KR102219054B1 - Photosensitive resin composition, photosensitive resin using the same and electronic device - Google Patents

Abstract

(A) alkali-soluble resin; (B) a photopolymerizable compound represented by the following formula (1); (C) photoinitiator; And (D) a photosensitive resin composition containing a solvent, a photosensitive resin film and an electronic device manufactured using the photosensitive resin composition are provided.
[Formula 1]
(R ¹ ) _n (OR ² ) _3-n -Si-L ¹ -Si-(R ³ ) _m (OR ⁴ ) _3-m
(In Chemical Formula 1, each substituent is as defined in the specification.)

Description

A photosensitive resin composition, a photosensitive resin film, and an electronic device using the same TECHNICAL FIELD [0001] PHOTOSENSITIVE RESIN USING THE SAME AND ELECTRONIC DEVICE

The present description relates to a photosensitive resin composition, a photosensitive resin film manufactured using the same, and an electronic device.

Currently, in the case of passivation materials for displays and semiconductors, the development of liquid material materials of a coating method, which is advantageous in terms of process, is being actively carried out, avoiding the deposition method of inorganic (SiNx).

These liquid materials can be largely divided into an acrylic-epoxy-based organic insulating film and a silicon-acrylic organic-inorganic hybrid insulating film having an organopolysiloxane structure. In the case of an organic insulating film composition, a pattern is formed by UV exposure and alkali phenomenon, or there are advantages in terms of adhesion and dielectric constant with the substrate, but there are disadvantages in terms of thermal stability, transmittance, and hardness. Materials are being actively developed.

In the case of LCD panels, there is a limit to the implementation of flexibility due to the BLU that illuminates the light and the color filter to implement the color, whereas OLED is a display that emits light by itself when passing current, so among many types of displays, OLED is flexible. It is in the spotlight as an optimal display to be implemented as a display.

For a flexible display to be implemented, the substrate itself must be made of an unbreakable material rather than a fragile glass. Here, TSP (Touch Screen Panel) and OCA (Optically Clear Adhesive) layers are used for flattening on OLED devices and TFTs, reducing thickness, improving effective flattening, and reducing noise and touch sensitivity between TFT internal circuits and touch sensors. For this reason, a silicone-based overcoat layer is being developed to replace the TSP and OCA layers.

One embodiment is to provide a photosensitive resin composition having excellent residual film rate, sensitivity, resolution, chemical resistance, and hardness.

Another embodiment is to provide a photosensitive resin film prepared by using the photosensitive resin composition.

Another embodiment is to provide an electronic device including the photosensitive resin film.

One embodiment of the present invention is (A) alkali-soluble resin; (B) a photopolymerizable compound represented by the following formula (1); It provides a photosensitive resin composition containing (C) a photoinitiator and (D) solvent.

[Formula 1]

(R ¹ ) _n (OR ² ) _3-n -Si-L ¹ -Si-(R ³ ) _m (OR ⁴ ) _3-m

In Formula 1,

R ¹ to R ⁴ are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group,

R ² and R ⁴ contain an acrylate group at the terminal,

L ¹ is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C20 arylene group, or *-L ² -XL ³ -* (L ² and L ³ are each independently substituted or unsubstituted A cyclic C1 to C10 alkylene group, X is O, S or NR ⁵ (R ⁵ is a substituted or unsubstituted C1 to C10 alkyl group)),

m and n are each independently an integer of 0 to 2.

The acrylate group may be represented by Formula 2 below.

[Formula 2]

In Chemical Formula 2,

R ⁶ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

The photopolymerizable compound may be represented by the following formula (3).

[Formula 3]

In Chemical Formula 3,

L ⁴ to L ⁶ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C20 arylene group, or *-NR ⁵ -* (R ⁵ is a substituted or unsubstituted C1 To C10 alkyl group)), provided that L ⁴ to L ⁶ are not a single bond at the same time,

R ⁷ to R ¹² are each independently a substituted or unsubstituted C1 to C20 alkyl group,

However, at least one of R ⁷ to R ⁹ and at least one of R ¹⁰ to R ¹² include an acrylate group at the terminal.

The photopolymerizable compound may be represented by any one selected from the group consisting of the following Chemical Formulas 4 to 7.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

The alkali-soluble resin may be a novolac resin or an acrylic resin.

