KR20220091266A - Photosensitive resin composition, photocurable pattern and display device formed from the same - Google Patents

Abstract

The present invention relates to a thiol compound having an ester bond by including a thiol compound (A) containing an ether bond, an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E) It relates to a photosensitive resin composition capable of producing a pattern having excellent water resistance, heat resistance, alkali resistance and chemical resistance as well as excellent storage stability compared to a resin composition having .

Description

Photosensitive resin composition, photocurable pattern and display device formed therefrom

The present invention relates to a photosensitive resin composition, a photocurable pattern formed therefrom, and a display device.

In the display field, the curable resin composition is used to form various cured patterns such as a photoresist, an insulating film, a protective film, a black matrix, and a column spacer. Specifically, the curable resin composition is selectively exposed and developed by a photolithography process to form a desired pattern. In this process, in order to improve the yield in the process and improve the physical properties of the target, the curable resin composition having high sensitivity is is being demanded The curable resin composition may be divided into a thermosetting resin composition and a photosensitive photosensitive resin composition according to a curing mechanism.

Specifically, the pattern formation of the photosensitive resin composition is caused by photolithography, that is, a change in polarity of a polymer and a crosslinking reaction caused by a photoreaction. In particular, the pattern formation utilizes a characteristic of changing solubility in a solvent such as an aqueous alkali solution after exposure.

The photosensitive resin composition is selectively exposed and developed by a photolithography process to form a desired photocurable pattern. In this process, in order to improve the yield in the process and to improve the physical properties of the target, photosensitivity having excellent chemical and physical properties A resin composition is calculated|required.

Recently, the use of a touch screen having a touch panel has been explosively increased, and recently, a flexible touch screen has been receiving great attention. Accordingly, materials such as various substrates used for touch screens must also have flexible characteristics, and the available materials are also limited to flexible polymer materials, so the manufacturing process is also required to be performed under milder low-temperature conditions. .

Accordingly, the curing conditions of the photosensitive resin composition are also required for low-temperature curing in the conventional high-temperature curing. However, the low-temperature curing conditions have problems of reduced reactivity and reduced durability of the formed pattern. In addition, not only the heat resistance is lowered, but in particular, by exposure to the solvent used in the post-process, the chemical resistance deterioration such as swelling and adhesion decrease due to surface penetration, damage to the pattern surface, and the difficulty of lowering adhesion to the underlying substrate existed.

In the case of Korean Patent Registration No. 10-1464312, a photosensitive resin composition that can be cured at a low temperature is disclosed, but curing is not initiated at less than 100 ° C. There is a limitation that it cannot be used when forming a pattern on

Republic of Korea Patent Registration No. 10-1464312 (2014.11.21. Announcement)

In order to solve the conventional problems, the present invention not only exhibits excellent water resistance, heat resistance, alkali resistance and chemical resistance characteristics even under low temperature curing process conditions, but also increases the developing speed so that the exposed and unexposed areas are clearly due to the excellent contrast ratio in the developing process. A photosensitive resin composition that exhibits a ratio, can exhibit excellent adhesion to the underlying substrate even when exposed to a stripper in a post-process, does not cause surface damage, swelling, or film shrinkage, and can produce a pattern with excellent storage stability; An object of the present invention is to provide a photocurable pattern and a display device formed therefrom.

In order to achieve the above object, the present invention provides a thiol compound (A) comprising an ether bond represented by Formula 1 or Formula 2, an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and A photosensitive resin composition comprising a solvent (E) is provided:

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

R1 is a straight-chain or branched alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups (-SH),

R2 to R4 are each independently hydrogen or a linear or branched alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups (-SH).

In addition, the present invention provides a photocurable pattern formed from the photosensitive resin composition.

In addition, the present invention provides a display device including the photocurable pattern.

Since the photosensitive resin composition of the present invention includes a thiol compound having an ether bond, it can exhibit excellent properties in water resistance, heat resistance, alkali resistance and chemical resistance as compared to a resin composition having a conventional thiol compound having an ester bond.

In addition, the photosensitive resin composition according to the present invention has excellent storage stability, and exhibits a ratio of the development speed so that the exposed and unexposed parts are clear due to the excellent contrast ratio in the developing process even in the low-temperature curing process. It can exhibit excellent adhesion to the underlying substrate even when it is used, and it is possible to manufacture a pattern in which surface damage, swelling, or film shrinkage does not occur.

