KR20130077589A - Photosensitive resin composition and dielectric layer using same - Google Patents

Abstract

PURPOSE: A photosensitive resin composition is provided to present excellent permeability while the composition maintains a chemical resistance, develops an alkali water solution, residue membrane rate and cohesive properties etc. CONSTITUTION: A photosensitive resin composition comprises (A) a copolymer with a recurring unit following the chemical formula 1, (B) a polymerizable compound with one or more ethylenically unsaturated double bond, and (C) a photopolymerization initiator. In the chemical formula1, R1 is hydrogen or a C1-C4 alkyl, R2 is a C1-C10 alkylene, and R3 is a C1-C10 alkylene or a C1-C10 heteroalkylene. The R3 can be substituted with one or more OH or SH. The photosensitive resin composition includes a functional silane compound, a surfactant solvent or their additional mixture.

Description

PHOTOSENSITIVE RESIN COMPOSITION AND DIELECTRIC LAYER USING SAME}

The present invention relates to a photosensitive resin composition and an insulating film using the same, and more particularly, to a photosensitive film for forming an insulating film used in an initial process of a thin film transistor (TFT) for a liquid crystal display (LCD). It relates to a resin composition and an insulating film produced using the same.

The TFT substrate used for the liquid crystal display element has an interlayer insulating film for protecting the TFT array element between the TFT element and the transparent conductive film forming the pixel electrode, and the insulating film is formed by the drain electrode and the transparent conductive film of the TFT array. Contact holes are formed for connecting the wirings, which are required for the insulating film to have high transmittance, chemical stability and excellent interlayer adhesion.

Positive and negative photosensitive compositions are used as materials for such interlayer insulating films.

Conventional positive photosensitive compositions comprising alkali-soluble resins and 1,2-quinonediazide compounds are thermally decomposed at the time of hard bake after exposure and development, and upon absorption of short wavelengths such as ultraviolet rays, resulting in coloration or impurities. There has been a problem that the afterimage occurs in the liquid crystal display device.

Therefore, in order to solve this problem, a negative photosensitive composition having high transmittance and sensitivity after thermosetting can be used.

As a negative photosensitive composition, JP-A-194-043643 discloses a copolymer obtained from (A) (a1) unsaturated carboxylic acid or unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compound, and (a3) monoolefin unsaturated compound, A photosensitive composition is described which comprises (B) a compound having at least one ethylenically unsaturated double bond, and (C) a photoinitiator.

However, recent trends in technology development require better permeability and residual film rate properties (properties on the thickness of films formed after the development process).

For example, Japanese Patent Laid-Open No. 2008-216489 includes (A) a block copolymer having two or more block segments, (B) a polymerizable unsaturated compound, and (C) a photopolymerization initiator, wherein the block copolymer has two unsaturated The photosensitive composition which consists of a specific compound which has a double bond is disclosed. Japanese Patent Laid-Open No. 2011-141538 discloses (A) a resin having a specific repeating unit including a double bond, (B) a polymerizable unsaturated compound, (C) a photopolymerization initiator, and (D) two types of acrylic ester and siloxane bonds. The photosensitive resin composition containing the copolymer with the unsaturated compound which has the thing is disclosed. Korean Patent Publication No. 10-2010-0114831 discloses a photosensitive resin comprising (A) a copolymer of an unsaturated carboxylic acid monoolefin unsaturated compound and an epoxy group-containing unsaturated compound, (B) a polymerizable unsaturated compound, and (C) a photopolymerization initiator. The composition is described. Korean Patent Publication No. 10-2011-0040640 discloses a photosensitive composition comprising (A) a resin having an epoxy group or an oxetane group, (B) a polymerizable unsaturated compound, (C) a functional silane compound, and (D) a specific triazine derivative compound Resin compositions are described. However, these four patents do not disclose the compounds of the present invention.

Furthermore, the inventors of the present invention have found that the photopolymerizable initiator results in a decrease in the transmittance and that the photosensitive resin composition comprising a copolymer having a specific repeating unit can solve the above problem, thus completing the present invention. .

JP 1994-043643 A JP 2008-216489 A JP 2011-141538 A KR 2010-0114831 A KR 2011-0040640 A

Accordingly, an object of the present invention is to provide a negative photosensitive resin composition and an insulating film prepared therefrom, which can provide better transmittance while maintaining properties such as chemical resistance, developability to an aqueous alkali solution, residual film ratio and adhesion. will be.