The novolac resin may include a structural unit represented by Formula 8 below.

[Formula 8]

In Chemical Formula 8,

R ¹³ is a hydroxy group, a carboxyl group, a cyano group, a nitro group, a halogen, a C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 To C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C1 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 alkenyl group , A substituted or unsubstituted C2 to C30 alkynyl group, or a combination thereof,

a is an integer of 0 to 3.

The mixed solid content of the alkali-soluble resin, the photopolymerizable compound, and the photopolymerization initiator may be 20% to 40% by weight based on the photosensitive resin composition.

The photosensitive resin composition comprises 1% to 40% by weight of the alkali-soluble resin, based on the total amount of the photosensitive resin composition; 0.5% to 25% by weight of the photopolymerizable compound; It may include 0.1% to 15% by weight of the photopolymerization initiator and the remaining amount of the solvent.

The photosensitive resin composition may further include an epoxy compound, a silane coupling agent, a leveling agent, a surfactant, or a combination thereof.

Another embodiment provides a photosensitive resin film prepared by using the photosensitive resin composition.

Another embodiment provides an electronic device including the photosensitive resin film.

Other specifics of aspects of the present invention are included in the detailed description below.

The photosensitive resin composition according to an embodiment may include a photopolymerizable compound having a specific structure, and may improve a residual film rate, sensitivity, resolution, chemical resistance, hardness, and the like.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

Unless otherwise specified in the specification, "substituted" to "substituted" means that at least one hydrogen atom in the functional groups of the present invention is a halogen atom (F, Br, Cl or I), a hydroxy group, a nitro group, a cyano group, an amino group ( NH ₂ , NH (R ²⁰⁰ ) or N (R ²⁰¹ ) (R ²⁰² ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different from each other, and each independently a C1 to C10 alkyl group), an amidino group, A hydrazine group, a hydrazone group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic organic group, a substituted or unsubstituted aryl group, and It means substituted with one or more substituents selected from the group consisting of substituted or unsubstituted heterocyclic groups.

Unless otherwise specified in the specification, “alkyl group” refers to a C1 to C20 alkyl group, specifically C1 to C15 alkyl group, and “cycloalkyl group” refers to a C3 to C20 cycloalkyl group, specifically C3 To C18 cycloalkyl group, "alkoxy group" refers to a C1 to C20 alkoxy group, specifically C1 to C18 alkoxy group, and "aryl group" refers to a C6 to C20 aryl group, specifically C6 to It means a C18 aryl group, and "alkenyl group" means a C2 to C20 alkenyl group, specifically C2 to C18 alkenyl group, and "alkylene group" means a C1 to C20 alkylene group, specifically C1 To C18 alkylene group, and "arylene group" refers to a C6 to C20 arylene group, and specifically refers to a C6 to C16 arylene group.

Unless otherwise specified in the specification, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid" It means both are possible.

Unless otherwise defined herein, "combination" means mixing or copolymerization. In addition, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.

Unless otherwise defined in the chemical formula in the present specification, when a chemical bond is not drawn at a position where a chemical bond is to be drawn, it means that a hydrogen atom is bonded at the position.

In addition, unless otherwise defined in the specification, "*" means a part connected to the same or different atoms or chemical formulas.

One embodiment is (A) alkali-soluble resin; (B) a photopolymerizable compound represented by the following formula (1); (C) photoinitiator; And (D) It provides a photosensitive resin composition containing a solvent.

[Formula 1]

(R ¹ ) _n (OR ² ) _3-n -Si-L ¹ -Si-(R ³ ) _m (OR ⁴ ) _3-m

In Formula 1,

R ¹ to R ⁴ are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group,

R ² and R ⁴ contain an acrylate group at the terminal,

L ¹ is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C20 arylene group, or *-L ² -XL ³ -* (L ² and L ³ are each independently substituted or unsubstituted A cyclic C1 to C10 alkylene group, X is O, S or NR ⁵ (R ⁵ is a substituted or unsubstituted C1 to C10 alkyl group)),

m and n are each independently an integer of 0 to 2.

