KR100995369B1 - Photo-crosslinking resin composition, its Dielectric insulating film and Electronic device - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition having good photosensitive characteristics such as resolution and residual film ratio, adhesion to a substrate in a low exposure region, light resistance to a UV region, and light transmittance in a visible region, and having an etching process margin, an exposure margin, and a light resistance. This is to provide a photosensitive resin composition for an interlayer organic insulating film for TFT-LCD which is required.

Description

Photo-crosslinking resin composition, its Dielectric insulating film and Electronic device}

The present invention provides an optical crosslinkable resin composition for forming an insulating film, an insulating film using the same, and a device including the same. More particularly, the present invention relates to a photosensitive crosslinked resin composition for forming an insulating film used in an initial process of a thin film transistor (TFT) for a liquid crystal display device (LCD).

The TFT substrate used in the liquid crystal display device 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 for connecting the wirings to be formed are formed.

A photosensitive thermosetting composition is used as a material of such an interlayer insulating film. For example, as a positive photosensitive composition, a photopolymerizable photosensitive composition is known as a composition consisting of an alkali-soluble resin and a 1,2-quinone diazide compound or a negative thermosetting composition. have.

However, in the case of the conventional positive photosensitive composition, the composition which consists of alkali-soluble resin and a 1, 2- quinonediazide compound is colored by thermal decomposition at the time of hard baking after exposure and image development. Therefore, when the light transmittance in the visible light is reduced, the organic insulating film is exposed to heat above a certain temperature for a predetermined time or absorbs short wavelengths such as ultraviolet rays, some components of the organic insulating film are decomposed to cause coloration or decompose to generate impurities. Therefore, a problem that causes an afterimage in the liquid crystal display is caused.

In addition, in the photopolymerizable negative photosensitive composition, as described above, the problem of impurities caused by coloring or partial component decomposition is not easily generated. However, due to the increase in molecular weight by photopolymerization, the alkali developer (KOH, NaOH, TMAH aq. Soln, etc.) Degradation to the resolution and adhesion to the substrate may occur.

In order to solve the problems of the prior art as described above, the present invention has excellent photosensitivity characteristics such as resolution and residual film ratio, adhesion to the substrate in a low exposure area, excellent light resistance to the UV region, and light transmittance in the visible region. It is intended to provide this good photosensitive resin composition.

In addition, the present invention provides a negative photosensitive resin composition used in an interlayer organic insulating film for TFT-LCD which requires etching process margin, exposure margin and light resistance.

Moreover, this invention provides the hardened | cured material formed by the negative photosensitive resin composition, the TFT substrate which uses this hardened | cured material as a protective film, and a liquid crystal display device.

In addition, the present invention has excellent photosensitivity characteristics such as resolution and residual film ratio when used as an interlayer insulating film of a TFT, excellent adhesion to a substrate even in a low exposure region, excellent light resistance to a UV region and a light transmittance in a visible region. It is to provide a photosensitive resin composition capable of satisfying all of the above-described characteristics, such as satisfactory, a liquid crystal display including an insulating film and an insulating film prepared by using the same.

The photosensitive resin composition for solving the above technical problem,

a) a1) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixture thereof a2) aromatic unsaturated compound a3) unsaturated compound having epoxy group-containing unsaturated compound and / or oxetane group a4) copolymer having monoolefin unsaturated compound as monomer ,

  b) a polymerizable compound having at least one ethylenically unsaturated double bond,

  c) photopolymerization initiator,

d) A functional silane compound.

The present invention also relates to a) a1) unsaturated carboxylic acids, unsaturated carboxylic anhydrides, or mixtures thereof a2) monoolefinically unsaturated compounds a3) unsaturated compounds having epoxy group-containing unsaturated compounds and / or oxetane groups a4) aromatic unsaturated compounds Copolymer,

b) a polymerizable compound having at least one ethylenically unsaturated double bond,

c) photopolymerization initiator,

d) functional silane compounds,

e) It is a composition containing a (meth) acrylate type monomer.

Moreover, this invention is a composition which further contains f) a ultraviolet absorber in the composition of this invention of each said aspect.

In another aspect of the present invention, the copolymer further comprises a5) a polymerizable unsaturated imide monomer, thereby providing an insulating film excellent in the stability and long-term stability of the process.

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

Copolymer (a) used in the present invention,

a1) 5 to 40 mol% of unsaturated carboxylic acids, unsaturated carboxylic anhydrides, or mixtures thereof,

a2) 5 to 70 mol% of aromatic unsaturated monomers,

a3) 1 to 10 mol% of an epoxy group-containing unsaturated compound and / or an unsaturated compound having an oxetane group,

a4) 5 to 50 mol% of monoolefinically unsaturated monomers.

