KR20040002492A - Composition for Forming Insulating Interlayers by Ink Jet Method and Process for Forming Insulating Interlayers - Google Patents

Abstract

PURPOSE: To provide a composition which satisfies various performances required as an interlayer insulating film, such as adhesion, surface hardness, transparency, heat-, light- and solvent resistances and is used for forming an interlayer insulating film by a low-cost ink jet system. CONSTITUTION: The composition comprises (A) a copolymer of (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride, (a2) an epoxy-containing unsaturated compound and (a3) other olefinic unsaturated compounds, (B) a 1,2-quinonediazide compound and (C) a solvent having >=180°C boiling point under ordinary pressure.

Description

Composition for Forming Insulating Interlayers by Ink Jet Method and Process for Forming Insulating Interlayers}

TECHNICAL FIELD The present invention relates to a composition suitable as a material for forming an interlayer insulating film used for an optical device such as a liquid crystal display device, an integrated circuit device, a solid-state imaging device by an inkjet method, and a method of forming the interlayer insulating film by an inkjet method.

In general, electronic components such as thin film transistors (hereinafter referred to as "TFT") type liquid crystal display elements, magnetic head elements, integrated circuit elements, and solid-state image pickup elements are provided with an interlayer insulating film in order to insulate the wiring arranged in layers. It is. When forming an interlayer insulating film, the photolithographic method using the radiation sensitive resin composition which has the characteristic of being able to obtain the interlayer insulation film which has a small number of processes for obtaining the required pattern shape interlayer insulation film, and has sufficient flatness is used widely. have.

As a method of forming such an interlayer insulating film, a conventional method such as a spray method, a roller coating method, a rotary coating method, a bar coating method, or the like is applied onto a substrate surface such as a TFT, and after removal of the solvent by prebaking to obtain a coating film, The method of forming a target interlayer insulation film by heat processing is known. However, in these methods, a large amount of resin composition is required for stable application | coating beyond the amount of resin composition required for interlayer insulation film formation. Therefore, there was a lot of waste of the resin composition, and therefore, there was a problem such as high cost.

On the other hand, Japanese Patent Laid-Open No. 59-75205, Japanese Patent Laid-Open No. 61-245106, Japanese Patent Laid-Open No. 63-235901 and the like use a inkjet head to form a colored layer of a color filter. The manufacturing method of the color filter of the inkjet system provided with the process of forming the form is disclosed, In this method, the control of the position which discharges the droplet of the resin composition for color filters is easy, and since the waste of the resin composition is small, manufacturing cost is produced. There is an advantage that can be reduced.

However, these publications do not sufficiently consider the composition suitable for the inkjet method for the interlayer insulating film composition of the electronic device.

This invention is made | formed in view of the said situation in the prior art, The subject satisfy | fills the various performance calculated | required as an interlayer insulation film, such as adhesiveness, surface hardness, transparency, heat resistance, light resistance, and solvent resistance, and at the same time low cost inkjet It is to provide a composition for forming an interlayer insulating film suitable for manufacturing by a method, and a method for forming an interlayer insulating film by an inkjet method.

BRIEF DESCRIPTION OF THE DRAWINGS The schematic diagram which shows the cross-sectional shape of an interlayer insulation film.

The present inventors have examined in detail the behavior in the manufacturing process of the interlayer insulating film by the inkjet method, and as a result, the clogging of the inkjet head used is eliminated, and the droplets of the composition for forming the interlayer insulating film can be ejected with good straightness. In order to do this, it is necessary to slow down the drying speed of the droplets upon discharging the interlayer insulating film composition, and to control the viscosity rise of the droplets due to excessively rapid solvent evaporation and to prevent the precipitation of solids. I knew it.

The present invention has been made by the above facts, and according to the present invention,

(A) Copolymer of (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group containing unsaturated compound, and (a3) other olefinic unsaturated compound (Hereinafter, "copolymer (A) "),

(B) 1,2-quinonediazide compound, and

(C) A composition for forming an interlayer insulating film by an inkjet method, characterized by containing a solvent having a boiling point at atmospheric pressure of 180 ° C or higher.

Moreover, according to this invention, the said subject is also achieved by the formation method of the interlayer insulation film characterized by including at least the following process.

(1) The process of forming the coating film of the said composition on the surface of a board | substrate with an inkjet apparatus.

(2) Irradiating at least a part of the formed coating film with radiation.

(3) Developing process.

Hereinafter, the other structural component used for the composition of this invention is demonstrated in detail.

Copolymer (A)

The copolymer (A) can be produced by radical polymerization of compound (a1), compound (a2), compound (a3) and compound (a4) in the presence of a polymerization initiator in a solvent.

The copolymer (A) used in the present invention preferably has a structural unit derived from compound (a1) with respect to the sum of the repeating units derived from compound (a1), compound (a2) and compound (a3). 40 wt%, particularly preferably 10 to 30 wt%. Copolymers having this structural unit of less than 5% by weight are difficult to dissolve in an aqueous alkali solution, while copolymers exceeding 40% by weight tend to have too high solubility in an aqueous alkali solution. As a compound (a1), For example, 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 divalent or more polyvalent carboxylic acid, such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Esters;

and mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at the sock end, such as? -carboxypolycaprolactone mono (meth) acrylate. Among these, 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. These are used alone or in combination.

