JP2000327877A - Radiation-sensitive resin composition, use thereof for interlayer insulation film and microlens, and interlayer insulation film and microlens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a radiation-sensitive resin composition which exhibits a sufficient process margin and has heat resistance, solvent resistance and transparency by compounding a copolymer formed from an unsaturated carboxylic acid and/or its anhydride, an epoxidized (meth)acrylate and other olefinic unsaturated compounds with a 1,2-quinonediazide compound. SOLUTION: This composition is prepared by compounding 100 pts.wt. copolymer formed from 5-40 wt.% unsaturated carboxylic acid and/or its anhydride, 5-60 wt.% monomer represented by formula I (wherein R is H or methyl; R1 is 1-4C alkyl; and n is 1-6) and/or monomer represented by formula II (wherein R2 is H or methyl; and p and q are each 1-6) and 10-70 wt.% olefinic unsaturated compounds other than the foregoing compounds with 5-100 pts.wt. 1,2- quinonediazide compound. The composition is suitable for forming an interlayer insulation film or a microlens.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a radiation-sensitive resin composition. More specifically, the present invention relates to a positive radiation-sensitive resin composition suitable for producing an interlayer insulating film and a microlens by a photolithography method. More specifically, a material for forming an interlayer insulating film, particularly, an interlayer insulating film such as a liquid crystal display device, an integrated circuit device, and a solid-state imaging device, and a lens array body in which minute optical lens bodies are regularly arranged The present invention relates to a radiation-sensitive resin composition suitable for the production of a resin composition. The present invention further relates to the use of the radiation-sensitive resin composition for an interlayer insulating film and a microlens. Further, the present invention relates to an interlayer insulating film and a microlens formed from the radiation-sensitive resin composition.

[0002]

2. Description of the Related Art Generally, a thin film transistor (hereinafter referred to as "T
FT ". 2. Description of the Related Art Electronic components such as a liquid crystal display device, a magnetic head device, an integrated circuit device, and a solid-state imaging device are provided with an interlayer insulating film for insulating between wirings arranged in layers. When forming an interlayer insulating film, a radiation-sensitive resin composition characterized in that the number of steps for obtaining an interlayer insulating film having a required pattern shape is small and an interlayer insulating film having sufficient flatness can be obtained. A photolithography method using an object is widely used. Also, in general,
Microlenses having a lens diameter of about 5 to 100 μm or microlenses thereof are regularly arranged as an imaging optical system of an on-chip color filter or an optical system material of an optical fiber connector such as a facsimile, an electronic copier, and a solid-state imaging device. A microlens array is used. Using a radiation-sensitive resin composition, a lens pattern is formed, and then the pattern is melt-flowed by heat treatment, and the method is used as it is as a lens, or the melt-flowed radiation-sensitive resin composition is masked. Radiation-sensitive resin compositions are widely used, in which a microlens having a desired radius of curvature can be obtained by a method of transferring a lens shape to a base by dry etching. In the process of forming an interlayer insulating film or a microlens using such a radiation-sensitive resin composition, a balance of performance such as resolution, high heat resistance, high solvent resistance, high transparency, and adhesion to a base is provided. In order to achieve this, optimal process conditions for each material are selected and adopted. However, due to factors such as the control capabilities and operating errors of the devices and machines used in the above steps, it is often necessary to use them under conditions that deviate from optimal process conditions. In particular, when the prebaking temperature is shifted to a higher temperature than the optimum value, the resolution at the time of development deteriorates, and the formation of an interlayer insulating film or a microlens itself may become impossible. However, a photosensitive resin composition having a sufficient process margin capable of responding to changes in process conditions, and having a combination of heat resistance, solvent resistance, transparency, and adhesion required for an interlayer insulating film and a microlens is required. Did not.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made based on the above circumstances, and its object is to provide:
Having a sufficient process margin, and the heat resistance, solvent resistance, transparency,
An object of the present invention is to provide a radiation-sensitive resin composition having both adhesion to a base and storage stability. Another object of the present invention is to use the radiation-sensitive resin composition for an interlayer insulating film and a microlens. Still another object of the present invention is to provide an interlayer insulating film and a microlens formed from the radiation-sensitive resin composition. Still other objects and advantages of the present invention will become apparent from the following description.