In addition, 0.5 to 20 mol% of an imide monomer compound having a5) polymerizable defects may be additionally used for stability and long term stability of the process. The composition ratio is based on the composition ratio with respect to the total content of the monomer alone, except for the solvent in the monomer composition as a whole.

The copolymer of the present invention can realize good planarization performance and heat resistance as a ratio only when it is controlled within the above-described content in the structural units, and can satisfy all the problems aimed at by the present invention. In preparing the copolymer of the present invention, it is polymerized using 50 to 500 parts by weight of an organic solvent as a polymerization solvent with respect to 100 parts by weight of the entire monomer.

As the unit constituting the copolymer, the structural unit derived from a1) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof contains 5 to 40 mol%. Copolymers of less than 5 mol% are difficult to dissolve in an aqueous alkali solution, and copolymers of more than 40 mol% are so soluble in an aqueous alkali solution is too large to control the thickness of the thin film during coating.

Examples of the 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; Etc. can be mentioned. Among them, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in view of copolymerization reactivity, solubility in aqueous alkali solution and easy availability, and the above components are used alone or in combination.

The aromatic unsaturated monomer which is (a2) component of this invention is an aromatic vinyl compound, The content is 5-70 mol%. Examples of the compound include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, fluoro styrene and chloro styrene And nitrogen-containing aromatic vinyls such as styrene monomers such as bromostyrene, dibromostyrene, iodine styrene, nitrostyrene, acetyl styrene, methoxy styrene and divinylbenzene, and vinylpyridine and vinyl carbazole.

The epoxy group-containing monomer or oxetanyl group-containing monomer (a3) used in the present invention is preferably an epoxy monomer copolymerizable with the above unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof.

As an epoxy-group-containing unsaturated compound, For example, glycidyl methacrylate, 2-methylglycidyl methacrylate, 6,7-epoxyheptyl methacrylic acid, 4-hydroxybutyl acrylate glycidyl ether, o Vinyl-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like, and 3- (methacryloyloxymethyl) oxetane as an oxetanyl group-containing unsaturated compound. , 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyl oxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane , 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, 3- (methacryloyl oxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -3 -Methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -3-methyloxetane and the like can be exemplified, but is not limited thereto.

The above components have a wide process margin of the resulting photosensitive resin composition, and have an effect of increasing the heat resistance of the obtained pattern and are used alone or in combination.

The a3) component of the present invention is preferably contained in 1 to 10 mol% with respect to the total monomer composition, when the content is in the above range is better in increasing the copolymerization reactivity and the adhesion of the obtained pattern. On the other hand, when the said component is less than 1 mol%, the heat resistance of the pattern obtained tends to fall, and when it exceeds 10 mol%, the storage stability of a copolymer tends to fall.

Specific examples of the monoolefinically unsaturated compound of component (a4) of the present invention include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate and methyl Acrylate, isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyloxyethyl methacrylate, isoboroyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl Acrylate, dicyclopentanyloxyethyl acrylate, isoboroyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate and the like. Mixed components may be used. The component is used in the range of 5 to 50 mol% serves to significantly improve the coating properties by increasing the reactivity of the copolymer and the solubility in the aqueous alkali solution.

In the present invention, a polymerizable maleimide compound (a5) may be additionally added to prevent defects of the insulating film in long-term stability or high temperature heat treatment in the process. Examples thereof include phenylmaleimide, cyclohexyl maleimide, benzyl maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide pro Cypionate, N- (9-acridinyl) maleimide and the like.

The organic solvent used for producing the copolymer of this invention is 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; Cellosolves 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; Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; Lactone, such as (gamma) -butyrolactone, etc. are mentioned. These organic solvents can be used individually by 1 type or in mixture of 2 or more types.

The copolymer (a) used in the present invention preferably has a polystyrene reduced weight average molecular weight (Mw) of 5000 to 50,000, more preferably 7000 to 30,000. In the case of the film obtained with Mw less than 7000, developability, residual film ratio, and the like tends to be low, and pattern shape, heat resistance, and the like tend to be inferior.

* The compound (b) which has an ethylenically unsaturated double bond of this invention gives a role which improves heat resistance, a sensitivity, etc. of the pattern obtained from the photosensitive resin composition, and is represented by following General formula (B-1) and general formula (B-2) ), And mixtures of one or more components selected from general formula (B-3). The composition ratio of 50 to 120 parts by weight based on 100 parts by weight of the copolymer can maintain the transmittance, improve the adhesiveness and surface smoothness, and is also good in workability.