The copolymer (A) used in the present invention preferably has a structural unit derived from compound (a2) with respect to the sum of the repeating units derived from compound (a1), compound (a2) and compound (a3). 70 wt%, particularly preferably 20 to 60 wt%. When this structural unit is less than 10 weight%, there exists a tendency for the heat resistance and surface hardness of the obtained interlayer insulation film or insulating film to fall, and when it exceeds 70 weight%, there exists a tendency for the storage stability of a copolymer to fall.

As the compound (a2), for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid -3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl , o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like. Among these, methacrylic acid glycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like are copolymerizable and reactive. And the point which raises heat resistance and surface hardness of the light-diffusion reflecting film obtained. These are used alone or in combination.

The copolymer (A) used in the present invention preferably has a structural unit derived from the compound (a3) with respect to the sum of the repeating units derived from the compound (a1), the compound (a2) and the compound (a3). 70% by weight, particularly preferably 15 to 50% by weight. When this structural unit is less than 10 weight%, there exists a tendency for the storage stability of a copolymer (A) to fall, and when it exceeds 70 weight%, there exists a tendency for a copolymer (A) to be insoluble in aqueous alkali solution.

Examples of the compound (a3) include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate; Acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2.6 ] decane-8-yl methacrylate (commonly known in the art as dicyclopentanyl methacrylate), dicyclo Methacrylic acid cyclic alkyl esters such as fentanyloxyethyl methacrylate and isoboroyl methacrylate; Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2.6 ] decane-8-yl acrylate (commonly known in the art as dicyclopentanyl acrylate), dicyclopentanyloxyethylacrylic Acrylic acid cyclic alkyl esters such as acrylate and isoboroyl acrylate; Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;

Hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate;

Bicyclo [2.2.1] hept-2-ene,

5-methylbicyclo [2.2.1] hept-2-ene,

5-ethylbicyclo [2.2.1] hept-2-ene,

5-hydroxybicyclo [2.2.1] hept-2-ene,

5-hydroxymethylbicyclo [2.2.1] hept-2-ene,

5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene,

5-methoxybicyclo [2.2.1] hept-2-ene,

5-ethoxybicyclo [2.2.1] hept-2-ene,

5,6-dihydroxybicyclo [2.2.1] hept-2-ene,

5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene,

5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene,

5,6-dimethoxybicyclo [2.2.1] hept-2-ene,

5,6-diethoxybicyclo [2.2.1] hept-2-ene,

5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene,

5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene,

5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene,

5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene,

5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene,

5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene,

5,6-di (t-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene

Bicyclo unsaturated compounds such as 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene; And

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N- Succinimidyl-4-maleimidobutylate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide, and the like. Can be mentioned.

Among them, styrene, t-butyl methacrylate, dicyclopentanyl methacrylate, p-methoxy styrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, bicyclo [2.2.1] hept-2-ene Phenyl maleimide, cyclohexyl maleimide, etc. are preferable from a copolymerization reactivity and the solubility with respect to aqueous alkali solution. These are used alone or in combination.

As a preferable specific example of the copolymer (A) used by this invention, for example,

Styrene / methacrylic acid / methacrylate glycidyl copolymer,

1,3-butadiene / styrene / methacrylic acid / methacrylic acid glycidyl copolymer,

Styrene / methacrylic acid / methacrylic acid glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate copolymer,

Styrene / methacrylic acid / methacrylic acid glycidyl / cyclohexylmaleimide copolymer,

Styrene / methacrylic acid / methacrylate glycidyl / phenylmaleimide copolymer,

Styrene / methacrylic acid / methacrylic acid glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / cyclohexylmaleimide copolymer, among which

Styrene / methacrylic acid / methacrylic acid glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate copolymer,

Particular preference is given to styrene / methacrylic acid / glycidyl glycidyl / cyclohexylmaleimide copolymers.

As a solvent used for manufacture of a copolymer (A), For example, Alcohol, such as methanol and ethanol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene;

Ketones such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; And methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxyacetic acid Ethyl, butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate ethyl, 3-hydroxypropionate propyl, 3-hydroxypropionate butyl, 2-hydroxy Methyl oxy-3-methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate propyl, butyl acetate, ethoxy acetate methyl, ethoxy acetate, ethoxy acetate propyl, butyl ethoxy acetate, pro Methyl acetate, ethyl propoxy acetate, propyl acetate, propoxy acetate, butyl acetate, methyl butoxy acetate, ethyl butoxy acetate, Propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid Ethyl, 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate , 3-methoxy ethyl propionate, 3-methoxy propyl propionate, 3-methoxy propionate, methyl 3-ethoxy propionate, 3-ethoxy propionate, 3-ethoxy propyl propionate, 3-ethoxy propionate, 3-propoxy propionate, 3-propoxy propionate, 3-propoxypropionate, 3-propoxy propionate, 3-butoxypropionate, 3-butoxypropionate, 3-butoxypropion Profile, may be mentioned esters such as butyl propionate, 3-butoxy.

