JP6644565B2 - Photosensitive resin composition, photocurable pattern formed therefrom, and image display device having the same - Google Patents

Description

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

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

The method of forming a spacer by photolithography is to apply a photosensitive resin composition on a substrate, irradiate ultraviolet rays through a mask, and then to a desired position on the substrate according to a pattern formed on the mask through a development process. Form a spacer.

More specifically, the photolithography process utilizes a radical generated by a photoinitiator to perform a radical polymerization reaction with a photopolymerizable monomer or a polymer having an unsaturated group capable of photopolymerization. Done.

On the other hand, in a coating film coated with a photosensitive resin composition capable of performing a photolithography process, oxygen diffused in the air is present, and when oxygen reacts with a generated radical, the oxygen is stabilized as a peroxy radical. Problem. That is, the radicals are in an inactivated state and do not participate in the polymerization reaction any more, so that the overall crosslinking density of the cured composition is significantly reduced. Such development is called oxygen inhibition, and various studies have been made to improve it.

In order to prevent oxygen inhibition, various studies have been conducted using additives capable of activating stabilized peroxy radicals.However, when such additives are used, high sensitivity is not achieved. Although it can be realized, there is a problem that the size of the pattern becomes excessively large and it is difficult to realize a fine pattern.

Japanese Patent Publication No. 2000-095896

An object of the present invention is to provide a photosensitive resin composition capable of simultaneously realizing high sensitivity and high resolution.

It is another object of the present invention to provide a photocurable pattern which can be embodied as a fine pattern and has excellent adhesion, a residual film ratio, and mechanical properties.

Still another object of the present invention is to provide an image display device having the photocurable pattern.

1. A photosensitive resin composition comprising a thiol-based compound having a value of the following formula 1 satisfying 20 to 35 and an ultraviolet absorber having a maximum absorption wavelength (λ _max ) of 335 to 365 nm.

(In the formula, A is a value indicating the weight (g / mol) of the entire compound when the SH group is converted to 1 mol in the molecule, and B is the number (integer) of the SH groups present in the molecule. is there.)

2. In the item 1, the value of the formula 1 is from 20 to 25.

3. In the item 1, the thiol-based compound is at least one selected from the compounds represented by the following chemical formulas 1 and 2.

(Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R _9, and R ₁₀ are each independently a hydrogen atom or a straight chain having 1 to 5 carbon atoms. Or a branched-chain alkyl group.)

4. In the above item 1, the photosensitive resin composition, wherein the ultraviolet absorbent is at least one selected from compounds represented by the following chemical formulas 3 to 5.

(Wherein, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ each independently represent a halogen atom, a carbon number An alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a thioether group, a cycloalkyl group having 3 to 12 carbon atoms, a bicycloalkyl group having 4 to 12 carbon atoms, a tricycloalkyl group having 6 to 12 carbon atoms, or An aryl group having 6 to 20 carbon atoms,
The aryl group includes a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a thioether group, a cycloalkyl group having 3 to 12 carbon atoms, a bicycloalkyl group having 4 to 12 carbon atoms, and a carbon atom. It can be substituted with at least one substituent selected from the group consisting of tricycloalkyl groups of the formulas 6 to 12. )

5. 2. The photosensitive resin composition according to item 1, wherein the ultraviolet absorber is contained in an amount of 30 to 90 parts by weight based on 100 parts by weight of the thiol compound.

6. 2. The photosensitive resin composition according to item 1, wherein the thiol-based compound is contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the total solid content of the composition.

7. 2. The photosensitive resin composition according to item 1, wherein the ultraviolet absorber is contained in an amount of 0.001 to 3 parts by weight based on 100 parts by weight of the total solid content of the composition.

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

9. In the above item 8, the alkali-soluble resin is a photosensitive resin comprising at least one of a first resin containing a repeating unit represented by the following chemical formula 6 and a second resin containing a repeating unit represented by the following chemical formula 7: Composition:

(In the formula, R ₁ ′ is a hydrogen atom or a methyl group, R ₂ ′ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₃ ′ is a hydrogen atom or a methyl group.)