The present invention relates to a photosensitive resin composition comprising a thiol compound (A) containing an ether bond represented by a specific formula (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E) , to a photocurable pattern and a display device formed therefrom.

The photosensitive resin composition according to the present invention, a photocurable pattern and a display device formed therefrom include a thiol compound having an ether bond, and thus have water resistance, heat resistance, alkali resistance and chemical resistance compared to a resin composition having a thiol compound having an ester bond. This excellent characteristic can be exhibited.

In addition, the photosensitive resin composition according to the present invention has excellent storage stability, and exhibits a ratio of the development speed so that the exposed and unexposed areas are clear due to the excellent contrast ratio in the developing process even in the low-temperature curing process. It can exhibit excellent adhesion to the underlying substrate even when it is used, and it is possible to manufacture a pattern in which surface damage, swelling, or film shrinkage does not occur.

Hereinafter, the present invention will be described in detail.

<Photosensitive resin composition>

The photosensitive resin composition according to the present invention includes a thiol compound (A) containing an ether bond, an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E).

Thiol compound (A)

The thiol compound of this invention contains the thiol compound containing an ether bond.

Specifically, the thiol compound of the present invention includes a thiol compound represented by the following formula (1) or formula (2).

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

R1 to R4 may each independently be hydrogen or an alkyl group, and at least one of them has a thiol group (-SH).

Preferably, R1 is a straight-chain or branched alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups (-SH), and more preferably, a straight-chain or branched chain alkyl group having a thiol group (-SH) at the terminal having 1 carbon number. to 10 alkyl groups.

Preferably, R2 to R4 are each independently hydrogen or a linear or branched alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups (-SH), more preferably, each independently, hydrogen or a terminal It is a linear or branched C1-C10 alkyl group having an thiol group (-SH).

As used herein, the alkylene group (alkylene group) refers to a straight-chain or branched divalent hydrocarbon composed of 1 to 20 carbon atoms, for example, methylene, ethylene, n-propylene, i-propylene, etc. are included, but It is not limited.

In addition, in one embodiment of the present invention, the photosensitive resin composition of the present invention may include a thiol compound (A) represented by the following Chemical Formula 3 or Chemical Formula 4.

[Formula 3]

In Formula 3,

R5 is each independently an alkylene group having 1 to 10 carbon atoms, m1 and n1 are integers of 1 to 3, and m1 + n1 = 4.

[Formula 4]

In Formula 4,

R5 is each independently an alkylene group having 1 to 10 carbon atoms, m2, m3, n2 and n3 are each independently an integer of 1 to 3, m2+n2=3, and m3+n3=3.

Pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) and Compounds such as pentaerythritol tetrakis (3-mercaptobutyrate) all contain an ester bond in their molecular structure. In the case of a thiol compound containing such an ester bond, the effect of water resistance and alkali resistance is remarkably reduced because it is highly reactive to solvent decomposition, and properties such as long-term storage stability and aging stability may also occur.

However, in the case of the photosensitive resin composition including the thiol compound having an ether bond according to the present invention, it may have excellent properties such as water resistance, heat resistance, alkali resistance and chemical resistance due to high solvent decomposition resistance.

In addition, the photosensitive resin composition of the present invention can exhibit excellent adhesion to the substrate due to the flexible skeleton of the thiol compound including an ether bond, and the ratio of the development speed to the exposed and unexposed areas due to the excellent contrast ratio even in the low temperature process , and there is no surface damage, swelling, or film shrinkage even when exposed to a stripper in the post-process, and excellent storage stability can be obtained.

The thiol compound of the present invention may be included in an amount of 1 to 25% by weight, preferably 1 to 9% by weight, more preferably 1 to 6% by weight based on the total weight of the photosensitive resin composition. When the content is less than the above content, swelling and film shrinkage may occur when exposed to the stripper in the subsequent process. There is a problem in that residues are generated.

Alkali-soluble resin (B)

The alkali-soluble resin included in the photosensitive resin composition according to the present invention is a component that imparts solubility to the alkali developer used in the developing process, and can be used without limitation as long as it is soluble in the alkali developer. The alkali-soluble resin is preferably prepared by copolymerizing (b1) an ethylenically unsaturated monomer having a carboxyl group in order to have solubility in the alkali developer used in the developing treatment step for forming the pattern.