(In Formula (B-1), (B-2), and (B-3), each B independently represents-(CH ₂ CH ₂ O)-,-(CH ₂ CH (CH ₃ ) O)-, and COCH. Any one of ₂ CH ₂ CH ₂ CH ₂ CH ₂ O-, X independently represents any one of acryloyl group, methacryloyl group and hydrogen atom, and the sum of acryloyl group and methacryloyl group Are 5 or 6 in formula (B-1), 3 or 4 in (B-2), 3 in (B-3), n each independently represents an integer of 0 to 6, and The sum of n is 2 to 24, m each independently represents an integer of 0 to 6, the sum of m is 2 to 16, and each independently represents an integer of 0 to 6, and the sum of l is 1 ~ 12)

Examples of the compounds commercialized as KAYARAD TPA-320, copper TPA-330, copper PET-30, copper D-310, copper D-330, copper DPCA-20, copper DPCA-30, copper DPCA-60, copper DPCA-120, copper DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.), NK ester A-TMPT-3EO, copper A-GLY-3E, copper A-GLY-6E, copper A-GLY-9E, copper A-GLY- 20E, East A-9300-1CL, East ATM-4E (above Shin-Nakamura), etc. are mentioned.

The compound b) may be used alone or as a mixture of two or more, and the amount of the compound is preferably used in an amount of 1 to 150 parts by weight, more preferably 50 to 120 parts by weight, based on 100 parts by weight of the a) copolymer.

The photoinitiator (c) used in the present invention has a function of initiating polymerization of the crosslinkable monomer by wavelengths such as visible light, ultraviolet light and far ultraviolet light.

Specifically, an initiator such as acetophenone series, benzophenone series, benzoin series and benzoyl series, xanthone series, triazine series, halomethyloxadiazole series, and lopin dimers can be used, and as long as it is a photoinitiator used in the art, Examples thereof include, but are not limited to, 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-phenylacrylic Dine, 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, o-benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl Carbonyl-diphenylphosphonyl oxide, hexafluorophosphoro-trial And a phenylphenylsulfonium salt, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide, and the like, but are not limited thereto.

The photopolymerization initiator is preferably included in the photosensitive resin composition of the present invention based on 100 parts by weight of 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight. If the content is less than 0.5 parts by weight, the degree of curing is lowered, the low sensitivity is difficult to implement a normal pattern shape, and there is a problem in that the straightness of the pattern is not good, if more than 5 parts by weight can be lowered due to the high degree of curing There exists a problem that a residual film tends to generate | occur | produce in parts other than the formed pattern.

The said functional silane compound (d) of this invention can be added in order to improve adhesiveness of the protective film formed and a board | substrate. As such a compound, a functional silane compound having a reactive substituent can be used. As said reactive substituent, a carboxyl group, methacryloyl group, an isocyanate group, an epoxy group, etc. are mentioned, for example. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, and γ-glycidoxypropyltrimethoxy Silane, (gamma)-glycidoxy propyl triethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyl trimethoxysilane, etc. are mentioned.

Such d) component is used in an amount of preferably 100 parts by weight or less, more preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight. When the d) component exceeds 30 parts by weight, the storage stability of the composition tends to decrease.

As the f) ultraviolet absorber of the present invention, derivatives such as benzotriazole-based, benzophenone-based, triazine derivatives, oxalic anhydride-based, pyrimidine-based, and salicylic acid derivatives may be used. It is preferable that it is a triazine derivative. This f) ultraviolet absorber is used in an amount of preferably 1 to 20 parts by weight or less, more preferably 5 to 10 parts by weight or less per 100 parts by weight of the copolymer. If the content is less than 1 part by weight, the light resistance is not sufficient, and if it exceeds 20 parts by weight, there is a problem in that it is difficult to implement the pattern due to the decrease in sensitivity.

In addition, the present invention is particularly good because the hindered amine light stabilizer may be used together to improve the light resistance and to maintain the pattern shape characteristics very well. The hindered amine compound is a 2,2,6,6-tetraalkylpiperidine derivative having a substituent at the 4-position with a molecular weight of 250 or more, and examples of the substituent at the 4-position are carboxylic acid residues and alkoxy. A group, an alkyl amino group, a hydroxyl group etc. are mentioned. In the N-position, an alkyl group and an acyl group are substituted.