10. A photocurable pattern produced with the photosensitive resin composition according to any one of the above items 1 to 9.

11. In the item 10, the photocurable pattern is selected from the group consisting of an adhesive layer, an array flattening film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a color filter pattern, a black matrix pattern, and a column spacer pattern. Light curing pattern.

12. Item 12. An image display device comprising the photocurable pattern according to item 11.

ADVANTAGE OF THE INVENTION The photosensitive resin composition of this invention can implement | achieve high sensitivity by relaxing oxygen inhibition, and can suppress the expansion of the line width of a pattern, and can implement | achieve high resolution by a fine pattern.

The photosensitive resin composition of the present invention is excellent in developing adhesion, and very excellent in residual film ratio and mechanical properties.

Since the photo-cured pattern manufactured using the photosensitive resin composition of the present invention can be formed in a fine pattern, high resolution can be realized when applied to a product.

It is a figure which shows the definition of T / B ratio schematically.

The present invention relates to a photosensitive resin composition, and more particularly, to a thiol-based compound satisfying a specific parameter value for a thiol substituent in a molecule, and an ultraviolet absorber having a maximum absorption wavelength (λ _max ) of 335 to 365 nm. By reducing oxygen inhibition, a photosensitive resin composition capable of effectively realizing high sensitivity and suppressing an increase in pattern line width and realizing high resolution when applied to a product. About.

Hereinafter, the present invention will be described in detail.
Conventionally, in a photolithography process, various additives have been used in order to suppress a problem of a decrease in reactivity (oxygen inhibition) due to oxygen present in a coating film. However, such additives could improve the curing reactivity, but could not control the direction in which the reaction occurred, so that not only the pattern height but also the width (line width ) Is also increased, and there is a problem that a fine pattern cannot be realized.

Thus, the present invention simultaneously reduces the oxygen inhibition by simultaneously using a thiol-based compound having a specific structure and a specific ultraviolet absorber, controls the direction of the curing reaction, and simultaneously achieves high sensitivity and high resolution. Can be embodied.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention contains a thiol-based compound satisfying a parameter for a thiol substituent, and an ultraviolet absorber having a maximum absorption wavelength (λ _max ) of 335 to 365 nm.

Thiol-based compound The thiol-based compound used in the present invention is a compound whose value of the following formula 1 satisfies 20 to 35.

(In the formula, A is a value indicating the weight (g / mol) of the entire compound when the SH group is converted to 1 mol in the molecule, and B is the number (integer) of the SH groups present in the molecule. is there.)

The thiol-based compound according to the present invention contains a thiol group (-SH) which is very excellent in reactivity, and the thiol group reacts with a stable peroxy radical to form an alkyl radical capable of a polymerization initiation reaction. In addition, oxygen inhibition can be effectively controlled, thereby realizing high sensitivity at the time of pattern formation.

In the present invention, Equation 1 is a parameter related to the concentration per unit weight of the thiol group (-SH) present in the molecule, and indicates the actual concentration of the SH group contained in the unit weight. Is 1 mol, the weight of the compound is determined, and the value is divided by the number in which the SH group is substituted in the molecule. When a thiol compound satisfying the value of Formula 1 satisfies 20 to 35, the curing efficiency is remarkably improved, and the above-described effects can be increased.

On the other hand, when a thiol-based compound having the value of Formula 1 exceeding 35 is used, the overall sensitivity of the photocuring reaction is insufficient, the residual film ratio is reduced, the oxygen inhibition relaxation on the surface is slowed, and the top of the pattern is reduced. The T / B ratio becomes low due to the decrease in the area, and a problem that the pattern shape changes to a round shape may occur. If the value of Formula 1 is less than 20, it is not suitable for use as a photosensitive resin composition.

In the present invention, when the thiol-based compound has the value of Formula 1 in the range of 20 to 25, it is more preferable in improving the T / B ratio and the adhesion.

The thiol-based compound according to the present invention is not particularly limited as long as it satisfies the above-described formula 1; for example, at least one compound selected from the compounds represented by the following formula 1 or 2 Can be

(Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent a hydrogen atom or a straight chain having 1 to 5 carbon atoms. Or a branched-chain alkyl group.)