As a polymerization initiator used for manufacture of a copolymer (A), what is generally known as a radical polymerization initiator can be used, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- Azo compounds such as (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, 1,1'-bis- (tert-butylperoxy) cyclohexane; And hydrogen peroxide. When using a peroxide as a radical polymerization initiator, a peroxide can also be used together with a reducing agent to make it a redox type initiator.

As for the copolymer (A) used by this invention, the polystyrene conversion weight average molecular weight (henceforth "Mw") is 2x10 <^3> -1 * 10 <^5> normally, Preferably it is 5x10 <^3> -5 * 10 <^4>. Is preferably. If Mw is less than 2 × 10 ³ , the resulting film may have low developability, residual film ratio, or the like, and poor pattern shape, heat resistance, and the like. On the other hand, if it exceeds 1 × 10 ⁵ , the sensitivity may be lowered or the patterning shape may be reduced. You may fall.

As described above, the copolymer (A) used in the present invention has a carboxyl group and / or a carboxylic anhydride group and an epoxy group, has appropriate solubility in an aqueous alkali solution, and is suitable for heating even without using a special curing agent. Can be easily cured.

The composition including the copolymer (A) does not generate developing residues in the developing process during the manufacturing process of the interlayer insulating film, and there is no film reduction, and it is possible to easily form a desired shape.

(B) 1,2-quinonediazide compound

(B) 1,2-quinonediazide compound used by this invention is a 1,2-quinonediazide compound which has a function which produces | generates a carboxylic acid by irradiation of radiation, such as an ultraviolet-ray, For example, 1,2 -Benzoquinone diazido sulfonic acid ester, a 1, 2- naphthoquinone diazido sulfonic acid ester, a 1, 2- benzoquinone diazido sulfonic acid amide, a 1, 2- naphthoquinone diazido sulfonic acid amide, etc. are mentioned.

Specific examples of these include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone azido-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone Diazido-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazido-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2 1,2-naphthoquinone diazido sulfonic acid ester of trihydroxy benzophenone, such as naphthoquinone diazido-5-sulfonic acid ester;

2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazido-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1,2 Naphthoquinone diazido-5-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinone diazido-4-sulfonic acid ester, 2,3,4,3 ' Tetrahydroxybenzophenone-1,2-naphthoquinone diazido-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazido-4-sulfonic acid Ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazido-5-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzo Phenone-1,2-naphthoquinone diazido-4-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinone diazido-5-sulfonic acid Ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinone diazido-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxy -3'-methoxybenzophenone-1,2-naph 1,2-naphthoquinone diazido sulfonic acid ester of tetrahydroxy benzophenone, such as a toquinone diazido-5-sulfonic acid ester;

2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinone diazido-4-sulfonic acid ester, 2,3,4,2', 6'-pentahydroxybenzophenone 1,2-naphthoquinone diazido sulfonic acid ester of pentahydroxy benzophenone, such as -1, 2- naphthoquinone diazido-5- sulfonic acid ester;

2,4,6,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone diazido-4-sulfonic acid ester, 2,4,6,3 ', 4', 5 ' Hexahydroxybenzophenone-1,2-naphthoquinone diazido-5-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone Hexahydroxy benzophene, such as diazido-4- sulfonic acid ester and 3,4,5,3 ', 4', 5'-hexahydroxy benzophenone- 1,2-naphthoquinone diazido-5- sulfonic acid ester Discussion 1,2-naphthoquinone diazido sulfonic acid ester;

Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazido-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazido -5-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinone diazido-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinone diazido -5-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinone diazido-4-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinone diazido -5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinone diazido-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl ) Ethane-1,2-naphthoquinone diazido-5-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinone diazido-4-sulfonic acid ester, bis ( 2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinone diazido-5-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyfe Nil) propane-1,2-naphthoquinone diazido-4-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinone diazido-5- Sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinone diazido-4-sulfonic acid ester, 1,1,3- Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinone diazido-5-sulfonic acid ester;

4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinone diazido-4-sulfonic acid ester, 4 , 4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinone diazido-5-sulfonic acid ester, bis ( 2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinone diazido-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl)- 2-hydroxyphenylmethane-1,2-naphthoquinone diazido-5-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7, 5 ', 6', 7'-hexanol-1,2-naphthoquinone diazido-4-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5 , 6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinone diazido-5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydrate Roxyflavan-1,2-naphthoquinone diazido-4-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinone diazide 5-sulfonic acid ester, such as (poly-hydroxy-phenyl) deulsu 1,2-naphthoquinonediazide sulfonic acid ester of the alkanoic map.

Moreover, the 1,2-naphthoquinone diazido sulfonic acid amides which changed the ester bond of the above-mentioned 1,2-naphthoquinone diazido sulfonic acid esters to an amide bond, for example, 2,3,4-trihydride Roxybenzophenone-1,2-naphthoquinone diazido-4- sulfonic acid amide etc. are also used preferably.

