 3.0 micrometers. The pattern thus obtained was measured using a dynamic ultra-fine hardness tester (HM-2000; Helmut Fischer GmbH + Co.KG) to determine its total displacement (D1, μm) and elastic displacement (D2, μm) according to the following measurement conditions. Using the measured values, the recovery rate (%) was calculated as follows.

Recovery rate (%) = [elastic displacement (μm)] / [total displacement (μm)] × 100

Measurement conditions are as follows.

Test mode; Load-Unload Test

Test force; 50.0mN

Load speed; 4.41mN / sec

Holding time; 5sec

Indenter; Square pyramid indenter (50㎛ diameter)

division pattern phenomenon
Adhesiveness
(Μm) Chemical resistance

evaluation
Mechanical property evaluation
Bottom CD Size (㎛) CD-Bias
(Μm) Total displacement
(D1, μm) Elastic recovery
(%) Example 1 13 1.0 12 5B 1.49 68.6 Example 2 12.4 0.4 10 5B 1.42 69.5 Example 3 13.4 1.4 13 5B 1.45 67.8 Example 4 13.7 1.7 9 5B 1.58 64.4 Example 5 12.1 0.1 12 5B 1.54 65.5 Example 6 11.9 -0.1 14 5B 1.51 66.2 Example 7 13.9 1.9 12 5B 1.57 64.8 Example 8 12.2 0.2 11 5B 1.43 69.2 Comparative Example 1 10.7 -1.3 20 4B 1.64 62.7 Comparative Example 2 15.1 3.1 16 1B 1.73 59.8 Comparative Example 3 13.8 1.8 14 3B 1.60 63.2 Comparative Example 4 12.6 0.6 15 0B 1.82 55.2 Comparative Example 5 12.2 0.2 17 0B 1.68 61.3 Comparative Example 6 14.8 2.8 16 0B 1.87 54.3 Comparative Example 7 14.3 2.3 14 2B 1.78 57.8

Referring to Table 3, it was confirmed that the bottom CD size of the pattern prepared using the example of the photosensitive resin composition of the present invention was close to 12㎛ and the CD-bias value was close to 0, the pattern formation was superior. In addition, it was confirmed that the pattern produced using the photosensitive resin composition according to the present invention has excellent development adhesiveness and chemical resistance to the lower substrate. In addition, the pattern produced using the photosensitive resin composition according to the present invention was confirmed that the elastic recovery rate is significantly higher than 64% compared to the comparative example, excellent mechanical properties.

However, in the case of a pattern manufactured using a comparative example other than the photosensitive resin composition of the present invention, it can be confirmed that the bottom CD size is greatly deviated from 12 μm or the CD-bias value is greatly deviated from 0, so that the pattern formation is not excellent. Development adhesiveness to the lower substrate was reduced, it was confirmed that the chemical resistance is significantly reduced compared to the embodiments.

In addition, in the case of the pattern manufactured using the comparative example it was confirmed that the elastic recovery rate is significantly lower than the example, the mechanical properties are reduced.

Claims (11)

An alkali-soluble first resin including a repeating unit represented by Formula 1 below;
An alkali-soluble second resin including a repeating unit represented by Formula 2 below;
Polymerizable compounds;
Photopolymerization initiator; And
A negative photosensitive resin composition comprising a solvent:
[Formula 1]

(Wherein R ₁ , R _{2 ,} R ₃ and R ₄ are each independently hydrogen or a methyl group,
R ₅ is a structure derived from a monomer represented by the following formula (1), R ₉ is hydrogen or a methyl group,

R ₆ is a structure derived from a monomer selected from the group consisting of the following formulas (2) to (4),

R ₇ is a structure derived from a monomer selected from the group consisting of the following formulas (5) to (7), X ₁ is an alkylene group having 1 to 12 carbon atoms, X ₂ is an alkyl group having 1 to 6 carbon atoms,

R ₈ is a group consisting of (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2- (meth) acryloyloxyethyl succinate Is a structure derived from a monomer selected from
a = 5 to 50 mol%, b = 20 to 60 mol%, c = 10 to 50 mol%, d = 5 to 30 mol%)
[Formula 2]

(Wherein R ₁₀ , R _11, and R ₁₂ are each independently hydrogen or a methyl group,
R ₁₃ is a structure derived from a monomer represented by the following formula (8), R ₁₆ is hydrogen or a methyl group,

R ₁₄ is a group consisting of (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2- (meth) acryloyloxyethyl succinate Is a structure derived from a monomer selected from
R ₁₅ is

or

R ₁₇ and R ₁₈ are each independently an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, and “*” represents a bond;
e = 20 to 70 mol%, f = 10 to 50 mol%, g = 10 to 50 mol%).
The negative photosensitive resin composition according to claim 1, wherein in the first resin, Chemical Formula 1 is a = 10 to 30 mol%, b = 40 to 60 mol%, c = 20 to 40 mol%, d = 5 to 20 mol%.
The negative photosensitive resin composition according to claim 1, wherein in the second resin, Chemical Formula 2 is e = 50 to 60 mol%, f = 10 to 30 mol%, g = 20 to 40 mol%.
The negative photosensitive resin composition of Claim 1 whose mixing weight ratio of the said 1st resin and said 2nd resin is 10: 90-90: 10.
The negative photosensitive resin composition of Claim 1 whose mixing weight ratio of the said 1st resin and said 2nd resin is 50:50-80:20.
The negative photosensitive resin composition of Claim 1 whose weight average molecular weights of a said 1st resin are 5,000-20,000.
The negative photosensitive resin composition of Claim 1 whose weight average molecular weights of a said 2nd resin are 10,000-30,000.
The negative photosensitive resin composition according to claim 1, further comprising a multifunctional thiol compound represented by the following Formula 3:
[Formula 3]

(Wherein Z ₁ is a methylene group or a linear or branched alkylene group or alkylmethylene group having 2 to 10 carbon atoms, Y is a single bond, -CO-, -O-CO- or -NHCO-, n is An integer of 3 to 10, X is an n-valent hydrocarbon group having 2 to 70 carbon atoms which may have one or a plurality of ether bonds, or n is 3 and X is a trivalent group represented by the following general formula (4):
[Formula 4]

(Wherein Z ₂ , Z ₃ and Z ₄ are each independently a methylene group or an alkylene group having 2 to 6 carbon atoms, and “*” represents a bond).
The photocuring pattern formed from the negative photosensitive resin composition of any one of Claims 1-8.
The photocuring pattern of claim 9, wherein the photocuring pattern is selected from the group consisting of an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, and a column spacer pattern.
An image display device comprising the photocuring pattern of claim 9.

Images