The value of Formula 1 for the compound represented by Formula 1 is 20 to 24, and the value of Formula 1 for the compound represented by Formula 2 is 30 to 35. The compound is a polyfunctional compound containing a thiol group at the terminal of the molecule, which has little steric hindrance during the reaction and is excellent in curing efficiency, and more preferably a compound of the formula 1 having six functions.

Ultraviolet absorber The ultraviolet absorber used in the present invention is a component that suppresses an increase in line width (width) due to the thiol-based compound and realizes a fine pattern.

When only a thiol-based compound is used, the acceleration of the curing reaction occurs only in the isotropic direction, and the height and width (line width) of the pattern are all increased. The height of the pattern (the sensitivity in the vertical direction) is maintained within an appropriate range, while reducing the light energy reaching the deep part of the coating film and increasing the width (line width) of the base portion of the pattern (in the horizontal direction). Sensitivity) can be effectively suppressed.

On the other hand, when using only the ultraviolet absorber, a fine pattern can be realized, but the cured density is reduced, and the adhesion and mechanical properties of the pattern may be reduced. By simultaneously using the compound and the ultraviolet absorber, the adhesiveness and mechanical properties of the pattern can be significantly improved.

The ultraviolet absorber has a maximum absorption wavelength (λ _max ) of 335 to 365 nm. When the maximum absorption wavelength is less than 335 nm, the increase in pattern line width cannot be controlled. When the maximum absorption wavelength exceeds 365 nm, the sensitivity is remarkable. , The photocuring reaction is inhibited, and the problem of excessively reducing the line width and deteriorating the adhesion may occur. When the maximum absorption wavelength is from 355 nm to 360 nm, the above-described problem can be more effectively complemented.

The type of the ultraviolet absorber is not particularly limited as long as it satisfies the above-described maximum absorption wavelength range. It is preferred that the ring contains hydroxy at the ortho position.

Specific examples of the UV absorber may include compounds represented by the following Chemical Formulas 3 to 5, which may be used alone or in combination of two or more.

(Wherein, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ each independently represent a halogen atom, a carbon number An alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a thioether group, a cycloalkyl group having 3 to 12 carbon atoms, a bicycloalkyl group having 4 to 12 carbon atoms, a tricycloalkyl group having 6 to 12 carbon atoms, or An aryl group having 6 to 20 carbon atoms,
The aryl group includes a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a thioether group, a cycloalkyl group having 3 to 12 carbon atoms, a bicycloalkyl group having 4 to 12 carbon atoms, and a carbon atom. It can be substituted with at least one substituent selected from the group consisting of tricycloalkyl groups of the formulas 6 to 12. )

In the present invention, the content ratio of the thiol compound and the ultraviolet absorber is not particularly limited, but the ultraviolet absorber can be included in 30 to 90 parts by weight, preferably 40 to 100 parts by weight of the thiol compound. It is good to be 80 parts by weight. When included in the above range, the effects of the present invention can be further improved, and the T / B ratio of the pattern can be significantly improved.

The T / B ratio is a value obtained by dividing the upper diameter of the pattern by the lower diameter, and the larger the T / B ratio, the more preferable. In the present invention, the upper part of the pattern is defined as a horizontal plane at a point that is 95% of the total height from the bottom with respect to the entire height of the pattern, and the lower part of the pattern is defined as a whole from the bottom with respect to the entire height of the pattern. It is defined as the horizontal plane at a point that is 5% of the height (see FIG. 1).

The content of the thiol compound in the composition is not particularly limited, but may be 0.01 to 5 parts by weight based on 100 parts by weight of the total solid content of the composition, and may be included in the above range. In this case, the sensitivity of the pattern can be increased, and the adhesion and the mechanical strength can be further improved.

The content of the ultraviolet absorber is not particularly limited, but may be included in an amount of 0.001 to 3 parts by weight based on 100 parts by weight of the total solid content of the composition. It is suitable for forming and can improve the residual film ratio of the pattern.