In general, the negative photosensitive resin composition includes an acrylic copolymer having a specific functional group such as an epoxy group, a polyfunctional acrylate monomer, a photoinitiator, and an organic solvent, and the polyfunctional acrylate monomer is usually dipentaerythritol hexaacrylate ( DPHA) and the like were common. However, it is difficult to improve sensitivity and chemical resistance only with polyfunctional monomers such as DPHA, and recently, 2-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, and 3-methacryl There have been attempts to use silicon-containing compounds such as oxyoctyl trimethoxysilane and 3-methacryloxypropyl methyldimethoxysilane as a photopolymerizable compound, but the silicon-containing compound cannot be used as a photoresist solution itself. Attempts to use it as a photopolymerizable compound in a photosensitive resin composition have failed.

According to an embodiment, by using the compound represented by Formula 1 as a photopolymerizable compound, it is possible to simultaneously improve the residual film rate, sensitivity, resolution, chemical resistance, and hardness, and thus 2-methacryloxypropyl tree, which has been attempted in the past. Providing silicone-containing compounds such as methoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxy octyl trimethoxysilane, and 3-methacryloxypropyl methyldimethoxysilane, or photosensitive resin composition superior to DPHA This is possible.

Hereinafter, each component will be described in detail.

(B) Photopolymerization compound

According to an embodiment, the photopolymerizable compound is represented by Formula 1, and since the photopolymerizable compound represented by Formula 1 contains two silicon atoms and two acrylate groups in a monomer, a photoresist preparation solution becomes possible, and further , It can have superior effects in terms of film residual rate, sensitivity, resolution, chemical resistance, and hardness than conventional materials used as photopolymerizable compounds (DPHA, etc.).

The acrylate group may be represented by Formula 2 below.

[Formula 2]

In Chemical Formula 2,

R ⁶ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

For example, the photopolymerizable compound may be represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

L ⁴ to L ⁶ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C20 arylene group, or *-NR ⁵ -* (R ⁵ is a substituted or unsubstituted C1 To C10 alkyl group)), provided that L ⁴ to L ⁶ are not a single bond at the same time,

R ⁷ to R ¹² are each independently a substituted or unsubstituted C1 to C20 alkyl group,

However, at least one of R ⁷ to R ⁹ and at least one of R ¹⁰ to R ¹² include an acrylate group at the terminal.

For example, in Formula 3, one of R ⁷ to R ⁹ and one of R ¹⁰ to R ¹² may include an acrylate group at the terminal.

The photopolymerizable compound may be represented by any one selected from the group consisting of Formulas 4 to 7 below, but is not limited thereto.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

For example, the photopolymerizable compound, an alkali-soluble resin and a photopolymerization initiator to be described later may be included in an amount of 20% to 40% by weight based on the total amount of the photosensitive resin composition. That is, the photosensitive resin composition according to an embodiment may include a solid content (the alkali-soluble resin, the photopolymerizable compound represented by Formula 1, and the photopolymerization initiator) 20% to 40% by weight and the balance of the solvent.

For example, the photopolymerizable compound represented by Formula 1 may be included in an amount of 0.5% to 25% by weight based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is included in the above content range, high-sensitivity pattern formation is easier and excellent hardness can be obtained.

(A) alkali-soluble resin

The alkali-soluble resin may be a novolac resin or an acrylic resin.

The novolac resin may include a structural unit represented by Formula 8 below.

[Formula 8]

In Chemical Formula 8,

R ¹³ is a hydroxy group, a carboxyl group, a cyano group, a nitro group, a halogen, a C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 To C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C1 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 alkenyl group , A substituted or unsubstituted C2 to C30 alkynyl group, or a combination thereof,

a is an integer of 0 to 3.

The weight average molecular weight of the novolac resin may be 1,000 g/mol to 30,000 g/mol. For example, the weight average molecular weight of the novolac resin is 1,000 g/mol to 20,000 g/mol, such as 2,000 g/mol to 20,000 g/mol, such as 3,000 g/mol to 20,000 g/mol, such as 3,000 g/mol. mol to 15,000 g/mol, such as 4,000 g/mol to 15,000 g/mol.

When the novolac resin has a weight average molecular weight within the above range, it may have an effect that a pattern collapse phenomenon does not occur.