The present invention to achieve the above object

It provides a photosensitive resin composition comprising (A) a copolymer comprising a repeating unit of formula (1), (B) a polymerizable compound having at least one ethylenically unsaturated double bond, and (C) a photopolymerization initiator:

In Formula 1, R ₁ is hydrogen or C ₁ -C ₄ alkyl; R ₂ is C ₁ -C ₁₀ alkylene; R ₃ is C ₁ -C ₁₀ Alkylene or C ₁ -C ₁₀ Heteroalkylene, wherein R ₃ may be substituted with one or more OH or SH.

The present invention also provides an insulating film produced using the photosensitive resin composition.

The present invention also provides an electronic component comprising the insulating film.

The photosensitive resin composition of the present invention can provide excellent transmittance while maintaining the properties such as chemical resistance, developability to an aqueous alkali solution, residual film rate and adhesion, and can be usefully used for the preparation of an insulating film for a liquid crystal display device. .

The photosensitive resin composition according to the present invention comprises (A) a copolymer comprising a repeating unit represented by the following formula (1), (B) a polymerizable compound having at least one ethylenically unsaturated double bond, and (C) a photopolymerization initiator.

[Formula 1]

In Formula 1, R ₁ is hydrogen or C ₁ -C ₄ alkyl; R ₂ is C ₁ -C ₁₀ alkylene; R ₃ is C ₁ -C ₁₀ Alkylene or C ₁ -C ₁₀ Heteroalkylene, wherein R ₃ may be substituted with one or more OH or SH.

Hereinafter, the constituent components of the present invention will be described in detail.

(A) copolymer

중에서 선택된 헤테로원자를 함유하는 알킬렌을 의미한다. As used herein, the term “heteroalkylene” refers to O, S, N,

It means an alkylene containing a hetero atom selected from.

Specific examples of R ₁ in formula (I) may be mentioned hydrogen, methyl, ethyl, propyl, n-butyl and tert-butyl (tertiary butyl), etc., it may preferably be hydrogen or methyl.

Specific examples of R ₂ include methylene, ethylene, propylene, butylene, octylene, and the like, and preferably methylene or ethylene.

Specific examples of R ₃ include methylene, ethylene, -C ₂ H ₄ -OC ₂ H _4- , -C ₄ H ₈ -OC ₄ H _8- , -C ₂ H ₄ -COO-C ₂ H _4- , -C ₄ H ₈ -COO-C ₄ H _8- , -C ₂ H ₄ -OCONH-C ₂ H _4- , -C ₂ H ₄ -SC ₂ H _4- , -C ₂ H ₄ -CH (OH) -C ₂ H ₄ -and —C ₂ H ₄ —CH (SH) —C ₂ H ₄ — and the like, and preferably methylene or hydroxymethylene (—CH (OH) —).

The term "copolymer" as used herein refers to a polymer consisting of two or more monomers, including all random copolymers, block copolymers and other copolymer forms, but preferably refers to random copolymers. The copolymer of the present invention may be a copolymer between a monomer and another monomer forming a repeating unit of formula (1).

Specific examples of the other monomers include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids; Mono [(meth) acryloyloxyalkyl] of bivalent or more polyvalent carboxylic acids, such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Esters; mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -carboxypolycaprolactone mono (meth) acrylate; And the like. Among them, acrylic acid, methacrylic acid, maleic anhydride and the like can be preferably used in view of having excellent copolymerization reactivity and solubility in aqueous alkali solution and easy availability, and the components can be used alone or in combination. have.

In addition, an aromatic vinyl compound which is an aromatic unsaturated monomer may be used as the monomer, and specific examples thereof include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, and hexyl. Styrene monomers such as styrene, heptylstyrene, octyl styrene, fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodine styrene, nitrostyrene, acetyl styrene, methoxy styrene and divinylbenzene; And nitrogen-containing aromatic vinyls such as vinylpyridine and vinyl carbazole. Examples of the epoxy group-containing unsaturated compound include glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether and the like, and an oxetanyl group-containing unsaturated compound. -Ethyl-3-methylmethacrylate oxetane, etc. are mentioned, but it is not limited to this.