The photosensitive resin composition according to the present invention may further include an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, in addition to the thiol-based compound and the ultraviolet absorber described above.

Alkali-soluble resin The alkali-soluble resin that can be used in the present invention is not particularly limited. For example, the resin is a first resin containing a repeating unit represented by the following chemical formula 6 and a repeating resin represented by the following chemical formula 7 At least one of the second resins including the unit may be included.

(In the formula, R ₁ ′ is a hydrogen atom or a methyl group, R ₂ ′ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₃ ′ is a hydrogen atom or a methyl group.)

The binder resin according to the present invention may further include, in addition to the first resin and the second resin, a repeating unit formed of another monomer known in the art. It may be a resin alone or a resin containing both the first resin and the second resin.

The first resin according to the present invention is not particularly limited as long as it includes a repeating unit represented by Chemical Formula 6, and may include, for example, a repeating unit represented by Chemical Formula 1-1 below.

(Wherein R ₄ , R ₅ , R ₆ and R ₇ are each independently hydrogen or a methyl group;
R ₈ is benzyl (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, (2-phenyl) phenoxyethoxy (meth) acrylate, 2-hydroxy- (2-phenyl) phenolpropyl (meth) ) Acrylate, 2-hydroxy- (3-phenyl) phenoxypropyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, (meth) styrene, vinyltoluene, vinylnaphthalene, N-benzylmaleimide, methyl (meth) acrylate, ethyl ( (Meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, meth A structure derived from a monomer selected from the group consisting of xetyleneethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate and tetrahydrofuryl (meth) acrylate,
R ₉ is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (7);
R ₁₀ represents (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2- (meth) acryloyl A structure derived from a monomer selected from the group consisting of oxyethyl succinate,
R ₁₁ is hydrogen or an alkyl group having 1 to 6 carbon atoms,
a = 20-60 mol%, b = 5-30 mol%, c = 10-50 mol%, d = 5-30 mol%. )

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

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

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

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

Since the second resin according to the present invention includes a repeating unit represented by the following Formula 7, a thermosetting reaction occurs through a ring-opening polymerization reaction between an epoxy functional group and a carboxylic acid in a post-bate step. The pattern formed of the resin composition can be formed more rigidly through radical polymerization of the first resin and a thermosetting reaction of the second resin.

The second resin according to the present invention is not particularly limited as long as it contains a repeating unit represented by Chemical Formula 7, and may include, for example, a repeating unit represented by Chemical Formula 2-1 below.

(Wherein R ₁₂ and R ₁₃ are each independently a hydrogen or a methyl group;
R ₁₄ is a structure derived from a monomer represented by the following formula (8):
R ₁₅ represents (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2- (meth) acryloyl A structure derived from a monomer selected from the group consisting of oxyethyl succinate,
e = 40-95 mol%, f = 5-60 mol%. )

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

(In the formula, R ₂₀ and R ₂₁ are each independently a hydrogen or a methyl group, and e = 50 to 95 mol% and f = 5 to 50 mol%.)

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

If necessary, the first resin and the second resin according to the present invention are independently formed of other monomers known in the art, in addition to the repeating units of Formula 1-1 and Formula 2-1. And may be formed of only the repeating units of Formula 2-1 and Formula 2-1.

When the first resin containing the repeating unit of Formula 6 and the second resin containing the repeating unit of Formula 7 are simultaneously used in the alkali-soluble resin according to the present invention, the mixing weight ratio is 20:80 to 80:20. And preferably 30:70 to 70:30. In the above range, the most excellent adhesion, developability and T / B ratio can be exhibited.

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

Although the content of the alkali-soluble resin is not particularly limited, for example, it can be included in an amount of 10 to 80 parts by weight, preferably 20 to 60 parts by weight, based on 100 parts by weight of the total solid content of the composition. Can be When contained in the above range, the solubility in a developer is sufficient, the developability is excellent, the adhesion to the lower substrate is good, and a photocurable pattern having excellent mechanical properties can be formed. .