(b1) an ethylenically unsaturated monomer having a carboxyl group

Specific examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and anhydrides of the dicarboxylic acids; Polymer mono(meth)acrylates having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate, etc. are mentioned, and acrylic acid and methacrylic acid are preferable.

In addition, the alkali-soluble resin can be prepared by polymerizing the ethylenically unsaturated monomer having a carboxyl group and an unsaturated monomer copolymerizable with (b2).

(b2) copolymerizable unsaturated monomers

Specific examples of the copolymerizable unsaturated polymerization monomer include,

glycidyl methacrylate which is an unsaturated monomer having a glycidyl group;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N -ethylenically unsaturated monomers having a hydroxyl group, such as hydroxyethyl (meth)acrylates such as hydroxyethyl acrylamide;

Styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinyl Aromatic vinyl compounds, such as benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether;

N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m -N-substituted maleimide compounds, such as methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, and N-p-methoxyphenylmaleimide;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl (meth) acrylate, 2- alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate and isobornyl (meth)acrylate;

aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate;

3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane; 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. of unsaturated oxetane compounds; and the like, but is not limited thereto.

Each of the above copolymerizable unsaturated monomers may be used alone or in combination of two or more.

The alkali-soluble resin according to the present invention may affect the patterning process of the photosensitive resin composition depending on the acid value and molecular weight.

The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be obtained by titration using an aqueous potassium hydroxide solution, and may affect pattern formation during the process.

The alkali-soluble resin may have an acid value of 10 to 200 mgKOH/g, preferably 20 to 100 mgKOH/g. When the acid value is in the above range, the solubility in the developer is improved, so that the non-exposed portion is easily dissolved and the sensitivity is increased, so that the pattern of the exposed portion remains at the time of development, which is preferable, thereby improving the film remaining ratio.

The weight average molecular weight of the alkali-soluble resin (eg, measured by gel permeation chromatography (GPC) using polystyrene as a standard material) is 1,500 to 30,000 in terms of improved reactivity and chemical resistance of the photosensitive resin composition under low temperature conditions. may be, preferably 1,500 to 10,000. When the above weight average molecular weight range is satisfied, the CD-Bias of the pattern is implemented in an appropriate range to form a pattern having excellent resolution, and chemical resistance and pencil hardness of the pattern can also be improved. On the other hand, when the weight average molecular weight of the alkali-soluble resin exceeds 30,000, the molecular weight is excessively large, and compatibility with other components of the photosensitive resin composition is lowered, so that whitening of the coating film may occur in the developing step, and the line width of the pattern is also increased. As a result, the CD-Bias characteristic may be deteriorated.

The alkali-soluble resin according to the present invention may be included in an amount of 8 to 80% by weight based on the total weight of the photosensitive resin composition. When the alkali-soluble resin is included in the above range, the solubility in the developer is sufficient, so that it is difficult to generate a developing residue on the substrate of the non-pixel portion, and it is difficult to reduce the film of the pixel portion of the exposed portion during development, so that the non-pixel portion is omitted It is preferable because the property tends to be good.

Photopolymerizable compound (C)

The photopolymerizable compound is a compound that can be polymerized by the action of the photopolymerization initiator (D) below, and a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer may be used, and preferably a bifunctional or more polyfunctional monomer may be used. .

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, or N-vinylpi Rollidone, and the like, but is not limited thereto.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. , bis(acryloyloxyethyl)ether of bisphenol A, or 3-methylpentanediol di(meth)acrylate, but is not limited thereto.

Specific examples of the polyfunctional compound 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) Monomers or oligomers such as acrylate or dipentaerythritol hexa(meth)acrylate, but not limited thereto.

The photopolymerizable compound of the present invention may be included in an amount of 1 to 70% by weight, preferably 9 to 70% by weight, based on the total weight of the photosensitive resin composition. When the photopolymerizable compound is included in the above range, pattern properties may be favorably formed, may have excellent hardness and durability, and developability of the composition may be improved.

Photoinitiator (D)

The photopolymerization initiator (D) of the present invention initiates a radical reaction of the photosensitive resin composition to cause curing and improve sensitivity.