In this invention, surfactant can also be further included in order to improve the application | coating performance of a resin composition as needed. Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and other surfactants.

For example, BM-1000, BM-1100 (manufactured by BM CHEMIE), Megapack F142 D, Copper F172, Copper F173, Copper F183 (manufactured by Dainippon Ink & Chemical Co., Ltd.), Florade FC-135, Copper FC-170C, copper FC-430, copper FC-431 (manufactured by Sumitomo 3M Co., Ltd.), Supron S-112, copper S-113, copper S-131, copper S-141, copper S-145 , S-382, SSC-101, SSC-102, SSC-103, SSC-104, SSC-105, SSC-106 (manufactured by Asahi Glass Co., Ltd.), F-Top EF301, S 303, East 352 (manufactured by Shin-Akita Kasei Co., Ltd.), SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (manufactured by Toray Silicone Co., Ltd.) Fluorine-based and silicone-based surfactants such as); 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.), (meth) acrylic acid-based copolymer polyflow No. 57, 95 (manufactured by Kyoeisha Oil Chemical Industries, Ltd.).

The addition amount of these surfactant is used per 100 weight part of polymers, Preferably it is 5 weight part or less, More preferably, it is used at 0.5-2 weight part or less.

The solvent of the photosensitive resin composition which concerns on this invention is 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; Cellosolves 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, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, and propionic acid Aliphatic carboxylic acid esters such as isopropyl, n-butyl propionate and isobutyl propionate; Other 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; Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolactone; Can be mentioned. These organic solvents can be used individually by 1 type or in mixture of 2 or more types.

Each component mentioned above is normally used so that solid content concentration may be 5 to 70% weight, Preferably it is the range of 10 to 50% weight.

The present invention has excellent photosensitivity characteristics such as resolution and residual film ratio when used as an interlayer insulating film of a TFT, and excellent adhesion to a substrate even in a low exposure area. In addition, it is possible to provide a liquid crystal display including a photosensitive resin composition capable of satisfying all of the above characteristics, such as excellent light resistance to a UV region and good light transmittance in a visible region, and an insulating film and an insulating film manufactured using the same. . In the case of forming the insulating film of the composition of the present invention, in particular, the pattern shape may give a very excellent effect.

Hereinafter, the present invention will be described by way of example for specific description of the present invention, but the present invention is not limited to the following examples.

Example 1

[Production of Photosensitive Resin Composition]

100 parts by weight of the monomer mixture having a composition of styrene / methyl methacrylate / methacrylic acid / glycidyl methacrylate = 50/20/25/5 (mol%) was added to 4 parts by weight of azobisisobutyronitrile. As a polymerization initiator, it melt | dissolved in 150 weight part of 3-methoxy propionate methyl solvents, and solution-polymerized at 65 degreeC for 6 hours, and obtained the copolymer (A) whose weight average molecular weight is 15,300.

The structure of KAYARAD DPCA20 (Nippon Kayaku Co., Ltd .: (B) in the general formula B-1 is COCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O-, and X: acryloyl group, n) based on 100 parts by weight of the photopolymerizable copolymer. The total of 2, molecular weight 807) 90 parts by weight, 5 parts by weight of 4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 1 part by weight of γ- glycidoxy propyl triethoxysilane And 3 parts by weight of 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -1,3,5-triazine, and then a pore diameter of 0.5 After filtration with a filter of μm, the photosensitive resin composition was prepared, and the following physical properties were evaluated using the same, and the results are shown in Table 1.

[Development evaluation] After spin-coating the said photosensitive resin composition on a silicon wafer, it prebaked for 90 second on the high temperature plate maintained at 105 degreeC, and formed the coating film of 5 micrometers in thickness.

The composition film was exposed to light at about 100 nm based on 365 nm using an aligner (trade name MA6) having a wavelength of 200 nm to 450 nm, and a developing solution consisting of an aqueous 2.38 wt% tetramething ammonium hydroxide solution was used at 23 ° C. Was developed through a spray nozzle. The thermosetting film was obtained by heating the obtained exposure film in 220 degreeC and 1 hour with a convection oven. The developability was evaluated through the shape of the developed fine pattern.

 RESOLUTION: The image of the thermosetting film was observed with the optical microscope, and the line width (micrometer) of the minimum contact hole resolved was made into the resolution.

[Pattern shape]: The pattern shape was evaluated by the following criteria by observing the pattern shape formed in the contact hole which has a 10 micrometer line width of a thermosetting film with a scanning microscope.