Photopolymerizable compound The photopolymerizable compound used in the photosensitive resin composition of the present invention can increase the crosslink density during the production process and enhance the mechanical properties of the photocurable pattern.

As the photopolymerizable compound usable in the present invention, those used in the art can be used without any particular limitation. For example, monofunctional monomers, difunctional monomers and other polyfunctional monomers can be used. It is a body and its type is not particularly limited, but the following compounds can be taken as examples.

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

The content of the photopolymerizable compound is not particularly limited. For example, the content of the photopolymerizable compound may be 30 to 80 parts by weight, preferably 40 to 60 parts by weight, based on 100 parts by weight of the total solid content of the composition. Good. When the content of the photopolymerizable compound is within the above range, the adhesiveness to the lower base material is good, the durability can be excellent, and the developability of the composition can be improved.

Photopolymerization initiator A photopolymerization initiator that can be used in the present invention can be used without any particular limitation as long as it is a compound that can polymerize a photopolymerizable compound, for example, a triazine-based compound, One or more compounds selected from the group consisting of acetophenone-based compounds, biimidazole-based compounds, and oxime compounds can be used. The photosensitive resin composition containing the photopolymerization initiator has high sensitivity, and the strength and surface smoothness of a spacer pattern formed using this composition are improved.

In addition, other photopolymerization initiators ordinarily used in this field may be additionally used as long as the effects of the present invention are not impaired. Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds. These can be used alone or in combination of two or more.

Further, a photopolymerization initiator having a group capable of causing a chain transfer with the photopolymerization initiator may be used. Examples of such a photopolymerization initiator include those described in Japanese Patent Publication No. 2002-544205.

Further, in the present invention, the photopolymerization initiator may be used in combination with a photopolymerization initiation auxiliary agent. It is preferable to use a photopolymerization initiation auxiliary agent in combination with the photopolymerization initiator, since the photosensitive resin composition containing these can further increase the sensitivity and improve the productivity when forming the spacer.

As the photopolymerization initiation aid, amine compounds and carboxylic acid compounds are preferably used.
Although the content of the photoinitiator is not particularly limited, for example, it may be included in 0.1 to 10 parts by weight based on 100 parts by weight of the entire photosensitive resin composition on a solid content basis, preferably 0.5 to 7. Satisfying the above range is preferable because the sensitivity of the photosensitive resin composition is increased, and the strength and smoothness of the spacer formed using this composition are improved.

Solvent The solvent can be used without any particular limitation as long as it is commonly 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; Glycol alkyl ether propionates; butyl diol monoalkyl ethers; butane diol monoalkyl ether acetates; butane diol monoalkyl ether propionates; dipropylene glycol dialkyl ethers; aromatic hydrocarbons; ketones; And esters; cyclic esters and the like. The solvents exemplified here may be used alone or in combination of two or more.

The above-mentioned solvent is preferably alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, ethyl 3-ethoxypropionate, or 3-methoxypropionic acid in consideration of coating properties and drying properties. Esters such as methyl can be preferably used, and more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, and 3-methoxy Methyl propionate and the like may be used.

The solvent may be included in an amount of 40 to 90 parts by weight, preferably 50 to 85 parts by weight, based on 100 parts by weight of the photosensitive resin composition containing the solvent. When the content of the solvent is in the above range, the applicability becomes good when applied with a coating apparatus such as a spin coater, a slit & spin coater, a slit coater (sometimes also referred to as a die coater or a curtain flow coater) or an ink jet. Therefore, it is preferable.

Additives The photosensitive resin composition according to the present invention may contain, if necessary, a filler, another polymer compound, a curing agent, a leveling agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an agglomeration inhibitor. And an additive such as a chain transfer agent.

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

The photo-cured pattern produced from the photosensitive resin composition can be controlled in CD-Bias, and is excellent in the value of T / B ratio, developability, adhesion, and mechanical properties. As a result, it is used for various patterns in an image display device, for example, an adhesive layer, an array flattening film, a protective film, an insulating film pattern, and is used for a photoresist, a black matrix, a column spacer pattern, and the like. In particular, it is very suitable as a spacer pattern.