The acrylic resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin comprising at least one acrylic repeating unit.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxy group, and specific examples thereof include 　acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, 　, or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5% to 50% by weight, such as 10% to 40% by weight, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzylmethylether; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth)acrylate and phenyl (meth)acrylate; Unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; Vinyl cyanide compounds such as (meth)acrylonitrile; Unsaturated amide compounds such as (meth)acrylamide; And the like, and these may be used alone or in combination of two or more.

Specific examples of the acrylic resin include (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate Rate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and these may be used alone or in combination of two or more. .

The weight average molecular weight of the acrylic resin may be 3,000 g/mol to 150,000 g/mol, such as 5,000 g/mol to 50,000 g/mol, such as 20,000 g/mol to 30,000 g/mol. When the weight average molecular weight of the acrylic resin is within the above range, the physical and chemical properties of the photosensitive resin composition are excellent, the viscosity is appropriate, and the adhesion between the prepared photosensitive resin film and the substrate is excellent.

The acid value of the acrylic resin may be 15 mgKOH/g to 60 mgKOH/g, such as 20 mgKOH/g to 50 mgKOH/g　. When the acid value of the acrylic resin is within the above range, the resolution of the pixel pattern is excellent.

The alkali-soluble resin may be included in an amount of 1% to 40% by weight based on the total amount of the photosensitive resin composition. When the alkali-soluble resin is included within the above range, developability is excellent and crosslinking property is improved when preparing the photosensitive resin film, thereby obtaining excellent surface smoothness.

(C) Light polymerization Initiator

The photopolymerization initiator is an initiator generally used in the photosensitive resin composition, for example, an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound, or a combination thereof. Can be used.

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloro acetophenone, pt -Butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4 '-Bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

Examples of the thioxanthone-based compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- And chloro thioxanthone.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethylketal, and the like.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3', 4'- Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis (Trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc. are mentioned.

Examples of the oxime-based compound include O-acyloxime-based compounds, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime )-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one Etc. can be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane- 1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione2 -Oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-one oxime-O-acetate, 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O- Acetate, etc. are mentioned.

In addition to the above compounds, the photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, a fluorene compound, or the like.

The photopolymerization initiator may be used together with a photosensitizer that absorbs light and becomes excited, and then transmits the energy to cause a chemical reaction.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, etc. Can be mentioned.

The photopolymerization initiator may be included in an amount of 0.1% to 15% by weight based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, curing occurs sufficiently during exposure in the pattern formation process to obtain excellent reliability, excellent heat resistance, light resistance and chemical resistance of the pattern, excellent resolution and adhesion, and due to unreacted initiators. It is possible to prevent a decrease in transmittance.

(D) solvent

The solvent may be materials that have compatibility with the alkali-soluble resin, the photopolymerizable compound, and the photopolymerization initiator, but do not react.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; Lactate esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxy acetate alkyl esters, such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl methoxy acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxypropionic acid alkyl esters such as 3-oxy methyl propionate and 3-oxy ethyl propionate; 3-alkoxy propionic acid alkyl esters such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate, and 3-ethoxy methyl propionate; 2-oxypropionic acid alkyl esters such as 2-oxy methyl propionate, 2-oxy ethyl propionate, and 2-oxy propionate propyl; 2-alkoxy propionic acid alkyl esters such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate, and 2-ethoxy methyl propionate; 2-oxy-2-methyl propionic acid esters such as 2-oxy-2-methyl methyl propionate and 2-oxy-2-methyl ethyl propionate, 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2- Monooxy monocarboxylic acid alkyl esters of alkyl 2-alkoxy-2-methyl propionate such as ethyl methyl propionate; Esters such as 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate, and 2-hydroxy-3-methyl methyl butanoate; Ketone acid esters such as ethyl pyruvate, etc., and also N-methylformamide, N,N-dimethylformamide, N-methylformanilad, N-methylacetamide, N,N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid High boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among these, in consideration of compatibility and reactivity, ketones such as cyclohexanone are preferred; Glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate may be used.

The solvent may be included in a balance, such as 50% to 80% by weight, based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, the photosensitive resin composition has an appropriate viscosity, and thus the processability is excellent in manufacturing the photosensitive resin film.

(E) other additives

The photosensitive resin composition according to an embodiment may further include an epoxy compound to improve adhesion to the substrate.