Among them, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone azido-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphtho Quinone diazido-4-sulfonic acid ester, 2,2 ', 4,4'- tetrahydroxy benzophenone-1,2-naphthoquinone diazido-4-sulfonic acid ester, bis (2, 4- dihydroxy phenyl ) Methane-1,2-naphthoquinone diazido-4-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] Bisphenol-1,2-naphthoquinone diazido-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinone Diazido-4-sulfonic acid ester is preferably used, among which 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone azido-4-sulfonic acid ester, 2,3,4,4 ' Tetrahydroxybenzophenone-1,2-naphthoquinone diazido-4-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl ] Ethylidene] bisphenol-1, 2-naphthoquinone diazido-4-sulfonic acid ester is especially preferable.

These 1,2-quinonediazide compounds can be used individually or in combination of 2 or more types.

The use ratio of the (B) 1,2-quinonediazide compound is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight based on 100 parts by weight of the copolymer (A).

When this ratio is less than 5 parts by weight, since the amount of acid generated by irradiation of the radiation is small, the difference in solubility between the irradiated portion and the unirradiated portion of the radiation to the alkaline aqueous solution serving as the developing solution becomes small, so that patterning becomes difficult. In addition, since the amount of acid involved in the epoxy group reaction decreases, sufficient heat resistance and solvent resistance cannot be obtained. On the other hand, when this ratio exceeds 100 weight part, in a short time irradiation, since unreacted (B) component remains in large quantities, the insolubilization effect to the said aqueous alkali solution becomes high too much and it becomes difficult to develop.

(C) a solvent having a boiling point of at least 180 ° C. at atmospheric pressure

The solvent in the present invention includes a solvent (hereinafter referred to as a "high boiling point solvent") having a boiling point (hereinafter referred to as "boiling point") at a normal pressure (1 atm) of 180 ° C or more. The boiling point of the point solvent is preferably 200 ° C. or more, and the upper limit of the boiling point of the high boiling point solvent is not particularly limited as long as the interlayer insulating film can be produced by the inkjet method, but the manufacturing process of the resin composition and the interlayer insulating film From the viewpoint of the operability in the production process of, a high boiling point solvent having a relatively low viscosity liquid at room temperature (20 ° C.) having a boiling point of 290 ° C. or lower, preferably 280 ° C. or lower is preferable. Preferable boiling range of a high boiling point solvent is 180-290 degreeC specifically, More preferably, it is 200-280 degreeC.

As the high boiling point solvent, for example, diethylene represented by the formula R ¹ -O (CH ₂ CH ₂ O) ₂ -R ² (wherein R ¹ and R ² independently represent an alkyl group having 2 to 10 carbon atoms) Glycol dialkyl ether solvents; Triethylene glycol dialkyl ether solvents represented by formula R ³ -O (CH ₂ CH ₂ O) ₃ -R ⁴ (wherein R ³ and R ⁴ independently represent an alkyl group having 1 to 10 carbon atoms);

Polyethylene glycol represented by the formula R ⁵ -O (CH ₂ CH ₂ O) _i -R ⁶ (wherein R ⁵ and R ⁶ independently represent an alkyl group having 1 to 10 carbon atoms, i is an integer of 2 to 30) Dialkyl ether solvents;

Propylene glycol dialkyl ethers represented by the formula R ⁷ -OCH (CH ₃ ) CH ₂ OR ⁸ (wherein R ⁷ and R ⁸ independently represent an alkyl group having 2 to 10 carbon atoms);

Ethylene glycol monoalkyl ethers, such as ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, and ethylene glycol monophenyl ether:

Ethylene glycol monoalkyl ether acetates such as ethylene glycol monobutyl ether acetate;

Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether and diethylene glycol mono-n-butyl ether;

Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propylether acetate and diethylene glycol mono-n-butylether acetate;

Other ethers such as ethylene glycol monophenyl ether acetate, diethylene glycol diethyl ether, benzyl ethyl ether, dihexyl ether;

Propylene glycol alkyl ether acetates such as propylene glycol butyl ether acetate;

Alcohols such as 1-octanol, 1-nonanol and benzyl alcohol;

Ketones such as methyl ethyl ketone, acetonyl acetone and isophorone;

Carboxylic acids such as caproic acid and caprylic acid;

Butyl lactate, ethyl benzoate, n-butyl benzoate, diethyl oxalate, diethyl maleate, di-n-butyl maleate, glycerin triacetate, di-n-butyl fumarate, dimethyl phthalate, diethyl phthalate, di-phthalate Ester solvents such as di-i-propyl phthalate, di-n-butyl phthalate, i-amyl salicylic acid, γ-butyrolactone, ethylene carbonate and propylene carbonate.

As a specific example of the high boiling point solvent preferable in this invention,

Ethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol, propylene glycol butyl ether acetate, diethylene glycol di-n-butyl ether, Tetraethylene glycol dimethyl ether, pentaethylene glycol dimethyl ether, hexaethylene glycol dimethyl ether, propylene glycol di-n-butyl ether, butyl lactate and the like.

The said high boiling point solvent can be used individually or in combination of 2 or more types.

The use amount of the high boiling point solvent is usually 100 to 10,000 parts by weight, preferably 1,000 to 10,000 parts by weight, more preferably 2,000 to 5,000 parts by weight based on 100 parts by weight of the copolymer (A).