An image display device having such a photocurable pattern or using the pattern during a manufacturing process includes a liquid crystal display device, an OLED, a flexible display, and the like, but is not limited thereto. All applicable image display devices known in the art can be exemplified.

The method for producing the photocurable pattern according to the present invention is not particularly limited, and may be a method known in the art. For example, the photosensitive resin composition of the present invention described above may be applied on a substrate, and (After the development step is performed in accordance with the above), a photocurable pattern is formed.

Hereinafter, preferred examples will be presented to assist the understanding of the present invention. However, these examples are merely illustrative of the present invention, and do not limit the scope of the appended claims. It will be apparent to those skilled in the art that various changes and modifications to the embodiments can be made within the scope of the technical idea, and such variations and modifications should also belong to the appended claims. .

Production example Production example 1. Synthesis of Alkali-Soluble Resin (First Resin (A-1)) Nitrogen was fed at 0.02 L / min into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to make a nitrogen atmosphere, and propylene glycol monomethyl was added. After introducing 200 g of ether acetate and heating to 100 ° C., 61.6 g (0.35 mol) of benzyl methacrylate and 22.0 g (0.10 mol) of tricyclo [5.2.02,6] decanyl methacrylate After adding 47.3 g (0.55 mol) of methacrylic acid, the mixture is stirred. Thereafter, a solution obtained by adding 3.6 g of 2,2′-azobis (2,4-dimethylvaleronitrile) to a mixture containing 150 g of propylene glycol monomethyl ether acetate was dropped into the flask over 2 hours from a dropping funnel, and the mixture was heated at 100 ° C. for 5 hours. Stirring was continued for an additional hour.

Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 42.6 g of glycidyl methacrylate [0.30 mol (55 mol% based on methacrylic acid used in this reaction)] was charged into the flask. The reaction was continued for an hour to obtain an unsaturated group-containing resin A-1 having an acid value of solid of 104 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 30,400, and the molecular weight distribution (Mw / Mn) was 2.4.

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

Production Example 2. Synthesis of Alkali-Soluble Resin (Second Resin (A-2)) Nitrogen was flowed into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer at a flow rate of 0.02 L / min. 150 g of ether was added and heated to 70 ° C. with stirring. Subsequently, 210.2 g (0.95 mol) of a mixture of the following chemical formulas 6-1 and 6-2 (molar ratio: 50:50) and 14.5 g (0.17 mol) of methacrylic acid were mixed with 150 g of diethylene glycol methyl ethyl ether. And the solution was dispensed.

After the prepared solution was dropped into the flask using a dropping funnel, 27.9 g (0.11 mol) of polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was added to diethylene glycol methyl ethyl ether. The solution dissolved in 200 g was dropped into the flask over 4 hours using a separate dropping funnel. After completion of the dropwise addition of the polymerization initiator solution, the temperature was maintained at 70 ° C. for 4 hours, and then cooled to room temperature, and the solid weight was 41.6% by mass, and the acid value was 65 mg-KOH / g (solid content conversion). A solution of the union (resin A-2) was obtained.
The weight average molecular weight Mw of the obtained resin A-2 was 8,300, and the molecular weight distribution was 1.85.

Production Example 3 As a synthetic monomer for the alkali-soluble resin (A-3), 47.3 g (0.55 mol) of methacrylic acid, 61.7 g (0.35 mol) of benzoyl methacrylate, and tricyclo [5.2.1.02, 6] Performed in the same manner as in Production Example 1 except that 22.0 g (0.10 mol) of decanyl methacrylate was used, the stirring time was 7 hours after the addition of the initiator, and no glycidyl methacrylate was added. .
After completion of the reaction, a resin A-3 having an acid value of 134 mgKOH / g of solid content was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 22,700, and the molecular weight distribution (Mw / Mn) was 2.5.