A: The rectangle is good and there is no bottom tail

B: Rectangle is good but has a little tail

C: poor rectangularity, or not resolved

Adhesion Evaluation: Using the substrate prepared in the above-mentioned photosensitive evaluation, a cross-cut test was conducted according to ASTM D3359, and the results are shown in Table 1 below. At this time, the adhesive force was evaluated according to the following criteria.

[Evaluation of Light Discoloration Resistance] In the above embodiment, except that the entire surface was exposed without using a photomask, the same cured film formed was about 365 nm using an aligner (trade name MA6) which gave a wavelength of 200 nm to 450 nm. Exposure was carried out for a period of time to 50J and the change in transmittance was evaluated at 300nm to 400nm. X: 5 ~ 10%, △: 3 ~ 5%, ○: 1 ~ 3%

[Storage Stability] The composition solution obtained in the above Example was stored at 23 ° C. using a low temperature thermostat and the viscosity change of the composition solution was measured.

(Circle) and the case where 5-10 were used for the case where a viscosity change was less than 5% were made into the case where (triangle | delta) and 10% were exceeded. The results are shown in Table 1.

[Example 2]

4 parts by weight of 100 parts by weight of a monomer mixture having a composition consisting of styrene / methyl methacrylate / methacrylic acid / glycidyl methacrylate / cyclohexylmaleimide = 32/25/29/5/10 (mol%) Using azobisisobutyronitrile as a polymerization initiator, solution polymerization was carried out for 6 hours at 65 ° C in a 3-methoxypropionate methyl solvent to obtain a copolymer (B) having a weight average molecular weight of 20,200. The same procedure was followed except that copolymer (B) was used instead of copolymer (A) of Example 1, and the results are listed in Table 1.

Example 3

100 weights of monomer mixture of composition consisting of styrene / methyl methacrylate / methacrylic acid / 4-hydroxybutyl acrylate glycidyl ether / cyclohexylmaleimide = 32/25/28/10/3 (mol%) 4 parts by weight of azobisisobutyronitrile was used as a polymerization initiator to carry out solution polymerization at 65 ° C for 6 hours in a 3-methoxypropionate methyl solvent to obtain a copolymer (C) having a weight average molecular weight of 20,400. The same procedure was followed except that copolymer (C) was used instead of copolymer (A) of Example 1, and the results are listed in Table 1.

Example 4

Styrene / methylmethacrylate / methacrylic acid / 3-ethyl-3-methylmethacrylate oxetane / cyclohexylmaleimide = 32/25/28/5/10 (mol%) monomer mixture 100 4 parts by weight of azobisisobutyronitrile was used as a polymerization initiator to carry out solution polymerization at 65 ° C for 6 hours in a 3-methoxypropionic acid solvent to obtain a copolymer (D) having a weight average molecular weight of 10,500. The same procedure was followed except that copolymer (D) was used instead of copolymer (A) of Example 1, and the results are listed in Table 1.

Example 5

100 parts by weight of a monomer mixture having a composition of styrene / methyl methacrylate / methacrylic acid /-(methacryloyloxymethyl) -3-ethyloxetane = 45/20/25/10 (mol%), 4 Using a weight part of azobisisobutyronitrile as a polymerization initiator, solution polymerization was carried out for 6 hours at 65 ° C. in 3-methoxypropionate methyl solvent to obtain a copolymer (E) having a weight average molecular weight of 10,000. With respect to 100 parts by weight of the photopolymerizable copolymer, NK ester A-9300-1CL (manufactured by Shin-Nakamura Co., Ltd .: in general formula B-3) has the structure of (CH) COCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O- and X Is an acryloyl group, and the total of n is 3) 90 parts by weight, 5 parts by weight of 4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine and? -Glycidoxypropyltriethoxysilane. 1 part by weight and 3 parts by weight of 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -1,3,5-triazine After filtration with a filter having a pore diameter of 0.5 μm to prepare a photosensitive resin composition, the following physical properties were evaluated using the results, and the results are shown in Table 1.

Comparative Example 1

100 parts by weight of the monomer mixture having a composition of styrene / methyl methacrylate / methacrylic acid / glycidyl methacrylate = 40/30/25/5 (mol%) was added to 4 parts by weight of azobisisobutyronitrile. As a polymerization initiator, the solution polymerization was carried out for 6 hours at 65 degreeC in the 3-methoxy propionate methyl solvent, and the copolymer which has a weight average molecular weight of 50,000 was obtained.