In this invention, the following effects can be exhibited by using a high boiling point solvent. In other words,

(1) When the interlayer insulating film is formed by the inkjet method, the interlayer insulating film composition gradually becomes viscous by evaporation of the solvent. However, when the boiling point of the solvent is low, it is difficult to control the viscosity change. While the degree of change of the composition discharged in the beginning and the end increases, which hinders the formation of the interlayer insulating film, the use of a high boiling point solvent makes it possible to control the change of the viscosity in an appropriate range so that the formation of the desired interlayer insulating film is easy. Done.

(2) Since clogging due to dryness of the composition in the inkjet head for discharging the interlayer insulating film composition can be prevented, and flight curvature can also be prevented when discharging the composition, thereby ensuring good straightness. The utilization efficiency of the interlayer insulation film forming composition and the cleaning efficiency of the interlayer insulation film manufacturing apparatus are improved.

In addition, in this invention, a part of said high boiling point solvent can also be substituted by the solvent whose boiling point is less than 180 degreeC (henceforth a "low boiling point solvent").

As such a low boiling point solvent, for example

Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;

Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monopropyl ether acetate;

Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate;

Other ethers such as diethylene glycol dimethyl ether and tetrahydrofuran;

Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether;

Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol propyl ether acetate;

Alcohols such as methanol and ethanol;

Aromatic hydrocarbons such as toluene and xylene;

Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, 2-heptanone, 3-heptanone, and methyl isoamyl ketone; And

Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2- Methyl hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, methyl 3-hydroxypropionate Ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, methoxyacetic acid, methoxyacetic acid propyl, methoxy butyl acetate, ethoxyacetic acid Methyl, ethyl ethoxy acetate, ethoxy acetate propyl, methyl propoxy acetate, ethyl propoxy acetate, methyl butoxy acetate, butoxy acetane Ethyl Tate, 2-Methoxypropionate, Ethyl 2-methoxy Propionate, Methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, Methyl 2-butoxypropionate, Ethyl 2-butoxypropionate, 3-methoxypropionic acid Methyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate Ester, such as these, is mentioned.

Of these, diethylene glycols, propylene glycol monoalkyl ethers, propylene glycol alkyl acetates, and esters are preferable, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate , Propylene glycol ethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl lactate, and ethyl lactate are preferable.

These low boiling point solvents can be used individually or in mixture of 2 or more types.

When using a low boiling point solvent, the use ratio is 50 weight% or less normally with respect to the sum total of a high boiling point solvent and a low boiling point solvent, Preferably it is 30 weight% or less. In this case, when the use ratio of the low boiling point solvent exceeds 50% by weight, the desired effect by using the high boiling point solvent may be impaired.

<Other optional ingredients>

In the radiation-sensitive resin composition of the present invention, in addition to the copolymer (A), (B) 1,2-quinonediazide compound, and (C) a high boiling point solvent, two (D) epoxy groups may be added to the molecule as needed. The compound containing the above, (E) thermosensitive acid production compound, (F) adhesion | attachment adjuvant, and (G) surfactant can be contained.

As a compound containing 2 or more of said (D) epoxy groups in a molecule | numerator, For example, Bisphenol-A type, such as Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (made by Yuka Shell Epoxy Co., Ltd.). Commercially available epoxy resin, bisphenol F-type epoxy resin commercially available products such as Epicoat 807 (manufactured by Yuka Shell Epoxy Co., Ltd.), epicoat 152, 154 (manufactured by Yuka Shell Epoxy Co., Ltd.), EPPN 201, 202 (Nipbon Kayaku Co., Ltd.) Phenol novolac-type epoxy resin commercial products, EOCN-102, 103S, 104S, 1020, 1025, 1027 (manufactured by Nippon Kayaku Co., Ltd.), and epicoat 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd.) Cresol novolak-type epoxy resin commercial item, CY-175, 177, 179 (made by Shiba-Geigi A.R.), ERL-4234, 4299, 4221, 4206 (manufactured by UCC), Shodine 509 (Showa Denko) (Manufactured by Co., Ltd.), Alderite CY-182, 192, 184 (manufactured by Ciba-Geigi A.R.), Epikron 200, 400 (manufactured by Dainippon Ink, Inc.), Epicoat 871, 872 Shell Cyclic aliphatic epoxy resin commercial items, such as epoxy (manufactured by Co., Ltd.), ED-5661, 5662 (manufactured by Ceranis Co., Ltd.), epolite 100 MF (manufactured by Kyoeisha Chemical Co., Ltd.), epiol TMP (Nippon) Aliphatic polyglycidyl ether commercial items, such as Yushi Corporation make), are mentioned.

Among these compounds, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and aliphatic polyglycidyl ethers are seen from the viewpoint of developing and shape control of reflective irregularities. It is preferably used in the invention.

In addition to the epoxy compound (D), for example, compounds such as glycidyl ether of bisphenol A and bisphenol F can also be used.