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

A: Alkaline binder resin A-1: Alkaline binder resin of Production Example 1 A-2: Alkaline binder resin of Production Example 2 A-3: Alkaline binder resin of Production Example 3 B: Dipentaerythritol hexaacrylate (KAYARAD DPHA, Japan) Chemical Co., Ltd.)
C: Photopolymerization initiator C-1: Biimidazole compound ([chemical formula a])
C-2: Oxime ester compound ([chemical formula b])
D: Thiol-based additive D-1:

D-2:
D-3:
D-4:
D-5:
E: UV absorber E-1:
E-2:
E-3:
E-4:
E-5:
E-6:
E-7:
E-8:
F: Additive (antioxidant)
4,4'-butylidenebis [6-tert-butyl-3-methylphenol] (BBM-S. Sumitomo Fine Chemical)
G: Solvent propylene glycol monomethyl ether acetate: diethylene glycol methyl ethyl ether (6: 4 volume ratio)

Test method A glass substrate (Eagle 2000; manufactured by Corning Incorporated) having a length and width of 2 inches was washed sequentially with a neutral detergent, water and alcohol, and then dried. The photosensitive resin compositions prepared in Examples and Comparative Examples were spin-coated on the glass substrate, respectively, and then pre-baked at 90 ° C. for 125 seconds using a hot plate. After cooling the prebaked substrate to room temperature, the distance between the prebaked substrate and the quartz glass photomask is set to 150 μm, and an exposure amount of 60 mJ / cm ² (based on 365 nm) using an exposure device (UX-1100SM; manufactured by Ushio Corporation). Was irradiated with light. At this time, a photomask in which the following pattern was formed on the same plane was used.

It has an octagonal opening (Hole pattern) which is a 14 μm octagonal pattern, the interval between them is 100 μm, and after light irradiation, contains 0.12% of nonionic surfactant and 0.04% of potassium hydroxide The coating film was immersed in an aqueous developer at 25 ° C. for 60 seconds for development, washed with water, and post-baked in an oven at 100 ° C. for 1 hour. The patterns thus obtained were evaluated for physical properties as follows, and the results are shown in Table 2 below.

(1) Measurement of the width ratio above and below the pattern (T / B ratio)
The obtained Dot pattern is observed with a three-dimensional shape measuring apparatus (SIS-2000 system; manufactured by SNUPrecision), and a point that is 5% of the total height from the floor of the pattern is a Bottom CD (a), and a point from the floor is the whole. A point at 95% of the height is defined as Top CD (b), and the value obtained by dividing the length of (b) by the length of (a) and multiplying by 100 (= b / a × 100) is obtained. It was defined as T / B ratio.

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

(3) Measurement of Adhesion Developing adhesion is a measure of the degree to which a pattern generated using a mask to which a half-tone mask (Half-tone Mask) having a transmittance of 25% is applied adheres to a substrate. In the case where 100% of the patterns formed with a thickness of 3 μm by using a photomask provided with 1000 Dot patterns each having an interval of 1 μm from 5 μm to 20 μm and having a thickness of 5 μm to 20 μm remain without missing, The actual size was measured for the line width using a three-dimensional shape measuring instrument SIS-2000 manufactured by SNU Precision. The value of the pattern line width was defined as the value of the Bottom CD at a point 5% of the total height from the floor of the pattern. The smaller the minimum pattern size remaining without missing, the better the development adhesion.

(4) Evaluation of Residual Film Ratio The resin compositions of Examples and Comparative Examples were applied to a substrate, spin-coated, and then pre-baked at 90 ° C. for 125 seconds using a hot plate. After cooling the prebaked substrate to room temperature, the entire surface of the coating film was irradiated with light at an exposure dose of 60 mJ / cm ² (based on 365 nm) using an exposure device (UX-1100SM; manufactured by Ushio Corporation).

After light irradiation, the coating film is immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 60 seconds to develop the film, washed with water, and then washed in an oven. At 230 ° C. for 30 minutes.

At this time, the film thickness after the exposure and the film thickness after the completion of the post-baking step were measured, and the residual film ratio of the development was measured using the following equation.
The higher the residual film ratio, the better the performance.