The photosensitive resin composition was produced and evaluated in the same manner as in Example 1 except that the above copolymer was used instead of the photopolymerizable copolymer of Example 1.

Comparative Example 2

100 parts by weight of a monomer mixture having a composition of styrene / methyl methacrylate / methacrylic acid / glycidyl methacrylate = 38/27/25/10 (mol%) was added 4 parts by weight of azobisisobutyronitrile. As a polymerization initiator, the solution polymerization was carried out for 6 hours at 65 degreeC in 3-methoxy propionate methyl solvent, and the copolymer which has a weight average molecular weight of 20,000 was obtained.

The photosensitive resin composition was produced and evaluated in the same manner as in Example 1 except that the above copolymer was used instead of the photopolymerizable copolymer of Example 1.

Comparative Example 3

4 parts by weight of azobis, 100 parts by weight of a monomer mixture having a composition of styrene / methyl methacrylate / methacrylic acid / 4-hydroxybutylacrylate glycidyl ether = 50/20/25/5 (mol%) Using isobutyronitrile as a polymerization initiator, solution polymerization was carried out for 6 hours at 65 ° C. in 3-methoxypropionate methyl solvent to obtain a copolymer having a weight average molecular weight of 20,000.

90 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd .: product wherein X is an acryloyl group and the total of n is 0) with respect to 100 parts by weight of the photopolymerizable copolymer and 4-bis (trichloromethyl 5 parts by weight of 6-p-methoxyphenyl-s-triazine, 1 part by weight of γ-glycidoxypropyltriethoxysilane and 2,4-bis (2,4-dimethylphenyl) -6- (2 3 parts by weight of -hydroxy-4-isooctyloxyphenyl) -1,3,5-triazine, and then filtered through a filter having a pore diameter of 0.5 µm to prepare a photosensitive resin composition. The physical properties were evaluated and the results are shown in Table 1.

<Table 1> Property comparison data

Claims (9)

delete delete a) 5 to 40 mol% of unsaturated carboxylic acids, unsaturated carboxylic anhydrides, or mixtures thereof; 5 to 70 mol% of aromatic unsaturated monomers; 1 to 10 mol% of an epoxy group-containing unsaturated compound, an unsaturated compound having an oxetane group or a mixture thereof; 5 to 50 mol% of monoolefinically unsaturated monomers; And 100 parts by weight of a copolymer of 0.5 to 8 mol% of an imide monomer having an unsaturated group
b) 1 to 150 parts by weight of any one or more compounds selected from the following general formulas (B-1), (B-2) and (B-3) as photopolymerizable ethylenic monomers;

(In Formula (B-1), (B-2), and (B-3), each B independently represents-(CH ₂ CH ₂ O)-,-(CH ₂ CH (CH ₃ ) O)-, and COCH. Represents any one of ₂ CH ₂ CH ₂ CH ₂ CH ₂ O-, and each X independently represents any one of an acryloyl group, a methacryloyl group, and a hydrogen group; , The sum of acryloyl group and methacryloyl group is 5 or 6 in formula (B-1), 3 or 4 in (B-2), 3 in (B-3), and n is Each independently represents an integer of 0 to 6, the total of each n is 2 to 24, m each independently represents an integer of 0 to 6, the total of m is 2 to 16, and l is each independently 0 The integer of -6 is shown, and the sum total of l is 1-12.)
c) 0.5 to 10 parts by weight of a photoinitiator
d) 0.5 to 30 parts by weight of the functionalized silane compound
Photosensitive crosslinked resin composition comprising a. delete The method of claim 3,
The functional silane compound may be a carboxyl group (carbocyl), methacryloyl group (methacryloyl), isocyanyl group (isocyanyl), epoxy group (epoxy), imidazole group (imadazol), thiol group (thiol), amine group (amino group) Photosensitive crosslinked resin composition, characterized in that the (silicon compound) having a reactive group selected from. The method of claim 3,
The ultraviolet absorber is a benzotrizols, benzophenones, benzophenons, trizines, oxalic anilides, pyrimidines, salicylic acids. Photosensitive crosslinked resin composition selected. The method of claim 6,
Substitutes selected from carboxylic residues, alkoxy groups, alkylamino groups, hydroxy groups in the 4-position and alkyl or subunits in the N-position Added steric hindered photo stabilizer selected from 2,2,6,6-tetraalkylpiperidine derivatives with substituents containing acyl The photosensitive crosslinking resin composition further comprising. An insulating film formed by curing the photosensitive resin composition of claim 3. An electronic component having the insulating film of claim 8.