The addition amount of the compound containing two or more of these (D) epoxy groups in a molecule | numerator is 100 weight part or less with respect to 100 weight part of copolymers (A), Preferably it is 1-100 weight part, More preferably, it is 5-50 weight part It is wealth. The hardened | cured material formed from the composition containing the compound containing two or more epoxy groups in a molecule in this range becomes excellent in heat resistance or adhesiveness. When the addition amount of the compound containing two or more epoxy groups in a molecule | numerator is less than 1 weight part, hardening reaction will not fully advance, and the cured film formed from such a composition may be inferior to heat resistance and solvent resistance. Moreover, when it exceeds 100 weight part, the softening point of the whole composition will fall, and the problem that it is difficult to maintain a shape during the heat processing at the time of forming the pattern used for a light-diffusion reflection film arises.

Moreover, although said copolymer (A) can also be called "a compound containing two or more epoxy groups in a molecule | numerator", it differs from (D) component in the point which has alkali solubility.

The said (E) thermosensitive acid generating compound can be used in order to improve heat resistance and hardness. Specific examples thereof include antimony fluoride, and examples of commercially available products include Sun Aid SI-L80, Sun Aid SI-L110, Sun Aid SI-L150 (above, manufactured by Sanshin Kagaku Kogyo Co., Ltd.), and the like.

The use ratio of (E) component becomes like this. Preferably it is 20 weight part or less, More preferably, it is 5 weight part or less with respect to 100 weight part of copolymers (A).

When this ratio exceeds 20 weight part, precipitates may arise and patterning may become difficult.

Moreover, in order to improve adhesiveness with a base, (F) adhesion | attachment adjuvant can also be used. As such an adhesion | attachment adjuvant, a functional silane coupling agent is used preferably, For example, the silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, is mentioned. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltri Methoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned.

Such adhesion aid is preferably used in an amount of 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer (A). When the amount of the adhesive aid exceeds 20 parts by weight, development residues may easily occur.

In order to improve applicability, (G) surfactant can be used. As the commercial item, for example, BM-1000, BM-1100 (manufactured by BM CHEMIE Co., Ltd.), Megapack F142D, Copper F172, Copper F173, Copper F183 (manufactured by Dainippon Ink Chemical Industries, Ltd.), Flowride 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, East S-382, East SC-101, East SC-102, East SC-103, East SC-104, East SC-105, East SC-106 (manufactured by Asahi Glass Co., Ltd.), F-Top EF301, East 303, copper 352 (manufactured by Shinsei Kasei Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (manufactured by Toray Silicone Co., Ltd.) Fluorine-based and silicone-based surfactants may be mentioned.

As the (G) component, in addition, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; Nonionic interfaces, such as polyoxyethylene dialkyl esters, such as polyoxyethylene aryl ethers, such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether, polyoxyethylene dilaurate, and polyoxyethylene distearate Active agent; Organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic-acid copolymer polyflow N0.57, 95 (made by Kyoeisha Chemical Co., Ltd.), etc. can be used.

These surfactants are preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of the copolymer (A). When the amount of the surfactant exceeds 5 parts by weight, film roughness may easily occur during application.

Composition for forming interlayer insulating film by inkjet method

The composition for forming an interlayer insulation film by the inkjet method of this invention is a solvent which the said copolymer (A), (B) 1,2-quinonediazide compound, and (C) boiling point are 180 degreeC or more, and the arbitrary addition It is manufactured by mixing an external compounding agent uniformly. Usually, the composition of the present invention is dissolved in a suitable solvent and used in solution. For example, the radiation sensitive resin composition of a solution state can be manufactured by mixing a copolymer (A), (B) 1,2-quinone diazide, and (C) boiling point solvent 180 degreeC or more by predetermined ratio. have.

Although the suitable solid content concentration can be used for the composition of this invention according to the use purpose, it can be used, for example in 10 to 40 weight% of solid content concentration.

The composition prepared as described above may be used after filtration separation using a Millipore filter having a pore size of 0.05 to 3.0 μm, preferably a pore size of 0.05 to 0.2 μm, or the like.

The composition of the present invention can form an interlayer insulating film by the following method.

Method of forming an interlayer insulating film

Next, the method of forming the interlayer insulation film of the present invention using the composition of the present invention will be described.

The method of forming the interlayer insulation film of this invention is characterized by including the following process at least.

(1) The process of forming the coating film of the said composition on the surface of a board | substrate with an inkjet apparatus.

(2) Irradiating at least a part of the formed coating film with radiation.

(3) Developing process.

(1) A step of forming a coating film of the composition on the substrate surface by an inkjet device

The composition of this invention can be apply | coated to the surface of a base substrate with an inkjet apparatus, Preferably a coating film can be manufactured by removing a solvent by prebaking.

As what can be used as said board | substrate, board | substrates, such as glass, quartz, a silicone, resin, can be used, for example. As resin, resin, such as a ring-opening polymer of polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, and cyclic olefin, and its hydrogenated substance, is mentioned, for example.

Although the conditions of prebaking differ according to the kind of each component, compounding magnification, etc., the conditions of about 0.5 to 15 minutes are usually optimal at 60-130 degreeC.

Although the film thickness after prebaking can be made into a desired value by solid content concentration and application | coating conditions of the radiation sensitive resin composition for interlayer insulation film formation, it can be made into about 0.25-6 micrometers.