In addition, an imide monomer having a polymerizable unsaturated group may be further used. Specific examples thereof include phenylmaleimide, cyclohexyl maleimide, benzyl maleimide, N-succinimidyl-3-maleimide benzoate, and N-succinimi. Di--4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide, and the like. Can be.

Among these monomers, methacrylic acid, methacrylic anhydride, methyl acrylate, methyl methacrylate, benzyl methacrylate, styrene, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl Ethers, phenylmaleimide and the like can be used, but is not limited thereto.

Copolymers of the photosensitive resin composition of the present invention are not included in (i) repeating units of formula (1), (ii) repeating units derived from ethylenically unsaturated carboxylic acids or anhydrides thereof, and (iii) above (i) and (ii). May include repeat units.

The repeating unit (iii) does not include a compound having an epoxy ring and may include one or more repeating units derived from an aromatic compound having an ethylenically unsaturated double bond.

The proportion of each monomer in the copolymer is (i) 1 to 50 mol% of repeating units of Formula 1, (ii) 1 to 70 mol% of repeating units derived from ethylenically unsaturated carboxylic acids or anhydrides thereof, and (iii) other monomers. 5 to 50 mol%. Preferably, (i) 10 to 35 mol% of repeating units of formula (1), (ii) 30 to 60 mol% of repeating units derived from ethylenically unsaturated carboxylic acids or anhydrides thereof, and (iii) 20 to 40 mol% of other monomers. Can be. If the ratio of the repeating unit (i) is 1 mol% or less, the photosensitive resin composition is not preferable because the residual film ratio is significantly lower after development, and if it is 50 mol% or more, the developability of the photosensitive resin composition is not preferable. .

The molecular weight of the copolymer used in the present invention may be 5,000 to 30,000, preferably 7,000 to 18,000, more preferably 10,000 to 15,000. The molecular weight refers to a value measured by gel permeation chromatography (GPC).

The copolymers used in the present invention can be synthesized by known methods.

The copolymer used in the present invention preferably includes a repeating unit of formula (1) which is a repeating unit having a hydroxyl group at the side chain and an unsaturated structure at the terminal. Thus, the terminal unsaturated structure in a random copolymer can maintain the outstanding residual film rate after image development, and the hydroxyl group of a side chain can enhance developability and adhesiveness to a board | substrate.

(B) a polymerizable compound having at least one ethylenically unsaturated double bond

The photosensitive resin composition according to the present invention comprises (B) a polymerizable compound having at least one ethylenically unsaturated double bond. Polymerizable compounds having at least one ethylenically unsaturated double bond include (meth) acrylic acid derivatives, and specific examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, carbitol (meth) acrylate, acryloyl morpholine, a half ester of a hydroxy group-containing (meth) acrylate and a polycarboxylic acid compound, polyethylene Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropanepolyethoxy tri (meth) acrylate, glycerin polypropoxy tri (meth) acrylic Di (meth) acrylate (e.g., KAYARAD DPHA, KAYARAD HX-220, HX-620, etc.), which is a reactant of latex, hydroxypivalate neopentyl glycol and ε-caprolactone ( Nippon Gunpowder Co., Ltd.), pentaerythritol tetra (meth) acrylate, poly (meth) acrylate and dipentaerythritol poly (meth) acrylate, which are reactants of dipentaerythritol and ε-caprolactone, etc. Can be mentioned.

The compound (B) may be used alone or in combination of two or more thereof, and may be used in an amount of 1 to 150 parts by weight, preferably 50 to 120 parts by weight, based on 100 parts by weight of the copolymer (A).

(C) photopolymerization initiator

The photosensitive resin composition which concerns on this invention contains the (C) photoinitiator. The photopolymerization initiator serves to initiate a polymerization reaction of monomers that can be cured by visible light, ultraviolet light, deep-ultraviolet radiation, and the like. The photopolymerization initiator may be a radical initiator, and examples thereof include acetophenone series, benzophenone series, benzoin series, benzoyl series, xanthone series, triazine series, halomethyloxadiazole series, ropindimer series initiators, and mixtures thereof. However, the photopolymerization initiator used in the art is not particularly limited.