The photopolymerization initiator is typically an acetophenone-based compound, a benzophenone-based compound, a biimidazole-based compound, a triazine-based compound, an oxime ester-based compound, and a thioxanthone-based compound.

In the present invention, the photopolymerization initiator may be used alone or in mixture of two or more, and it is preferable to use one or more oxime ester-based compounds.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-( 2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, and the like.

Examples of the benzophenone-based compound include benzophenone, 2,2'-hydroxy-4,4'-dimethoxybenzophenone, methyl o-benzoylbenzoate, 4-phenylzophenone, and 4-benzoyl-4 '-methyldiphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1; 2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimi Dazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl) )-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5 '-Tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4, 6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc. are mentioned.

Examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl). )-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5- Triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloro methyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino) -2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4 dimethoxyphenyl)ethenyl]-1,3, 5-triazine etc. are mentioned.

Examples of the oxime ester compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, 1,2-octadione, and-1-(4-phenylthio)phenyl. , -2-(o-benzoyloxime), ethanone, -1-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-,1-(o-acetyloxime), and the like; Commercially available products include CGI-124 (Ciba Geig), CGI-224 (Ciba Geig), Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (Adeka) , NCI-831 (Adeka Corporation), and the like.

As the thioxanthone-based compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Chloro-4-propoxythioxanthone etc. are mentioned.

The photopolymerization initiator (D) may further include a photopolymerization initiation auxiliary agent. When the photopolymerization initiator (D) further includes a photopolymerization initiation auxiliary agent, the sensitivity of the photosensitive resin composition containing them may be further increased, thereby improving the degree of curing and polymerization efficiency.

As the photopolymerization initiation adjuvant, for example, at least one compound selected from the group consisting of carboxylic acid and sulfonic acid compounds may be preferably used.

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

The sulfonic acid compound is a generic term for compounds having a sulfonic acid group (-SO3H), cyclic or chain hydrocarbon-based sulfonic acid compounds such as methanesulfonic acid, aromatic sulfonic acids such as benzenesulfonic acid and toluenesulfonic acid, and inorganic sulfonic acid compounds such as aminosulfonic acid; It may include at least one selected from the group consisting of halosulfonic acid and sulfamic acid.

The photopolymerization initiator (D) according to the present invention may be included in an amount of 1 to 10 wt%, preferably 2 to 8 wt%, based on the total weight of the photosensitive resin composition. When included within the above range, it is easy to control the pattern formation, and it is preferable in terms of curing degree and straightness improvement.

In addition, when the photopolymerization initiation adjuvant is further included, it is usually 10 moles or less, preferably 0.01 to 5 moles per 1 mole of the photopolymerization initiator. When the photopolymerization initiation auxiliary agent is used within the above range, the polymerization efficiency is increased, the sensitivity of the photosensitive resin composition is further increased, and the effect of improving productivity can be expected.

Solvent (E)

In the present invention, the solvent (E) may be used without any particular limitation on organic solvents commonly used in the art. Examples of the solvent (E) include ethers, acetates, aromatic hydrocarbons, ketones, alcohols, and esters.

For example, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Diethylene glycol dialkyl ethers such as ethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene alkylene glycol alkyl ether acetates such as glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; methyl ethyl ketone; Ketones such as acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin, ethyl 3-ethoxypropionate, 3-methyl Esters, such as methyl oxypropionate, Cyclic esters, such as (gamma)-butyrolactone, etc. are mentioned.

Preferably, an organic solvent having a boiling point of 100 to 200° C. may be used in order to increase the applicability and drying efficiency of the solvent, and more preferably, alkylene glycol alkyl ether acetates, ketones, 3-ethoxypropionate ethyl or , 3-methoxy methyl propionate, etc. can be used, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropionate ethyl, 3-methoxypropionic acid methyl and the like can be used. These solvents can be used individually or in mixture of 2 or more types, respectively.

The content of the solvent may be included in a residual amount such that the total weight of the photosensitive resin composition is 100% by weight. Specifically, in the present invention, "residual amount" means a remaining amount such that the total weight of the composition further including the essential components and other additional components of the present invention becomes 100% by weight, and due to the meaning of the "residual amount", the It is not limited to the absence of additional ingredients in the composition. For example, the solvent may be included in an amount of 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the photosensitive resin composition, but is not limited thereto.