[0004]

Means for Solving the Problems The object of the present invention is to provide [A] (a1) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride (hereinafter also referred to as "compound (a1)"). (A2) The following formula (1)

[0005]

Embedded image In the formula, R is a hydrogen atom or a methyl group, R ¹ is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6,
And / or the following formula (2)

[0006]

Embedded image In the formula, R ² is a hydrogen atom or a methyl group, and p is 1 to
And q is an integer of 1 to 6 (hereinafter also referred to as “compound (a2)”), and (a3) other than (a1) and (a2): A copolymer obtained by copolymerizing an olefinically unsaturated compound (hereinafter, also referred to as "compound (a3)") (hereinafter, also referred to as "copolymer [A]") and [B] 1,2. -It is achieved by a radiation-sensitive resin composition containing a quinonediazide compound. Another object of the present invention is achieved by using the radiation-sensitive resin composition for an interlayer insulating film and a microlens. Still another object of the present invention is achieved by an interlayer insulating film and a microlens formed from the radiation-sensitive resin composition. In the present invention, “radiation” refers to ultraviolet rays, far ultraviolet rays, X rays.
Includes radiation, electron beam, molecular beam, gamma ray, synchrotron radiation, proton beam and the like.

Hereinafter, the radiation-sensitive resin composition of the present invention will be described in detail. The radiation-sensitive resin composition of the present invention comprises a copolymer [A] and a 1,2-quinonediazide compound [B].

Copolymer [A] The copolymer [A] comprises a compound (a1), a compound (a2),
And the compound (a3) can be synthesized by, for example, radical polymerization in a solvent in the presence of a polymerization initiator.

The copolymer [A] used in the present invention comprises a structural unit derived from the compound (a1), preferably 5 units.
-40% by weight, particularly preferably 10-35% by weight. A copolymer containing less than 5% by weight of the structural unit is less likely to be dissolved in an aqueous alkaline solution, while a copolymer containing more than 40% by weight tends to have too high a solubility in an aqueous alkaline solution. Examples of the compound (a1) 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. Can be Among them, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in view of copolymerization reactivity, solubility in an aqueous alkali solution and easy availability. These may be used alone or in combination.

The copolymer [A] used in the present invention comprises a structural unit derived from the compound (a2), preferably 5 units.
To 60% by weight, particularly preferably 10 to 50% by weight. If this constituent unit is less than 5% by weight, the heat resistance of the resulting coating film tends to decrease, while if it exceeds 60% by weight, the storage stability of the copolymer tends to decrease.

The compound (a2) is represented by the formula (1) or the formula (2). In the formula (1), R is a hydrogen atom or a methyl group, R ¹ is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6. The alkyl group having 1 to 4 carbon atoms of R ¹ may be linear or branched.

The compound (a2) represented by the formula (1) includes, for example, β-methylglycidyl (meth) acrylate,
Β-ethylglycidyl (meth) acrylate, β-propylglycidyl (meth) acrylate, β-methylglycidyl α-ethylacrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, 3-Ethyl-3,4-epoxybutyl (meth) acrylate, 4- (meth) acrylate
Methyl-4,5-epoxypentyl, (meth) acrylic acid
And -5-methyl-5,6-epoxyhexyl.

In the formula (2), R ² is a hydrogen atom or a methyl group, p is an integer of 1 to 6, and q is an integer of 1 to 6. In the formula (2), the epoxy group can be bonded to any position of the cyclohexane ring, for example, at the 3- or 4-position. It should be understood that compounds of formula (2) represent such regioisomers alone or as a mixture.
The compound (a2) represented by the formula (2) includes, for example, the following formulas (3) to (8):

[0014]

Embedded image

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image And the like.

Among them, β-methylglycidyl (meth) acrylate, 3-methyl-3,3 (meth) acrylate,
4-epoxybutyl, the compounds represented by the above formulas (7) and (8), etc. are preferably used from the viewpoint that the photosensitive resin composition has a wide process margin and particularly enhances the solvent resistance. Commercial products of these compounds include M-GMA and CYMA300 (all manufactured by Daicel Chemical Industries, Ltd.). These may be used alone or in combination.