Specific examples of such a photoinitiator include p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzyldimethyl ketal, benzophenone, benzoinpropyl ether, diethyl thioxanthone , 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 9-phenyla Chridine, 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer , 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1- [4- (phenylthio) phenyl] -octane-1,2-dione-2- (O-benzoyl Oxime), o-benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyloxide, hexafluorophosphoro-trialkylphenylsulfonium salt , 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide and mixtures thereof, but is not limited thereto. The.

The photopolymerization initiator may be used in an amount of 0.1 to 20 parts by weight, preferably 3 to 17 parts by weight based on 100 parts by weight of the copolymer (A). When used in the above content range is preferred because it can exhibit a residual film rate after development.

(D) other components

The present invention may further include other components for improving the properties of the photosensitive resin composition. For example, the other components include (D1) functional silane compounds, (D2) surfactants and / or (D3) solvents, and the like.

(D1) Functional Silane Compounds

The photosensitive resin composition according to the present invention may further include a functional silane compound in order to improve the adhesion between the protective film and the substrate. Such functional silane compounds may have reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, epoxy groups, imidazole groups, thiol groups, amine groups and the like.

Specific examples of the functional silane compound include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, and γ-glyci Doxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-oxycyclohexyl) ethyltrimethoxysilane, and mixtures thereof, but are not limited thereto.

The functional silane compound may be used in an amount of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the copolymer (A). If the amount of use exceeds 30 parts by weight, the storage stability of the composition tends to decrease, which is not preferable.

(D2) surfactant

The photosensitive resin composition according to the present invention may further include a surfactant to improve coating performance. Such surfactants include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and other surfactants.

As a surfactant, for example, FZ2122 (Dow Corning Toray Co., Ltd.), BM-1000, BM-1100 (manufactured by BM CHEMIE Co., Ltd.), Megapack F142 D, Copper F172, Copper F173, Copper F183 (Dai Nippon Ink Chemical Industries, Ltd.) Shiki Kaisha), Florade FC-135, Copper FC-170 C, Copper FC-430, Copper FC-431 (manufactured by Sumitomo 3M Limited), Supron S-112, Copper S-113, Copper S-131, East S-141, East S-145, East S-382, East SC-101, East SC-102, East SC-103, East SC-104, East SC-105, East SC-106 (Asahi Glass Co., Ltd.) Kaisha), F-top EF301, 303, 352 (new Kashikawa Kaisha), SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC- Fluorine-based and silicone-based surfactants such as 190 (manufactured by Toray Silicone Co., Ltd.); Polyoxyethylene aryl ethers such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene nonylphenyl ether Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) or (meth) acrylic acid copolymer polyflow Nos. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) alone or two kinds. The above may be used in parallel, but is not limited thereto.

The surfactant may be used in an amount of 5 parts by weight or less, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the copolymer (A).

(D3) solvent

The photosensitive resin composition which concerns on this invention is manufactured by mixing the above-mentioned component with an organic solvent, and melt | dissolving in an organic solvent.

Specific examples of the organic solvent used to prepare the copolymer of the present invention include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate; Cellosolve such as ethyl cellosolve and butyl cellosolve; Carbitols such as butyl carbitol; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, and isopropyl lactate; Aliphatic carboxylic acid esters, such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, and isobutyl propionate ; Esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate and ethyl pyruvate; Aromatic hydrocarbons such as toluene and xylene; 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as? -butyrolactone; And mixtures thereof, but is not limited thereto.

The photosensitive resin composition according to the present invention may include an organic solvent such that the solid content is in the range of 5 to 70% by weight, preferably 10 to 50% by weight, based on the total weight of the composition.

The photosensitive resin composition according to the present invention may be coated on a substrate and then cured to form an insulating film. The insulating film may be used as an electronic component.

Moreover, the insulating film manufactured using the photosensitive resin composition of this invention can be used for a liquid crystal display element.

The insulating film may be prepared by a method known in the art, for example, the photosensitive resin composition is coated on a silicon wafer by a spin coating method, and dried at 60 to 130 ° C. for 60 to 130 seconds (preliminary curing (pre -bake)) and a developer (eg, tetramethylammonium hydroxide solution (TMAH)) to form a pattern on the coating layer. Thereafter, the patterned coating layer may be thermally cured (post-bake) at 180 to 250 ° C. for 10 minutes to 5 hours to obtain a desired insulating film.

The exposure may be performed at an intensity of 40 to 100 mJ in a wavelength band of 200 to 450 nm.