(2) Irradiating at least a portion of the formed coating film with radiation

Next, at least a part of the formed coating film is irradiated with radiation. At this time, radiation can be irradiated to at least a part of the formed coating film, for example by irradiating radiation through a predetermined pattern mask. Examples of the radiation used herein include ultraviolet rays such as g rays (wavelength 436 nm), i rays (wavelength 365 nm), far ultraviolet rays such as KrF excimer lasers, X rays such as synchrotron radiation, and charged particle beams such as electron beams. Can be mentioned. Among these, g line and i line are preferable.

The exposure dose of these radiations is usually 50 to 10,000 J / m ² , preferably 100 to 5,000 J / m ² .

(3) developing process

After irradiation with radiation, a desired pattern can be obtained by developing using a developer to remove the irradiation portion of radiation. As a developing solution used here, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Alcohol amines such as dimethylethanolamine and triethanolamine; Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline or pyrrole, piperidine, 1,8-diazabicyclo- (5.4.0) -7-undecene, 1,5- An aqueous alkali solution in which cyclic amines such as diazabicyclo- (4.3.0) -5-nonane is dissolved in water is preferably used. In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the developer. Moreover, various organic solvents which melt | dissolve the composition of this invention can also be used as a developing solution.

As the developing method, a paddle developing method, a dipping method, a rocking dipping method and the like can be used.

After the development treatment, the patterned film may be subjected to a rinse treatment, for example, by running water washing.

In addition, decomposition of the 1,2-quinonediazide compound remaining in the film may be performed by irradiating the entire surface with radiation by a high pressure mercury lamp or the like.

After that, the desired interlayer insulating film can be preferably formed by heat curing the film using a heating apparatus such as a hot plate or oven. The heating temperature in this hardening process can be 150-280 degreeC, for example, and when it bakes on a hotplate, it can be made into 5 to 30 minutes, and when baking in oven, it can be made into 30 to 90 minutes. .

The interlayer insulating film thus formed satisfies adhesion, surface hardness, transparency, heat resistance, light resistance, solvent resistance, and the like.

<Example>

Although a synthesis example and an Example are shown to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example.

Preparation of Copolymer (A)

Hereinafter, the manufacture example of the copolymer (A) used for this invention is shown in the synthesis examples 1 and 2.

Synthesis Example 1

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 25 parts by weight of styrene, 20 parts by weight of methacrylic acid, 45 parts by weight of glycidyl methacrylate, and 10 parts by weight of methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl were substituted with nitrogen. After that, stirring was slowly started. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). Solid content concentration of the obtained polymer solution was 33.0%. In addition, the weight average molecular weight (Mw) of copolymer (A-1) was 6,000.

Synthesis Example 2

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 18 parts by weight of styrene, 20 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate and 22 parts by weight of cyclohexylmaleimide were added, and after nitrogen replacement, stirring was gradually started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-2). Solid content concentration of the obtained polymer solution was 33.0%. In addition, the weight average molecular weight (Mw) of the copolymer (A-2) was 12,000.

Preparation and Evaluation of the First Composition

<Example 1>

As a copolymer (A), the solution containing the copolymer (A-1) obtained by the synthesis example 1 (amount corresponded to 100 weight part (solid content) of copolymer (A-1)), and 2,3 as component (B). Condensate of 2,3,4,4'-tetrahydride with 1,4,4'-tetrahydroxybenzophenone (1 mol) and 1,2-naphthoquinone diazido-4-sulfonic acid chloride (2 mol) Oxybenzophenone-1,2-naphthoquinone diazido-4-sulfonic acid ester) 30 parts by weight, diethylene glycol monobutyl ether acetate as component (C), 800 parts by weight, γ-glycis as component (H) adhesion aid 15 parts by weight of doxypropyltrimethoxysilane and 0.1 parts by weight of SH-28PA (manufactured by Toray Silicone Co., Ltd.) as component (G) surfactants were added, and diethylene glycol methylethyl ether was added so that the solid content concentration was 10%. After addition, the first composition was prepared by filtration with a Millipore filter having a pore diameter of 0.2 μm.

Formation of Interlayer Insulator

After apply | coating the said composition on the glass substrate using the inkjet apparatus, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film. Then, after exposing with Canon Aliner-PLA-501F through a 5-30 micrometers insulating film pattern mask, it developed for 1 minute at 25 degreeC with the tetramethylammonium hydroxide 0.4weight% aqueous solution. Thereafter, the water was washed with water, dried and a pattern was formed on the wafer. This pattern was further heat-processed at 220 degreeC for 60 minutes in oven, and the insulation film pattern of 2.0 micrometers in film thickness was formed.

(1) evaluation of sensitivity

The minimum exposure amount which can form the pattern of 5-30 micrometers as mentioned above was investigated. This value is shown in Table 1. When this value is 2,000 J / m <^2> or less, it can be said that radiation sensitivity is favorable.

(2) Evaluation of pattern cross-sectional shape

As a result of observing the cross-sectional shape of the pattern with a scanning electron microscope, Table 1 shows which shape corresponds to A to C shown in FIG. 1. Like A or B, when the pattern edge is formed in the forward tapered shape or vertically, the pattern shape is said to be good. When the reverse taper is shown as in C, the adhesiveness is a problem because it is a problem.