The copolymer [A] used in the present invention comprises a structural unit derived from the compound (a3), preferably 1
The content is 0 to 80% by weight, particularly preferably 20 to 70% by weight. If this constituent unit is less than 10% by weight, the storage stability of the copolymer [A] tends to decrease, while if it exceeds 80% by weight, the copolymer [A] is difficult to dissolve in an alkaline aqueous solution. Become.

Examples of the compound (a3) include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate; alkyl acrylates such as methyl acrylate and isopropyl acrylate; Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate (commonly referred to in the art as "dicyclopentanyl methacrylate"),
Methacrylic acid cyclic alkyl esters such as dicyclopentanyloxyethyl methacrylate and isobornyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.
1.0 ^2,6 ] decane-8-yl acrylate (commonly referred to in the art as "dicyclopentanyl acrylate"), acrylic acid such as dicyclopentanyloxyethyl acrylate, isobornyl acrylate Cyclic alkyl esters; aryl methacrylates such as phenyl methacrylate and benzyl methacrylate; aryl acrylates such as phenyl acrylate and benzyl acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; 2-hydroxyethyl methacrylate And hydroxyalkyl esters such as 2-hydroxypropyl methacrylate; and styrene, α-
Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, , 3-dimethyl-1,3-butadiene, phenylmaleimide, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, glycerol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene Ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, glycerol dimethacrylate and the like. That. Of these, styrene, t-
Butyl methacrylate, dicyclopentanyl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, phenylmaleimide, 1,3-butadiene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, etc. are copolymerization reactivity and molecular weight. It is preferable from the viewpoint of controllability of distribution and solubility in an aqueous alkali solution. These may be used alone or in combination.

Examples of the solvent used for the synthesis of the copolymer [A] include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Glycol ethers; 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 methyl ether; Propylene glycol ethyl ether, professional Glycol propyl ether,
Propylene glycol monoalkyl ethers such as 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 propylene glycol butyl ether acetate; propylene glycol methyl ether propionate Propylene glycol alkyl ether acetates such as propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, Ketones such as roxy-4-methyl-2-pentanone; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2 -Ethyl methyl propionate,
Methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate,
Ethyl 3-hydroxypropionate, Protyl 3-hydroxypropionate, Butyl 3-hydroxypropionate, Methyl 2-hydroxy-3-methylbutanoate, Methyl methoxyacetate, Ethyl methoxyacetate, Propyl methoxyacetate, Butyl methoxyacetate, Methyl ethoxyacetate , Ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate,
Methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-
Propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxy Ethyl propionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-ethoxypropion Methyl acrylate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxyp Acid propyl, 3-propoxy-propionic acid butyl, 3-butoxy-propionic acid methyl 3- butoxy-propionic acid ethyl, 3-butoxy-propionic acid propyl, 3-butoxy-propionic acid butyl, esters such as is.

As the polymerization initiator used in the production of the copolymer [A], those generally known as radical polymerization initiators can be used. For example, 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-
Azo compounds such as methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-
Organic peroxides such as bis- (t-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

In the production of the copolymer [A], a molecular weight modifier can be used to regulate the molecular weight. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan;
mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, and thioglycolic acid; xanthogens such as dimethyl xanthogen sulfide and diisopropyl xanthogen disulfide; terpinolene and α-methyl styrene dimer.

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, and has an appropriate solubility in an aqueous alkali solution. It can be easily cured by heating without using a special curing agent.

The radiation-sensitive resin composition containing the above-mentioned copolymer [A] can be produced without developing residue during development.
Further, a coating film having a predetermined pattern can be easily formed without film thinning.

1,2-quinonediazide compound [B] As the 1,2-quinonediazide compound [B] used in the present invention, as the 1,2-quinonediazide compound, 1,2-benzoquinonediazidesulfonic acid ester, 2-naphthoquinonediazidosulfonic acid ester, 1,2-benzoquinonediazidosulfonic acid amide,
Examples thereof include 1,2-naphthoquinonediazidosulfonic acid amide.