The cured film obtained by the photosensitive resin composition of this invention shows a high residual film rate after image development, and has a high transmittance, and is suitable for the material for LCD.

The residual film rate after development represents the ratio of the thickness of the film formed after development to the thickness of the film initially applied. The residual film rate after such development should preferably be 85% or more, and more preferably 87% or more. The thickness of the membrane was measured with a non-contact thickness measuring instrument. The transmittance should preferably be at least 85%, more preferably at least 90%. The transmittance was measured by an ultraviolet / visible absorbance meter.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the present invention, but the scope of the present invention is not limited thereto.

Manufacturing example  1: Preparation of Copolymer (A)

150 parts by weight of methyl 3-methoxypropionate as a solvent was added to a flask equipped with a cooling tube and a stirrer, and the temperature of the solvent was raised to 60 ° C. while stirring slowly. 100 parts by weight of a monomer mixture consisting of 27 mole% of acid and 19 mole% of oxirane-2-ylmethyl-3-methylbut-3-enoate of the following repeating unit 1 was added, followed by azobisisobutyronitrile as a polymerization initiator. After the addition of 4 parts by weight of the polymerization reaction was carried out over 2 hours.

4 parts by weight of acrylic acid and azobisisobutyronitrile in the same mole% as the compound of repeating unit 1 were added to the resultant solution, and solution polymerization was performed at 60 ° C. for 3 hours to give a random air having a weight average molecular weight of 13,000 including repeating unit 2 below. Union (A) was obtained.

[Repeat unit 1]

[Repeat unit 2]

Manufacturing example  2: Preparation of Copolymer (B)

100 parts by weight of a monomer mixture consisting of 50 mol% of styrene, 20 mol% of methyl methacrylate, 25 mol% of methacrylic acid and 5 mol% of glycidyl methacrylate were added, except that the solution was polymerized at 65 DEG C for 5 hours. In the same manner as in Production Example 1, a random copolymer (B) having a weight average molecular weight of 13,000 was obtained.

Example  One

100 g of copolymers (A) synthesized in Production Example 1, 70 g of dipentaerythritol hexaacrylate (trade name DPHA, Nippon Kayaku Co., Ltd.) as a polymerizable unsaturated compound, and a photopolymerization initiator 12,4-bis (trichloromethyl) -6 13 g of -p-methoxyphenyl-s-triazine, 0.5 g of surfactant FZ-2110 (trade name, manufactured by Dow Corning Toray Co., Ltd.), and 100 g of methyl-3-methoxy propionate as a solvent were prepared using a shaker. Mixing for a time to prepare a photosensitive resin composition in liquid form.

Example  2 to 4

Except for changing the content of the components used as shown in Table 1 below, the same process as in Example 1 was carried out to prepare a photosensitive resin composition.

Comparative example  1 to 4

The same process as in Example 1 was carried out except that the copolymer (B) prepared in Preparation Example 2 was used instead of the copolymer (A), and the content of the components used was changed as shown in Table 1 below. It was carried out to prepare a photosensitive resin composition.

Photosensitive resin composition Example Comparative example One 2 3 4 One 2 3 4 Copolymer A 100g 100g 100g 100g - - - - Copolymer B - - - - 100g 100g 100g 100g Polymerizable Compound A 70g 70g 70g 70g 70g 70g 70g 70g Photopolymerization Initiator A 13g 9.0 g - - 13g 18.5 g - - Photopolymerization initiator B - - 10.5 g 7.5g - - 10.5 g 15.1 g Surfactant A 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g Functional Silane Compound A 1 g 1 g 1 g 1 g 1 g 1 g 1 g 1 g Solvent A 100g 100g 100g 100g 100g 100g 100g 100g

* Photopolymerization initiator A = 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine

* Photoinitiator B = 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone

* Polymerizable Compound A = dipentaerythritol hexaacrylate (trade name DPHA, Nippon Kayaku)

* Surfactant A = FZ-2110 (manufactured by Dow Corning Toray Corporation)

Functional silane compound A = γ-glycidoxypropyltriethoxysilane

Solvent A = methyl-3-methoxypropionate

The membranes were prepared from the photosensitive resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 4, and the residual film ratio, transmittance, adhesion, and chemical resistance of the cured film were measured, and the results are shown in Table 2 below.