Polyfunctional thiol compound (F)

If necessary, the photosensitive resin composition of the present invention may further include a polyfunctional thiol compound (F).

The polyfunctional thiol compound (F) may function to further improve the crosslinking density to further improve the durability of the photocurable pattern and adhesion to the substrate, and to prevent yellowing at high temperatures.

The polyfunctional thiol compound may be a 2 to 9 functional thiol compound having an ester bond.

Examples of the polyfunctional thiol compound include pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), and dipentaerythritol hexakis (3-mercaptopropionate). cionate) and pentaerythritol tetrakis (3-mercaptobutyrate).

The polyfunctional thiol compound (F) may be included in an amount of 0.1 to 10 wt%, preferably 1 to 8 wt%, based on the total weight of the photosensitive resin composition. When included within the above range, the surface hardening of the coating film can be improved with excellent photosensitive properties, thereby exhibiting an excellent residual film rate with respect to an alkali developer.

Additive (G)

In addition, the photosensitive resin composition according to the present invention may further include known additives for various purposes. Preferably, a silane coupling agent or a leveling agent may be further included in order to improve coating properties and adhesion.

The silane coupling agent is for increasing adhesion to the substrate, and may include a silane coupling agent having a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and combinations thereof.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)-silane, N-(2-aminoethyl)-3-aminopropylmethyl Dimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyl Triethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-ethoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxy silane, 3-methacryloxypropyltrimethoxysilane, or 3-mercaptopropyltrimethoxysilane may be used, but is not limited thereto.

The leveling agent is added to improve the smoothness and applicability of the coating film when the composition is applied, and a silicone leveling agent, a fluorine-based leveling agent, and an acrylic-based leveling agent may be used.

The silicone-based leveling agent may include a leveling agent having a siloxane bond in a molecule, and the fluorine-based leveling agent may include a leveling agent having a fluorocarbon chain in the molecule.

Commercial products of the leveling agent include BYK-323, BYK-331, BYK-333, BYK-337, BYK-373, BYK-375, BYK-377, BYK-378 by Chemi, TEGO Glide 410, TEGO Glide by Daegu. 411, TEGO Glide 415, TEGO Glide 420, TEGO Glide 432, TEGO Glide 435, TEGO Glide 440, TEGO Glide 450, TEGO Glide 455, TEGO Rad 2100, TEGO Rad 2200N, TEGO Rad 2250, TEGO Rad 2300, TEGO Rad 3M's FC-4430, FC-4432, etc. can be used.

The additive according to the present invention may be included in an amount of 0.1 to 10% by weight, preferably 1 to 8% by weight, based on the total weight of the photosensitive resin composition. When included within the above range, it is possible to achieve the purpose of improving adhesion or coating properties with the lower substrate without impairing the physical properties of the photosensitive resin composition.

<Photocuring pattern>

The present invention includes a photocurable pattern formed on a substrate using a photosensitive resin composition.

The pattern according to the present invention may be prepared by a method known in the art, except that it is formed of the above-described photosensitive resin composition. In the photocurable pattern formation, the pattern may be formed by coating the above-described photosensitive resin composition on a substrate, then exposing and developing, and in this case, a pre-baking or post-baking process may be performed between each step. .

The photocurable pattern includes an array planarization layer pattern, a protective layer pattern, an insulating layer pattern, a photoresist pattern, a black matrix pattern, a column spacer pattern, a black column spacer, a color resist pattern, a pattern including a scattering body, and a pattern including quantum dots. It may be a photocuring pattern selected from the group.

The photocurable pattern according to the present invention uses a polyfunctional thiol compound having an ether structure to prevent radicals from receiving oxygen hindrance during the exposure process, thereby forming a coating film exhibiting an excellent development film remaining rate. When exposed to the stripper, there is an advantage in that it is possible to suppress the decomposition of the solvent, thereby preventing swelling or shrinkage of the coating film, and deterioration in adhesion.

<Display device>

The present invention provides a display device including a photocurable pattern prepared from the above-described photosensitive resin composition.

The display device is specifically, a liquid crystal display (liquid crystal display device; LCD), an organic EL display (including an organic EL display device, OLED and QLED), a flexible display, a liquid crystal projector, a display device for a game machine, a portable terminal such as a mobile phone a display device, a display device for a digital camera, a display device for navigation, and the like, but is not limited thereto.