Specific examples thereof include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone azide-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide- 5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4
1,2-naphthoquinonediazidesulfonic acid esters of trihydroxybenzophenone, such as -sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester;
2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5 Sulfonate, 2,3,4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide 5-
Sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-
4-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone- 1,2-
Naphthoquinonediazide-4-sulfonic acid ester, 2,
3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-
3'-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4 '
-Tetrahydroxy-3'-methoxybenzophenone-
1,2-naphthoquinonediazidosulfonic acid ester of tetrahydroxybenzophenone such as 1,2-naphthoquinonediazide-5-sulfonic acid ester;
2 ', 6'-pentahydroxybenzophenone-1,2
-Naphthoquinonediazide-4-sulfonic acid ester,
1,2 of pentahydroxybenzophenone such as 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester
-Naphthoquinonediazidesulfonic acid ester;
6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2 -Naphthoquinonediazide-
5-sulfonic acid ester, 3,4,5,3 ′, 4 ′,
5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4
1,2- of hexahydroxybenzophenone such as 5,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester
Naphthoquinonediazidesulfonic acid ester; bis (2,
4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4
-Dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane- 1,2-naphthoquinonediazide-5
Sulfonate, tri (p-hydroxyphenyl)
Methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, tri (p-hydroxyphenyl) methane-
1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p -Hydroxyphenyl)
Ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4- Trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5
Sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) ) Propane-
1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester , 1,
1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 ′-[1
-[4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-
1,2-naphthoquinonediazide-4-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene]
Bisphenol-1,2-naphthoquinonediazide-5
Sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-
1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3
3 ′, 3′-Tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol
1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'- Hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ',
4'-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-
1,2-Naphthoquinonediazide-5-sulfonic acid ester and other (polyhydroxyphenyl) alkane 1,2-
And naphthoquinonediazidesulfonic acid esters. These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

The proportion of the component (B) used is (A) 10
5 to 100 parts by weight relative to 0 parts by weight, preferably 10 to 10 parts by weight
50 parts by weight. When this ratio is less than 5 parts by weight, the amount of acid generated by irradiation with radiation is small,
The difference in solubility between the irradiated part and the unirradiated part in an aqueous alkali solution as a developing solution is small, and patterning becomes difficult. In addition, since the amount of the acid involved in the reaction of the epoxy group decreases, sufficient heat resistance and solvent resistance cannot be obtained. On the other hand, if this proportion exceeds 100 parts by weight, the unreacted component (B) remains in a large amount by irradiation with radiation for a short time, so that the effect of insolubilization in the alkaline aqueous solution is too high to perform development. Becomes difficult.

<Other Components> In the radiation-sensitive resin composition of the present invention, in addition to the above components (A) and (B), if necessary, a heat-sensitive acid-generating compound (C) may be used. Component, a component (D) comprising a polymerizable compound having at least one ethylenically unsaturated double bond, a component (E) comprising an epoxy resin, a component (F) comprising a methylol compound, and a component comprising a surfactant (G ) Component and (H) component consisting of an adhesion aid.

The heat-sensitive acid-generating compound as the component (C) can be used for improving heat resistance and hardness. Specific examples thereof include antimony fluorides. Sun-Aid SI-L80, Sun-Aid SI-L110, and Sun-Aid SI-L150 (all manufactured by Sanshin Chemical Industry Co., Ltd.).

The proportion of the component (C) used is preferably 20 parts by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight of the alkali-soluble resin of the component (A). If this proportion exceeds 20 parts by weight, precipitates are generated, making patterning difficult.