Examples of the epoxy compound include a phenol novolac epoxy compound, a tetramethyl biphenyl epoxy compound, a bisphenol A type epoxy compound, an alicyclic epoxy compound, or a combination thereof.

The epoxy compound may be included in an amount of 0.01 to 20 parts by weight, for example, 0.1 to 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is included within the above range, adhesion and storage properties are excellent.

In addition, the photosensitive resin composition may further include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group to improve adhesion to the substrate.

Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidok Cypropyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like, and these may be used alone or in combination of two or more.

The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is included within the above range, adhesion and storage properties are excellent.

In addition, the photosensitive resin composition may further include a leveling agent or a surfactant to improve coating properties and prevent defects from being generated, if necessary.

Examples of the surfactants include, BM Chemie BM-1000 ^® of社, BM-1100 ^®, and the like; Mecha Pack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^® , F 554 ^{® of} Dai Nippon Inki Chemical High School Co., Ltd.; Sumitomo M. (Note)社Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Saffron S-112 ^® of社, such S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; Toray silicone (Note)社SH-28PA ^®, copper -190 ^®, may be used copper ^® -193, fluorine-based surfactants and commercially available under the name, such as ^{SZ-6032 ®, SF-8428} ®.

The surfactant may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included within the above range, coating uniformity is ensured, stains do not occur, and wettability to the glass substrate is excellent.

In addition, a certain amount of other additives such as antioxidants and stabilizers may be added to the photosensitive resin composition within a range that does not impair physical properties.

The photosensitive resin composition may be a negative photosensitive resin composition.

According to another embodiment, a photosensitive resin film manufactured using the photosensitive resin composition according to the embodiment is provided.

The pattern formation process in the photosensitive resin film is as follows.

Applying the photosensitive resin composition onto a supporting substrate by spin coating, slit coating, inkjet printing, or the like; Drying the applied photosensitive resin composition to form a photosensitive resin composition film; Exposing the photosensitive resin composition film to light; Developing the exposed photosensitive resin composition film with an aqueous alkali solution to prepare a photosensitive resin film; And a step of heat treating (curing) the photosensitive resin film. Since the above process conditions are widely known in the art, detailed descriptions thereof will be omitted herein.

The photosensitive resin film may be an insulating film such as a thin film transistor type liquid crystal display device, a solid-state imaging device, or an organic light emitting diode (OLED), but is not limited thereto.

According to another embodiment, an electronic device including the photosensitive resin film is provided. The electronic device may be a display device such as a liquid crystal display, a light emitting diode, a plasma display or an organic light emitting device (eg, OLED), or a color filter.

The photosensitive resin composition may be usefully used to form an insulating film, a passivation layer, or a buffer coating layer in a device.

Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples are only preferred examples of the present invention, and the present invention is not limited to the following examples.

( Photopolymerization Compound)

Synthesis example 1: Synthesis of a compound represented by Formula 4

In a 1000 ml reactor equipped with a cooling tube and a stirrer, 100 ml of dichloromethane, 100 g of 4-hydroxybutyl acrylate (Shin-Nakamura Co., Ltd.) and 84 g of triethylamine were added, and the temperature in the flask was lowered to 0°C, and then p-toluene. A solution in which 139 g of sulfonyl chloride was dissolved in 100 ml of dichloromethane was added dropwise for 2 hours and stirred. After further stirring for 5 hours, the residual solvent was removed by distillation. 60 g of the obtained compound was added to 500 ml of acetonitrile, 110 g of potassium carbonate and 20 g of 1,2-bistriethoxysilylethane were added thereto, followed by stirring at 80°C. The residual solvent and the reaction residue were removed to obtain a compound represented by the following formula (4).

[Formula 4]

Synthesis example 2: Synthesis of the compound represented by Formula 5

In a 1000 ml reactor equipped with a cooling tube and a stirrer, 100 ml of dichloromethane, 100 g of 4-hydroxybutyl acrylate (Shin-Nakamura Co., Ltd.) and 84 g of triethylamine were added, and the temperature in the flask was lowered to 0°C, and then p-toluene. A solution in which 139 g of sulfonyl chloride was dissolved in 100 ml of dichloromethane was added dropwise for 2 hours and stirred. After further stirring for 5 hours, the residual solvent was removed by distillation. 60 g of the obtained compound was put into 500 ml of acetonitrile, 110 g of potassium carbonate and 20 g of 1,4-BIS (HYDROXYDIMETHYLSILYL) BENZENE were added thereto, followed by stirring at 80°C. The residual solvent and the reaction residue were removed to obtain a compound represented by the following formula (5).