The display device may further include a configuration commonly used in the art except for having the photocurable pattern.

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

However, the following examples are provided to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

In addition, "%" and "part" indicating the content hereinafter are based on weight unless otherwise specified.

Synthesis Example 1: Synthesis of pentaerythritol tripropanethiol (A-1)

After putting 1.37 mol of pentaerythritol triallyl ether in a round flask, it heated to 40 degreeC. After 4.51 mol of thioacetic acid was added dropwise at a molar ratio of pentaerythritol triallyl ether to 1:3.3, the mixed liquid was stirred at 40° C. for 4 hours. After adding 560 g of a 20% aqueous ammonia solution to the reaction mass, the reaction was carried out at 55 °C for 15 hours. After separating the organic layer, 490 g of toluene and 350 g of a 5% sulfuric acid aqueous solution were added and washed, and the organic layer was separated and taken, and 350 g of water was added to the organic layer.

The organic layer was separated and concentrated to dryness, and pentaerythritol tripropanethiol (478 g, yield 98%) (referred to as PEPT) was synthesized as a colorless and transparent oil, and the results of NMR analysis are shown below.

<Pentaerythritol tripropanethiol NMR analysis result>

1H-NMR (400MHz, CDCl3): δ 1.35 (t,3H), δ 1.80-1.86 (m,6H), δ 2.55-2.61 (m, 6H), δ 2.79 (br, 1H), δ 3.40 (s, 6H), δ 3.48 (t, 6H), δ 3.65 (s, 2H)

Synthesis Example 2: Synthesis of dipentaerythritol tetrapropanethiol (A-2)

It was synthesized in the same manner as in Synthesis Example 1 except that thioacetic acid was added dropwise at a molar ratio of 1:4.4 by changing to dipentaerythritol tetraallyl ether instead of pentaerythritol triallyl ether of Synthesis Example 1.

Synthesis Example 3: Synthesis of dipentaerythritol pentapropanethiol (A-3)

It was synthesized in the same manner as in Synthesis Example 1 except that thioacetic acid was added dropwise at a molar ratio of 1:5.5 by changing to dipentaerythritol pentaallyl ether instead of pentaerythritol triallyl ether of Synthesis Example 1.

Synthesis Example 4: Synthesis of alkali-soluble resin (B)

120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of 2,2'-azobisisobutyronitrile, 10 g of isodecyl methacrylate, 5 g of acrylic acid, 35 g of glycidyl methacrylate, 50 g of vinyltoluene, and 3 g of n-dodecyl mercaptan were added, followed by nitrogen substitution.

After that, the temperature of the reaction solution was raised to 70 °C with stirring, and the reaction was carried out for 8 hours. The alkali-soluble resin thus synthesized had a solid content acid value of 58 mgKOH/g, and a weight average molecular weight Mw measured by GPC of about 7,450.

<Production of photosensitive resin composition>

According to the composition and parts by weight described in Table 1 below, photosensitive resin compositions according to Examples and Comparative Examples were prepared.

etheric bond
thiol compounds comprising polyfunctional thiol compound alkali
availability
Suzy photopolymerization
compound light curing
initiator solvent A-1 A-2 A-3 F-1 F-2 F-3 F-4 B C D E Example One 1.0 - - - - - - 9.5 12.5 2.0 75.0 2 - 1.0 - - - - - 9.5 12.5 2.0 75.0 3 - - 1.0 - - - - 9.5 12.5 2.0 75.0 4 2.0 - - - - - - 9.0 12.0 2.0 75.0 5 6.0 - - - - - - 8.0 9.0 2.0 75.0 6 2.0 - - 2.0 - - - 9.0 10.0 2.0 75.0 7 2.0 - - - 2.0 - - 9.0 10.0 2.0 75.0 8 2.0 - - - - 2.0 - 9.0 10.0 2.0 75.0 9 2.0 - - - - - 2.0 9.0 10.0 2.0 75.0 10 10.0 - - - - - - 6.0 7.0 2.0 75.0 11 - 10.0 - - - - - 6.0 7.0 2.0 75.0 12 - - 10.0 - - - - 6.0 7.0 2.0 75.0 comparative example One - - - 4.0 - - - 9.0 10.0 2.0 75.0 2 - - - - 4.0 - - 9.0 10.0 2.0 75.0 3 - - - - - 4.0 - 9.0 10.0 2.0 75.0 4 - - - - - - 4.0 9.0 10.0 2.0 75.0 5 - - - - - - - 10 13.0 2.0 75.0