(3) presence or absence of developing residue

After the insulating film pattern was formed in the same manner to the above on the glass substrate, the presence or absence of the development residue was investigated by the following two methods.

① Observe visually using green lamp (manufactured by Pnatech Co., Ltd.).

② Observed at 40,000 times magnification using a scanning electron microscope (Hitachi Seisakusho Co., Ltd., model "S-4200").

The observation results are shown in Table 1.

(4) evaluation of heat resistance

When forming an insulating film as mentioned above, Table 1 shows the change rate of the film thickness before and behind heat processing at 230 degreeC for 60 minutes in oven. When the absolute value of this value is within 5% before and behind heating, it can be said that heat resistance is favorable.

(5) Evaluation of solvent resistance

The insulating film pattern formed as mentioned above was immersed for 20 minutes in the dimethyl sulfoxide temperature-controlled at 70 degreeC, and the film thickness change rate by immersion was measured. The results are shown in Table 1. When the absolute value of this value is less than 5%, solvent resistance can be said to be favorable.

(6) evaluation of inkjet coating property

After using the inkjet apparatus, the said composition was apply | coated so that it might become a film thickness of 2.0 micrometers on a glass substrate, and it prebaked at 90 degreeC for 2 minutes on a hotplate, and formed the coating film. The surface unevenness | corrugation of this coating film was measured by the contact type film thickness measuring apparatus (alpha) -step (made by Tencol Japan Co., Ltd.) by the measurement length 2,000 micrometers, the measurement range 2,000 micrometers x 2,000 micrometers, and the measurement number n = 5. Table 1 shows the difference between the highest and lowest elevations (nm) for each measurement. When this value is 500 nm or less, it can be said that inkjet coating property is favorable.

(7) Evaluation of dryness characteristics

The composition was aspirated by a fixed needle microsyringe (Hamilton microsyringe, model No. 701, needle inner diameter 0.13 mm), the microsyringe was held vertically with the needle facing downward, and 1 μl of the composition was extruded in front of the needle. The state of the composition was observed after leaving for 24 hours in a room temperature of 25 ℃. The results are shown in Table 1. In Table 1, it is described as good if the composition is not dried at the front of the needle and bad if it is dried and the needle hole is blocked.

<Examples 2, 3, 4, 5>

In Example 1, the composition solution was manufactured like Example 1 except having set the kind and quantity of (A) component, (B) component and (C) component, and the kind of other solvent as shown in Table 1. Evaluated.

In addition, in Table 1, the addition amount of each component is a weight part, and "-" in a table | surface shows that the corresponding component was not added. The abbreviation of (B) component, (C) component, and another solvent shows the following, respectively.

B-1: Condensate of 2,3,4,4'-tetrahydroxybenzophenone (1 mol) with 1,2-naphthoquinone diazido-4-sulfonic acid chloride (2 mol) (2,3, 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazido-4-sulfonic acid ester)

B-2: Condensate of 2,3,4-trihydroxybenzophenone (1 mol) and 1,2-naphthoquinone azido-4-sulfonic acid ester (2.6 mol) (B-2: 2,3 , 4-trihydroxybenzophenone-1,2-naphthoquinone azido-4-sulfonic acid ester)

B-3: 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonedia Condensate with MAP-5-sulfonic acid ester (2 mol)

C-1: diethylene glycol monobutyl ether acetate

C-2: diethylene glycol monoethyl ether acetate

S-1: diethylene glycol dimethyl ether

S-2: diethylene glycol ethyl methyl ether

<Example 6, 7>

In Example 2, the composition solution was produced and evaluated similarly to Example 2 except having added the component (D) further according to the kind and addition amount of Table 1. The results are shown in Table 1.

In addition, abbreviated-name of (D) component shows the following, respectively.

D-1: Epolight 100MF manufactured by Kyoeisha Chemical Co., Ltd.

D-2: Yukata Shell Epoxy Co., Ltd.

<Comparative Examples 1 and 2>

In Example 2, the composition solution was produced and evaluated similarly to Example 2 except not adding (C) component and using S-1 and S-2 as a solvent instead. The results are shown in Table 1.

According to the present invention, an inkjet interlayer insulating film composition, which is preferable as a material for forming an interlayer insulating film used in an optical device such as a liquid crystal display device, an integrated circuit device, a solid-state imaging device, by an inkjet method, and an interlayer insulating film by an inkjet method Formation methods are provided.

The interlayer insulation film obtained from the composition of the present invention satisfies various performances required as an interlayer insulation film such as adhesion, surface hardness, transparency, heat resistance, light resistance, solvent resistance, and the like.

Claims (2)

(A) a copolymer of (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compound, and (a3) other olefinically unsaturated compound, (B) 1,2-quinonediazide compound, and (C) A composition for forming an interlayer insulating film by an inkjet method, comprising a solvent having a boiling point at atmospheric pressure of 180 ° C or higher. (1) forming a coating film of the composition according to claim 1 on the surface of the substrate by an inkjet device; (2) irradiating at least a part of the formed coating film with radiation, and (3) developing process Method for forming an interlayer insulating film, characterized in that it comprises at least.