As the polymerizable compound having at least one ethylenically unsaturated double bond as the component (D), a compound having at least one (meth) acrylate structure in the molecule is preferably used. it can. Examples of the compound having one (meth) acrylate structure in the molecule include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, and 3-methoxybutyl (meth) acrylate , 2- (meth) acryloyloxyethyl-
Examples thereof include 2-hydroxypropyl phthalate, and commercially available products thereof include, for example, Aronix M-101, M-111, and M-114 (manufactured by Toagosei Co., Ltd.), KAY
ARAD TC-110S and TC-120S (manufactured by Nippon Kayaku Co., Ltd.), and Viscort 158 and 2311 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Examples of the compounds having two (meth) acrylate structures in the molecule include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange acrylate, and the like. Commercial products thereof include, for example, Aronix M-210, M-240, M-6200 (manufactured by Toagosei Co., Ltd.), KAYARAD H
DDA, HX-220, R-604 (Nippon Kayaku Co., Ltd.)
And HP Coats 260, 312 and 335 HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Examples of the compound having three or more (meth) acrylate structures in the molecule include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tri ((meth) acryloyloxyethyl). ) Phosphate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, and examples of commercially available products thereof include Aronix M-309 and M-400. , M-405, M-450, M-71
00, M-8030, M-8060 (Toagosei Co., Ltd.)
KAYARAD TMPTA, DPHA, D
PCA-20, DPCA-30, DPCA-60,
DPCA-120 (Nippon Kayaku Co., Ltd.), VISCOAT 2
95, 300, 360, GPT, 3PA, 4
00 (manufactured by Osaka Organic Chemical Industry Co., Ltd.). These compounds having one or more (meth) acrylate structures in the molecule are used alone or in combination.

The proportion of the component (D) to be used is as follows.
It is preferably 50 parts by weight or less, particularly preferably 30 parts by weight or less based on 0 parts by weight. By containing the component (D) at such a ratio, the heat resistance, strength, and the like of the patterned thin film obtained from the radiation-sensitive resin composition can be improved. When this proportion exceeds 50 parts by weight, the compatibility of the component (A) with the alkali-soluble resin becomes insufficient, and the film may be roughened at the time of coating.

The epoxy resin as the component (E) is not limited as long as the compatibility is not affected, but is preferably a bisphenol A type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, Examples thereof include a cycloaliphatic epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, a heterocyclic epoxy resin, and a resin obtained by (co) polymerizing glycidyl methacrylate.
Among these, bisphenol A type epoxy resin, cresol novolak type epoxy resin, glycidyl ester type epoxy resin and the like are preferable.

The proportion of the component (E) is preferably 30 parts by weight or less based on 100 parts by weight of the alkali-soluble resin. By containing the component (E) at such a ratio, the heat resistance, strength, and the like of the coating film obtained from the radiation-sensitive resin composition can be further improved.
If this proportion exceeds 30 parts by weight, the compatibility with the alkali-soluble resin becomes insufficient, and a sufficient film-forming ability cannot be obtained.

The methylol compound as the component (F) is represented by the following formula (9):

[0041]

Embedded image In the formula, R ³ is a hydrogen atom or a carbon atom number, usually 1 to
6, preferably a compound having at least two monovalent organic groups in a molecule, which represents an alkyl group of 1 to 4, preferably a compound in which the monovalent organic group is bonded to a nitrogen atom, N-methylol group and / or N-
Examples include compounds containing an alkoxymethyl group. When two or more organic groups of the general formula (9) are present in one molecule, R ³ of those groups may be the same or different. In the composition of the present invention, the organic group represented by the general formula (9)
(A) Reacts with the carboxyl group of the copolymer of the component to form a crosslinked structure.

As the component (F), for example, the formula (10)

[0043]

Embedded image Wherein R ³ is the same or different and is an alkyl group, for example, an alkyl group having 1 to 4 carbon atoms.
Alkoxymethylated melamines such as N ', N', N ", N"-(hexaalkoxymethyl) melamine, and formula (11)

[0044]

Embedded image In the formula, R ³ is the same or different and has the same meaning as in formula (10), alkoxymethylated glycoluril such as N, N ′, N ″, N ″ ′-(tetraalkoxymethyl) glycoluril The crosslinking agent may be urea-formaldehyde resin, thiourea-formaldehyde resin, melamine-formaldehyde resin, guanamine-
Formaldehyde resins, benzoguanamine-formaldehyde resins, glycoluril-formaldehyde resins, and polyvinylphenols have the general formula (9)
A compound into which the group represented by is introduced may be used.