(5) Evaluation of Mechanical Properties (Overall Displacement and Recovery Ratio) In the cured films of Examples and Comparative Examples obtained above, a pattern having a Bottom line width of 14 μm was obtained by using a dynamic ultra-micro hardness tester (HM-2000; The total displacement (μm) and the elastic displacement (μm) were measured using Helmut Fischer GmbH + Co.KG) under the following measurement conditions, and the recovery rate (%) was determined as follows using the measured values. Calculated. It was determined that the smaller the total displacement and the larger the recovery rate, the better.

Recovery rate (%) = [elastic displacement (μm)] / [total displacement (μm)] × 100
The measurement conditions are as follows.
Test mode; Load-Unload test test force; 50.0 mN
Load speed: 4.41 mN / sec
Maintenance time: 5 sec
Indenter: square pyramid rod indenter (50 μm diameter)

Referring to Table 2, it was confirmed that, in the example using the photosensitive resin composition according to the present invention, a pattern having a small size was embodied as a whole, and CB-Bias could be controlled. Was completed.

Further, it was confirmed that the examples of the present invention were excellent in the value of the T / B ratio of the pattern, the adhesion to the substrate was improved, and the developability was good.

On the other hand, in the case of the comparative example using no thiol-based additive and ultraviolet absorber according to the present invention, the pattern size is large as a whole, and the deviation of CD-bias is large, which is not suitable for realizing high resolution. It can be confirmed that the mechanical properties are significantly lower than those of the examples.

Claims (10)

An alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a thiol-based compound having a value of the following formula 1 satisfying 20 to 35, and an ultraviolet absorber having a maximum absorption wavelength (λ _max ) of 335 to 365 nm And a solvent ,
The photosensitive resin composition, wherein the alkali-soluble resin includes at least one of a first resin including a repeating unit represented by the following Chemical Formula 6 and a second resin including a repeating unit represented by the following Chemical Formula 7 .
(In the formula, A is a value indicating the weight (g / mol) of the entire compound when the SH group is converted to 1 mol in the molecule, and B is the number (integer) of the SH groups present in the molecule. is there.)
(In the formula, R ₁ ′ is a hydrogen atom or a methyl group, R ₂ ′ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₃ ′ is a hydrogen atom or a methyl group. ) The photosensitive resin composition according to claim 1, wherein the value of Formula 1 is from 20 to 25. The photosensitive resin composition according to claim 1, wherein the thiol-based compound is at least one selected from compounds represented by the following Chemical Formulas 1 and 2.
(Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R _9, and R ₁₀ are each independently a hydrogen atom or a straight chain having 1 to 5 carbon atoms. Or a branched-chain alkyl group.) The photosensitive resin composition according to claim 1, wherein the ultraviolet absorber is at least one selected from compounds represented by the following chemical formulas 3 to 5.
(Wherein, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ each independently represent a halogen atom, a carbon number An alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a thioether group, a cycloalkyl group having 3 to 12 carbon atoms, a bicycloalkyl group having 4 to 12 carbon atoms, a tricycloalkyl group having 6 to 12 carbon atoms, or An aryl group having 6 to 20 carbon atoms, wherein the aryl group is a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a thioether group, a cycloalkyl group having 3 to 12 carbon atoms, (It can be substituted with at least one substituent selected from the group consisting of a bicycloalkyl group having 4 to 12 carbon atoms and a tricycloalkyl group having 6 to 12 carbon atoms.) The photosensitive resin composition according to claim 1, wherein the ultraviolet absorber is contained in an amount of 30 to 90 parts by weight based on 100 parts by weight of the thiol-based compound. The photosensitive resin composition according to claim 1, wherein the thiol-based compound is contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the total solid content of the composition. The photosensitive resin composition according to claim 1, wherein the ultraviolet absorber is contained in an amount of 0.001 to 3 parts by weight based on 100 parts by weight of the total solid content of the composition. Photocured pattern produced in the photosensitive resin composition according to any one of claims 1-7. The photocurable pattern, the adhesive layer, an array flattening film pattern, the protective film pattern, an insulating film pattern, a photoresist pattern, a color filter pattern is selected from the group consisting of a black matrix pattern and a column spacer pattern, claim 8 Light curing pattern described in 1. An image display device comprising the photocurable pattern according to claim 8 .