[Formula 5]

Synthesis example 3: Synthesis of the compound represented by Formula 6

In a 1000 ml reactor equipped with a cooling tube and a stirrer, 100 ml of dichloromethane, 100 g of 4-hydroxybutyl acrylate (Shin-Nakamura Co., Ltd.) and 84 g of triethylamine were added, and the temperature in the flask was lowered to 0°C, and then p-toluene. A solution in which 139 g of sulfonyl chloride was dissolved in 100 ml of dichloromethane was added dropwise for 2 hours and stirred. After stirring for an additional 5 hours, the residual solvent was removed by distillation. 60 g of the obtained compound was added to 500 ml of acetonitrile, 110 g of potassium carbonate and 20 g of 4,4′-Bis(triethoxysilyl)-1,1′-biphenyl were added, followed by stirring at 80°C. The residual solvent and the reaction residue were removed to obtain a compound represented by the following formula (6).

[Formula 6]

Synthesis example 4: Synthesis of a compound represented by Formula 7

In a 1000 ml reactor equipped with a cooling tube and a stirrer, 100 ml of dichloromethane, 100 g of 4-hydroxybutyl acrylate (Shin-Nakamura Co., Ltd.) and 84 g of triethylamine were added, and the temperature in the flask was lowered to 0°C, and then p-toluene. A solution in which 139 g of sulfonyl chloride was dissolved in 100 ml of dichloromethane was added dropwise for 2 hours and stirred. After stirring for an additional 5 hours, the residual solvent was removed by distillation. 60 g of the obtained compound was put into 500 ml of acetonitrile, 110 g of potassium carbonate and 20 g of Bis(3-(methylamino)propyl)trimethoxysilane were added thereto, followed by stirring at 80°C. The residual solvent and the reaction residue were removed to obtain a compound represented by the following formula (7).

[Formula 7]

(Synthesis of photosensitive resin composition)

Example 1 to Example 8 and Comparative example One, Comparative example 2 and Reference example One

Example One

The photopolymerizable compound of Synthesis Example 1, an acrylic resin (T-82, Samsung SDI Co., Ltd.), and a photopolymerization initiator (IRGARCURE OXE01, BASF Co., Ltd.) Co., Ltd.), and then filtered through a 0.2 μm Millipore filter to remove impurities, thereby preparing a photosensitive resin composition.

Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the photopolymerizable compound of Synthesis Example 2 was used instead of the photopolymerizable compound of Synthesis Example 1.

Example 3

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the photopolymerizable compound of Synthesis Example 3 was used instead of the photopolymerizable compound of Synthesis Example 1.

Example 4

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the photopolymerizable compound of Synthesis Example 4 was used instead of the photopolymerizable compound of Synthesis Example 1.

Example 5

Except that the solid content of the photopolymerizable compound of Synthesis Example 1, an acrylic resin (T-82, Samsung SDI, Inc.) and a photoinitiator (IRGARCURE OXE01, BASF, Inc.) is 20% by weight, In the same manner as in Example 1, a photosensitive resin composition was prepared.

Example 6

Except that the solid content of the photopolymerizable compound of Synthesis Example 1, an acrylic resin (T-82, Samsung SDI, Inc.) and a photoinitiator (IRGARCURE OXE01, BASF, Inc.) is 40% by weight, In the same manner as in Example 1, a photosensitive resin composition was prepared.

Example 7

Except that the solid content of the photopolymerizable compound of Synthesis Example 1, an acrylic resin (T-82, Samsung SDI, Inc.) and a photoinitiator (IRGARCURE OXE01, BASF Corp.) is 10% by weight, In the same manner as in Example 1, a photosensitive resin composition was prepared.

Example 8

Except that the solid content of the photopolymerizable compound of Synthesis Example 1, an acrylic resin (T-82, Samsung SDI, Inc.) and a photoinitiator (IRGARCURE OXE01, BASF Corp.) is 50% by weight, In the same manner as in Example 1, a photosensitive resin composition was prepared.