- A-1: thiol compound according to Synthesis Example 1

- A-2: thiol compound according to Synthesis Example 2

- A-3: thiol compound according to Synthesis Example 3

- F-1: trimethylolpropane dipropanethiol (TMPT) having the following formula (a) structure, manufactured by SC Organic Chemical

- F-2: 1,4-bis (3-mercaptobutylyloxy) butane (1,4-bis (3-mercaptobutylyloxy) butane, manufactured by Showa Denko)

- F-3: dipentaerythritol hexakis (3-mercaptopropionate), manufactured by SC Organic Chemical

- F-4: glycoluril derivative (TS-G), manufactured by Shikoku Chemical

- B: alkali-soluble resin according to Synthesis Example 4

- C: dipentaerythritol hexaacrylate (KAYARAD DPHA), manufactured by Japan Explosives

- D: Irgacure OXE-01, manufactured by BASF

- E: propylene glycol monomethyl ether acetate, manufactured by Sigma-Aldrich

Experimental Example 1: Evaluation of the physical properties of the pattern

A 5×5 cm glass substrate (Eagle 2000; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol, and then dried. Each of the photosensitive resin compositions prepared in Examples and Comparative Examples were spin-coated on the glass substrate and then pre-baked at 80° C. for 120 seconds using a hot plate. After cooling the pre-baked substrate to room temperature, the distance from the quartz glass photomask was set to 50 μm, and the exposure machine (MA6; manufactured by Karl suss Co., Ltd.) was used at an exposure dose of 30 mJ/cm 2 (based on 365 nm) to light. was investigated.

In this case, a photomask having a 30 µm square pattern of square openings (Hole pattern) and a pattern having an interval of 100 µm formed on the same plane was used. After light irradiation, it was developed in a 2.38 wt% aqueous tetramethyl ammonium hydroxide solution for 60 seconds, washed with ultrapure water, and dried under nitrogen to form a pattern on the photosensitive resin composition layer. Post-bake in oven at 85° C. for 2 hours.

The following (1) to (4) physical property evaluation was performed on the pattern, the results are shown in Table 2 below, and the physical property evaluation of the following (5) to (6) is performed, and the results are shown in Table 3 shown in

(1) Residue evaluation

The presence or absence of residues in the hole pattern was evaluated with an optical microscope.

<Evaluation criteria>

No residue: ○

Residue: X

(2) moisture resistance evaluation

The pattern was stored in a chamber at a temperature of 25° C. and a humidity of 85% for 24 hours, respectively, to evaluate the change in film thickness before and after.

(3) Heat resistance evaluation

The pattern was placed in an oven at a temperature of 85° C. for 1 hour, respectively, and the film thickness change before and after was evaluated.

(4) Alkali resistance evaluation

The pattern was placed in a 2.38 wt% tetramethyl ammonium hydroxide aqueous solution for 5 minutes, respectively, and the film thickness change before and after was evaluated.

The film thickness change evaluation criteria in (2) to (4) are as follows:

<Evaluation criteria>

(double-circle): Film thickness change less than 1%

○: Film thickness change 1% or more, less than 2%

△: film thickness change 2% or more, less than 5%

X: film thickness change 5% or more

residue moisture resistance heat resistance alkali resistance Example 1 ○ ◎ ◎ ◎ Example 2 ○ ◎ ◎ ◎ Example 3 ○ ◎ ◎ ◎ Example 4 ○ ◎ ◎ ◎ Example 5 ○ ◎ ◎ ◎ Example 6 ○ ◎ ◎ ◎ Example 7 ○ ◎ ◎ ◎ Example 8 ○ ◎ ◎ ◎ Example 9 ○ ◎ ◎ ◎ Example 10 ○ ○ ○ ○ Example 11 ○ ○ ○ ○ Example 12 ○ ○ ○ ○ Comparative Example 1 X ○ ○ ○ Comparative Example 2 X ○ △ △ Comparative Example 3 X ○ ○ ○ Comparative Example 4 X ○ △ △ Comparative Example 5 ○ △ X X

(5) Evaluation of chemical resistance (adhesion)

The pattern was evaluated as the minimum area closely adhered to the line and space mask pattern after each of the patterns were immersed in the NMP aqueous solution for 6 minutes.