As the surfactant as the component (G), for example, BM-1000, BM-1100 (BM C
HEMIE), MegaFac F142D, F17
2, F173, F183 (Dainippon Ink and Chemicals, Inc.)
Co., Ltd.), Florado FC-135, FC-170
C, FC-430, FC-431 (Sumitomo 3M)
Co., Ltd.), Surflon S-112, S-113, S
-131, S-141, S-145, S-38
2, SC-101, SC-102, SC-10
3, SC-104, SC-105, SC-106
(Manufactured by Asahi Glass Co., Ltd.), F-top EF301, 303,
352 (manufactured by Shin-Akita Chemical Co., Ltd.), SH-28PA, S
H-190, SH-193, SZ-6032, SF-8
Fluorine and silicone surfactants such as 428, DC-57 and DC-190 (manufactured by Toray Silicone Co., Ltd.); polyoxyethylene alkyls such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether Ethers; polyoxyethylene octyl phenyl ether,
Polyoxyethylene aryl ethers such as polyoxyethylene nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; organosiloxane polymer KP
341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and (meth) acrylic acid-based copolymer polyflow Nos. 57 and 95 (all manufactured by Kyoeisha Yushi Kagaku Kogyo KK).

These surfactants are copolymers [A] 1
It is preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less based on 00 parts by weight. When the amount of the surfactant is more than 5 parts by weight, the film tends to be rough at the time of coating.

As the adhesive aid (H) component, a functional silane coupling agent is preferably used. For example, a carboxyl group, a methacryloyl group, an isocyanate group,
Examples include silane coupling agents having a reactive substituent such as an epoxy group. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and γ-isocyanate. Natopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

[0048] Such an adhesion aid is a copolymer [A] 1
It is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less based on 00 parts by weight. When the amount of the adhesion aid exceeds 20 parts by weight, development residue tends to occur.

The radiation-sensitive resin composition of the present invention comprises the copolymer [A] and the 1,2-quinonediazide compound [B].
Is prepared by uniformly mixing Usually, the radiation-sensitive resin composition of the present invention is dissolved in an appropriate solvent and used in a solution state. For example, copolymer [A], 1,2
-The radiation-sensitive resin composition in a solution state can be prepared by mixing quinonediazide [B] and other compounding agents at a predetermined ratio.

As the solvent used for preparing the radiation-sensitive resin composition of the present invention, the components of the copolymer [A] and the 1,2-quinonediazide compound [B] are uniformly dissolved and reacted with each component. Those that do not are used. Specifically, for example, alcohols 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 acetate such as methyl cellosolve acetate and ethyl cellosolve acetate Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl 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 Propylene glycol alkyl ether acetates such as tyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate propylene glycol butyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether pro Propylene glycol alkyl ether acetates such as pionate 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; Methyl acetate, ethyl acetate, propyl acetate, butyl acetate , Ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropionic acid methyl,
Ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate,
Butyl lactate, methyl 3-hydroxypropionate, 3-
Ethyl hydroxypropionate, protyl 3-hydroxypropionate, butyl 3-hydroxypropionate,
Methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate,
Propyl propyl acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxypropionic acid Butyl, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate Butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-ethoxypropionate Methyl phosphate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxypropion Esters such as butyl acid, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

Among these solvents, glycol ethers, ethylene glycol alkyl ether acetates, propylene glycol alkyl ether acetates, esters and the like are preferred in view of solubility, reactivity with each component, and ease of forming a coating film. And diethylene glycols are preferably used.

Further, a high boiling point solvent can be used in combination with the above-mentioned solvent. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol,
1-nonanol, benzyl alcohol, benzyl acetate,
Examples include ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

The composition solution prepared as described above can be used after being filtered using a Millipore filter having a pore size of about 0.5 μm.

[0054] Formation of patterned coating film Next, an interlayer insulating film of the present invention using the radiation-sensitive resin composition of the present invention, describes a method of forming a microlens. The radiation-sensitive resin composition of the present invention can be applied to the surface of a base substrate, and the solvent can be removed by pre-baking to form a coating film. As a coating method, various methods such as a spray method, a roll coating method, and a spin coating method can be adopted. In addition, the conditions of pre-bake vary depending on the type of each component, the mixing ratio, etc.,
Usually, conditions of 70 to 90 ° C. for about 1 to 15 minutes are optimal. The radiation-sensitive resin composition of the present invention has a process margin that can sufficiently cope with a pre-bake temperature of about 110 ° C. Next, the prebaked coating film is irradiated with radiation such as ultraviolet rays via a predetermined pattern mask, and further developed with a developer to remove unnecessary portions to form a predetermined pattern. The developing method may be any of a liquid filling method, a dipping method, a shower method and the like, and the developing time is usually 30 to 180 seconds.