Comparative example One

A photosensitive resin composition was prepared in the same manner as in Example 1, except that pentaerythritol tetraacrylate was used instead of the photopolymerizable compound of Synthesis Example 1.

Comparative example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that dipentaerythritol hexaacrylate (DIPENTAERYTHRITOL HEXAACRYLATE; DPHA) was used instead of the photopolymerizable compound of Synthesis Example 1.

Reference example One

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the following photosensitive silicone resin was used instead of the acrylic resin.

(Photosensitive silicone resin synthesis method of Reference Example 1)

In a 1 L flask, 0.3 mol of phenyltriethoxy silane, 0.4 mol of 3-methacryloxypropyltrimethoxysilane, and 0.3 mol of tetraethoxy silane were used as a solvent using propylene glycol monomethyl ether acetate, and the reaction product (methyltriethoxy silane , 3-methacryloxypropyltrimethoxysilane, tetraethoxysilane) was mixed at room temperature in 50 parts by weight based on 100 parts by weight, and then 3.65 moles of 0.01N HCl were slowly dropped. After that, the reaction temperature was raised to 80°C, and the reaction was performed for 5 hours. Subsequently, while cooling to room temperature, flophyllene glycol monomethyl ether acetate was added in an amount of 50 parts by weight based on 100 parts by weight of the reactants (phenyltriethoxy silane, 3-methacryloxypropyltrimethoxysilane, tetraethoxy silane). . Thereafter, evaporation was performed at 60° C. to remove adducts such as water and alcohol generated during the reaction to synthesize a photosensitive silicone resin.

evaluation

The photosensitive resin compositions prepared in Examples 1 to 8, Comparative Examples 1, 2, and Reference Example 1 were coated on a glass substrate to a thickness of 3 μm using a spin coater (Mikasa Corporation, Opticoat MS-A150). Thereafter, a film was formed by soft-baking at 85°C for 120 seconds using a hot-plate, and then an ultraviolet ray having an intensity of 25.0 mW/cm ³ at 365 nm was applied to the film ( UX-1200SM-AKS02, USHIO) was used for 8 seconds. Subsequently, it was developed with an aqueous solution of 2.38% by weight of tetramethylammonium hydroxide at 25° C. for 60 seconds, washed with ultrapure water for 60 seconds, and dried by blowing with compressed air. Thereafter, the dried film was cured by heating in an oven at 85° C. for 60 minutes to obtain a photoresist film.

(1) Calculation of resolution

The minimum pattern size after development was calculated as the resolution after development, and the minimum pattern size after curing was calculated as the resolution after curing, and the results are shown in Table 1 below.

(2) Pencil hardness evaluation

The pencil hardness was measured at room temperature using a pencil hardness tester KP-M5000M (Maker: Kipae E&T) based on the ASTM D3363 test standard on the photoresist film, and the results are shown in Table 1 below.

(3) Sensitivity evaluation

The photosensitive resin compositions prepared in Examples 1 to 8, Comparative Examples 1, 2, and Reference Example 1 were coated on a glass substrate to a thickness of 3 μm using a spin coater (Mikasa Corporation, Opticoat MS-A150). Thereafter, a film was formed by soft-baking at 85° C. for 120 seconds using a hot-plate, and a line width of 10 μm pattern was 11 μm by using a predetermined pattern mask on the film. Using an exposure machine (UX-1200SM-AKS02, USHIO) was used to irradiate ultraviolet rays with an intensity of 25.0 mW/cm ³ at 365 nm, and measure the sensitivity while measuring the ultraviolet irradiation time, and the results are shown in the table below. It is shown in 1.