<Evaluation criteria>

10: Minimum adhesion line pattern mask width 10 μm

20: Minimum adhesion line pattern mask width 20 μm

30: Minimum adhesion line pattern mask width 30 μm

40: minimum adhesion line pattern mask width 40 μm

X: peeling occurs

(6) Chemical resistance (film thickness change) evaluation

The thickness change of the pattern before and after immersing the pattern in the NMP aqueous solution for 6 minutes, respectively, was measured.

Experimental Example 2: Storage stability evaluation

The photosensitive resin compositions prepared according to Examples and Comparative Examples were placed in an oven at 40° C., and the viscosity change after 24 hours was evaluated, as shown in Table 3 below.

<Evaluation criteria>

◎: Viscosity change less than 1%

○: Viscosity change 1% or more and less than 2%

△: Viscosity change 2% or more and less than 5%

X: Viscosity change 5% or more

adhesion change in film thickness storage stability Example One 10 0 ◎ 2 10 -0.01 ◎ 3 10 -0.03 ◎ 4 10 -0.01 ◎ 5 10 0 ◎ 6 10 0 ◎ 7 10 -0.01 ◎ 8 10 0.02 ◎ 9 10 0.01 ◎ 10 20 0.06 ○ 11 20 0.05 ○ 12 20 0.07 ○ comparative example One 50 -0.57 △ 2 50 -0.74 △ 3 50 -0.43 △ 4 50 -0.81 △ 5 peeling peeling ◎

Referring to the evaluation results in Tables 2 and 3, it can be seen that, in the case of the example containing the thiol compound having an ether bond according to the present invention, no residue is left, and moisture resistance, heat resistance and alkali resistance properties are excellent. In addition, it can be confirmed that the properties of chemical resistance and storage stability are also excellent.

On the other hand, when the thiol compound according to the present invention is out of the structure or contains a thiol compound containing an ester bond rather than an ether bond, a pattern residue is generated, and moisture resistance, heat resistance, alkali resistance and chemical resistance are poor. It could be confirmed, and it can be confirmed that the storage stability is also inferior to that of the Example.

Claims (9)

A thiol compound (A) containing an ether bond represented by Formula 1 or Formula 2, an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E) comprising , photosensitive resin composition:
[Formula 1]

[Formula 2]

In Formulas 1 to 2,
R1 is a straight-chain or branched alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups (-SH),
R2 to R4 are each independently hydrogen or a linear or branched alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups (-SH).
According to claim 1,
The thiol compound (A) is characterized in that represented by Formula 3 or Formula 4, the photosensitive resin composition:
[Formula 3]

In Formula 3,
R5 is an alkylene group having 1 to 10 carbon atoms,
m1 and n1 are each independently an integer of 1 to 3, and m1 + n1 = 4.
[Formula 4]

In Formula 4,
R5 is each independently an alkylene group having 1 to 10 carbon atoms,
m2, m3, n2 and n3 are each independently an integer of 1 to 3, m2+n2=3, and m3+n3=3.
The method of claim 1,
The thiol compound (A) is characterized in that included in 1 to 25% by weight based on the total weight of the photosensitive resin composition, the photosensitive resin composition.
The method of claim 1,
The alkali-soluble resin (B) has a weight average molecular weight (Mw) of 1,500 to 10,000, the photosensitive resin composition.
The method of claim 1,
The photosensitive resin composition, characterized in that the acid value of the alkali-soluble resin (B) is 20 mgKOH / g to 100 mgKOH / g.
According to claim 1,
The photosensitive resin composition, characterized in that it further comprises a 2 to 9 functional thiol compound containing an ester bond.
A photocurable pattern formed of the photosensitive resin composition of any one of claims 1 to 6.
8. The method of claim 7,
The photocurable pattern includes an array planarization layer pattern, a protective layer pattern, an insulating layer pattern, a photoresist pattern, a black matrix pattern, a column spacer pattern, a black column spacer, a color resist pattern, a pattern including a scattering body, and a pattern including quantum dots. A photocurable pattern, characterized in that at least one selected from the group.
A display device comprising the photocurable pattern of claim 7 .