Examples of the developer include an aqueous alkali solution, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine. And diethylamine, di-n
Secondary amines such as -propylamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; tertiary amines such as dimethylethanolamine, methyldiethanolamine and triethanolamine; pyrrole, piperidine and N
-Methylpiperidine, N-methylpyrrolidine, 1,8-
Diazabicyclo [5.4.0] -7-undecene, 1,
Cyclic tertiary amines such as 5-diazabicyclo [4.3.0] -5-nonene; aromatic tertiary amines such as pyridine, collidine, lutidine and quinoline; tetramethylammonium hydroxide and tetraethylammonium hydroxide An aqueous solution of a quaternary ammonium salt can be used. Also, methanol,
An aqueous solution to which an appropriate amount of a water-soluble organic solvent such as ethanol and / or a surfactant has been added can also be used as a developer.

After the development, running water washing is performed for 30 to 90 seconds.
A pattern is formed by removing unnecessary portions and air-drying with compressed air or compressed nitrogen. The formed pattern is irradiated with radiation such as ultraviolet rays, and then the pattern is heated by a heating device such as a hot plate or an oven at a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, 5 to 30 minutes on the hot plate. By performing a heat treatment in an oven for 30 to 90 minutes, a patterned coating film corresponding to the intended interlayer insulating film or microlens can be obtained.

[0057]

EXAMPLES The present invention will be described more specifically with reference to Synthesis Examples, Examples and Comparative Examples below, but the present invention is not limited to the following Examples.

Synthesis Example 1 In a flask equipped with a condenser and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and propylene glycol monomethyl ether acetate 220 were added.
The parts by weight were charged. Followed by 22 parts by weight of methacrylic acid,
38 parts of dicyclopentanyl methacrylate, 40 parts by weight of -β-methylglycidyl methacrylate, and 1.5 parts of α-methylstyrene dimer were charged, and the mixture was slowly stirred while being replaced with nitrogen. The temperature of the solution was raised to 70 ° C., and the mixture was heated at this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-1]. The solid content concentration of the obtained polymer solution was 31.
The polymer had a weight average molecular weight of 18,500 and a molecular weight distribution of 1.8. The weight average molecular weight is
The average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography (HLC-8020 manufactured by Tosoh Corporation)).

Synthesis Example 2 In a flask equipped with a condenser and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and propylene glycol monomethyl ether acetate 220 were added.
The parts by weight were charged. Subsequently, 20 parts by weight of styrene, 25 parts by weight of methacrylic acid, 20 parts by weight of phenylmaleimide, 35 parts by weight of methacrylic acid-β-methylglycidyl, and 1.5 parts of α-methylstyrene dimer were charged and slowly stirred while replacing with nitrogen. . The temperature of the solution was raised to 70 ° C., and the mixture was heated at this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-2]. The solid content concentration of the obtained polymer solution was 31.0%, and the weight average molecular weight of the polymer was 210%.
At 00, the molecular weight distribution was 2.1.

Synthesis Example 3 In a flask equipped with a condenser and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 150 parts of propylene glycol monomethyl ether acetate were added.
The parts by weight were charged. Subsequently, 20 parts by weight of styrene, 25 parts by weight of methacrylic acid, 20 parts by weight of phenylmaleimide, 35 parts by weight of methacrylic acid-β-methylglycidyl, and 1.5 parts of α-methylstyrene dimer were charged and slowly stirred while replacing with nitrogen. . The temperature of the solution was raised to 70 ° C., and the mixture was heated at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A-3]. The solid content concentration of the obtained polymer solution was 39.8%, and the weight average molecular weight of the polymer was 230
At 00, the molecular weight distribution was 2.4.