[Production of Thermosetting Film]

The photosensitive resin composition was applied on a silicon wafer by a spin coating method, and then pre-baked for 90 seconds on a hot plate maintained at a temperature of 105 ° C. to form a coating film having a thickness of 5 μm. The film was exposed to 40 mJ at a wavelength of 365 nm using a MA6 exposure machine (manufactured by SUSS Microtec), and developed through a spray nozzle at 23 ° C. with a developer composed of an aqueous 2.38 wt% tetramethylammonium hydroxide solution. The obtained exposure film was post-baked at 230 ° C. for 1 hour in a convection oven to obtain a thermosetting film.

One. Residual film ratio  evaluation

The remaining film percentage (%) after development of the manufactured thermosetting film was obtained by the following equation.

[Equation 1]

Residual rate after development = ( After development Film Thickness / Initial Coating Film Thickness (5 ㎛ ) X 100

The thickness of the membrane was measured using a non-contact thickness measuring instrument (product name: Nanospec 6500). After development, the residual film ratio was derived by averaging values obtained at exposure energies of 10 mJ, 20 mJ, 30 mJ, 40 mJ, 50 mJ, and 60 mJ.

2. Measurement of permeability

After the thermosetting film was formed on the glass substrate in the same manner as in the thermosetting film formation, the transmittance (%) of the 400 nm wavelength was measured by using an ultraviolet / visible absorbance meter (varian UV100).

3. Adhesion  evaluation

The prepared thermosetting film was subjected to a cross-cut test in accordance with ASTM D3359. At this time, the adhesive strength was evaluated according to the following criteria.

0B: broken into flakes, falling more than 65%

1B: The tip and the lattice of the cut part fell off, and the area was 35% to 65%.

2B: The tip of the cut portion and a part of the lattice fell off, and the area was 15% to 35%.

3B: A small area fell off at the end and intersection of the cut portion, and the area was 5% to 15%.

4B: A small area fell off at the intersection of the cut and the area is less than 5%

5B: The edge of the cut is smooth and there is no grating off

4. Chemical resistance evaluation

The thermosetting film thus prepared was immersed in 20 wt% hydrochloric acid at 40 ° C. for 20 minutes, and evaluated according to the following criteria.

(Circle): A hole and surface roughness (unevenness) are not observed even by the surface observation by an optical microscope.

X: A hole and surface roughness (unevenness | corrugation) are observed by surface observation by an optical microscope, or the haze is observed by visual observation.

Photosensitive resin
Composition Example Comparative example One 2 3 4 One 2 3 4 Post-development residual rate 93% 88% 93% 88% 87% 93% 87% 93% Permeability 82% 94% 85% 96% 82% 71% 84% 74% Adhesion 5B 5B 5B 5B 4B 5B 5B 5B Chemical resistance ○ ○ ○ ○ ○ ○ ○ ○

As can be seen from Table 1 and Table 2, in Examples 1 to 4 using the copolymer (A), a smaller amount of the photopolymerization initiator was used as compared to the comparative example using the copolymer (B). In the case of Examples 2 and 4 it can exhibit a residual film ratio after development of a relatively good level. Therefore, it can be seen that the photosensitive resin composition of the present invention comprising the copolymer (A) can provide a better transmittance even though the residual film rate after the same level of development.

Claims (5)

A photosensitive resin composition comprising (A) a copolymer comprising a repeating unit of formula (1), (B) a polymerizable compound having at least one ethylenically unsaturated double bond, and (C) a photoinitiator:
[Formula 1]

In Formula 1, R ₁ is hydrogen or C ₁ -C ₄ alkyl; R ₂ is C ₁ -C ₁₀ alkylene; R ₃ is C ₁ -C ₁₀ Alkylene or C ₁ -C ₁₀ Heteroalkylene, wherein R ₃ may be substituted with one or more OH or SH.
The method of claim 1,
The photosensitive resin composition, wherein the copolymer comprises a repeating unit derived from an ethylenically unsaturated carboxylic acid or an anhydride thereof, and a repeating unit derived from an aromatic compound having an ethylenically unsaturated double bond.
The method of claim 1,
The photosensitive resin composition further comprises a functional silane compound, a surfactant, a solvent, or a mixture thereof.
The insulating film manufactured using the photosensitive resin composition of any one of Claims 1-3.
An electronic component comprising the insulating film of claim 4.