(4) Evaluation of residual film rate

The photosensitive resin compositions prepared in Examples 1 to 8, Comparative Examples 1, 2, and Reference Example 1 were coated on a glass substrate to a thickness of 3 μm using a spin coater (Mikasa Corporation, Opticoat MS-A150). Then, soft-baking for 120 seconds at 85°C using a hot-plate to form a film, and then measure the thickness immediately after the film formation (Alpha-step, Surface profiler KLA tencor) ). And, by using a predetermined pattern mask on the film, an ultraviolet ray having an intensity of 25.0 mW/cm ³ at 365 nm is realized with a line width of 11 μm in a 10 μm pattern using an exposure machine (UX-1200SM-AKS02, USHIO) And irradiated for 8.0 seconds. Subsequently, it was developed with an aqueous solution of 2.38% by weight of tetramethylammonium hydroxide at 25° C. for 60 seconds, washed with ultrapure water for 60 seconds, and dried by blowing with compressed air. Thereafter, the dried film was cured by heating in an oven at 85° C. for 60 minutes to obtain a photoresist film, and the thickness of the photoresist film was immediately measured (Alpha-step, Surface Profiler KLA tencor). The thickness of the film immediately after the soft-baking was compared with the thickness of the photoresist film, the thickness reduction ratio of the film was measured, and the residual film rate was calculated, and the results are shown in Table 1 below.

(5) Chemical resistance evaluation

After measuring the initial thickness of the photoresist film, it was allowed to stand in a solution or NMP solvent in which MEA (monoethanolamine) and DMSO were mixed in a ratio of 7:3 at 50° C. for 3 minutes, washed with ultrapure water for 30 seconds, and then compressed air. And dried by blowing. After that, the thickness was re-measured (Alpha-step, Surface Profiler KLA tencor) to confirm the chemical resistance through the rate of change in the thickness of the film, and the results are shown in Table 1 below.

Film remaining rate (%) Sensitivity (mJ/cm ² ) Resolution after curing (㎛) MEA:DMSO(7:3) Chemical resistance (%) NMP chemical resistance (%) Pencil hardness Example 1 90.03 35 5 1.2 0.5 4H Example 2 91.74 40 4 1.4 0.6 4H Example 3 89.68 35 5 1.3 0.5 4H Example 4 90.14 35 5 1.8 0.7 4H Example 5 82.51 55 8 2.3 1.9 3H Example 6 85.98 50 7 2.0 1.5 3H Example 7 83.79 60 9 2.4 2.2 2H Example 8 86.58 45 6 1.9 1.2 4H Comparative Example 1 76.16 85 15 3.2 3.2 2H Comparative Example 2 78.53 70 10 3.1 3.0 3H Reference Example 1 81.12 65 9 2.7 2.8 3H

From Table 1, it can be seen that the photosensitive resin composition using the compound represented by Chemical Formula 1 as a photopolymerizable compound is superior to the photosensitive resin composition which does not have a film residual rate, sensitivity, resolution, chemical resistance, and hardness.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the claims, the detailed description of the invention, and the accompanying drawings. It is natural to fall within the scope of the invention.

Claims (11)

(A) alkali-soluble resin;
(B) a photopolymerizable compound represented by any one selected from the group consisting of the following formulas 4 to 7;
(C) photoinitiator; And
(D) solvent
Photosensitive resin composition comprising a.
[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

delete delete delete The method of claim 1,
The alkali-soluble resin is a novolac resin or an acrylic resin photosensitive resin composition.
The method of claim 5,
The novolac resin is a photosensitive resin composition comprising a structural unit represented by Formula 8 below:
[Formula 8]

In Chemical Formula 8,
R ¹³ is a hydroxy group, a carboxyl group, a cyano group, a nitro group, a halogen, a C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 To C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C1 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 alkenyl group , A substituted or unsubstituted C2 to C30 alkynyl group, or a combination thereof,
a is an integer of 0 to 3.
The method of claim 1,
The mixed solid content of the alkali-soluble resin, the photopolymerizable compound, and the photopolymerization initiator is 20% to 40% by weight based on the photosensitive resin composition.
The method of claim 1,
The photosensitive resin composition is based on the total amount of the photosensitive resin composition,
1% to 40% by weight of the alkali-soluble resin;
0.5% to 25% by weight of the photopolymerizable compound;
0.1% to 15% by weight of the photopolymerization initiator, and
The residual amount of the solvent
Photosensitive resin composition comprising a.
The method of claim 1,
The photosensitive resin composition further comprises an epoxy compound, a silane coupling agent, a leveling agent, a surfactant, or a combination thereof.
A photosensitive resin film produced by using the photosensitive resin composition of any one of claims 1 and 5 to 9.
An electronic device comprising the photosensitive resin film of claim 10.