Synthesis Example 4 In a flask equipped with a condenser and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and propylene glycol monomethyl ether acetate 220 were added.
The parts by weight were charged. Subsequently, styrene (20 parts by weight), methacrylic acid (30 parts by weight), methacrylic acid-β-methylglycidyl (50 parts by weight) and α-methylstyrene dimer (2.0 parts) were charged and the mixture was slowly stirred while being replaced with nitrogen. The temperature of the solution was raised to 70 ° C., and the mixture was heated at this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-4]. The solid content concentration of the obtained polymer solution was 31.0%, the weight average molecular weight of the polymer was 19000, and the molecular weight distribution was 1.7.

Synthesis Example 5 In a flask equipped with a condenser and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and propylene glycol monomethyl ether acetate 220 were added.
The parts by weight were charged. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 50 parts by weight of CYMA300 (manufactured by Daicel Chemical Industries, Ltd.), and 2.0 parts of α-methylstyrene dimer were charged and slowly stirred while being replaced with nitrogen. The temperature of the solution was raised to 70 ° C.
The mixture was heated for a time to obtain a polymer solution containing the copolymer [A-5]. The solid content concentration of the obtained polymer solution was 30.9%, the weight average molecular weight of the polymer was 21,000, and the molecular weight distribution was 1.8.

Comparative Synthesis Example 1 A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 23 parts by weight of methacrylic acid, 47 parts of dicyclopentanyl methacrylate, 30 parts by weight of glycidyl methacrylate, and 2.0 parts of α-methylstyrene dimer were charged, and the mixture was slowly stirred while being replaced with nitrogen. 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-1R]. The solid content concentration of the obtained polymer solution was 32.8%, the weight average molecular weight of the polymer was 24,000, and the molecular weight distribution was 2.3.

Comparative Synthesis Example 2 A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 25 parts by weight of methacrylic acid, 35 parts by weight of dicyclopentanyl methacrylate, 40 parts by weight of 2-hydroxyethyl methacrylate, and 2.0 parts of α-methylstyrene dimer were charged and slowly stirred while being replaced with nitrogen. 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-2R]. The solid concentration of the obtained polymer solution was 32.8%, the weight average molecular weight of the polymer was 25,000, and the molecular weight distribution was 2.4.

Example 1 Preparation of Radiation-Sensitive Resin Composition A solution containing the copolymer [A-1] obtained in Synthesis Example 1 (corresponding to 100 parts by weight (solid content) of the copolymer [A-1]). ) And 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] as component [B]
Ethylidene] bisphenol (1 mol) and 1,2-
30 parts by weight of a condensate with naphthoquinonediazide-5-sulfonic acid chloride (2 mol) and 5 parts by weight of γ-methacryloxypropyltrimethoxysilane are mixed, and propylene glycol monomethyl ether is mixed so that the solid content concentration becomes 30% by weight. After dissolving in acetate, a pore size of 0.5
The solution (S-1) of the radiation-sensitive resin composition was prepared by filtration with a μm millipore filter.

(I) Formation of Patterned Thin Film After applying the above composition solution (S-1) on a glass substrate using a spinner, prebaking on a hot plate at 90 ° C. for 2 minutes to form a coating film. did.

The coating film obtained above was irradiated with ultraviolet rays having an intensity at 365 nm of 10 mW / cm 2 for 15 seconds using a predetermined pattern mask. Then, a 0.5% by weight aqueous solution of tetramethylammonium hydroxide was added at 25 ° C for 1 hour.
After developing for 1 minute, the substrate was rinsed with pure water for 1 minute. Unnecessary portions were removed by these operations.

The pattern formed above was irradiated with ultraviolet rays having an intensity at 365 nm of 10 mW / cm 2 for 30 seconds, and then heated and cured in an oven at 200 ° C. for 60 minutes to obtain a patterned thin film having a thickness of 3 μm. . Further, the same operation as described above was performed except that the pre-bake temperatures were set to 100 ° C. and 110 ° C., to form three types of patterned thin films having different pre-bake temperatures.

(II) Evaluation of Resolution In the patterned thin film obtained in the above (I), a case where a punched pattern (5 μm × 5 μm hole) can be resolved was evaluated as ○ (good), and a case where resolution was not resolved was evaluated as ×. (Poor).
Table 1 shows the results.

(III) Evaluation of Heat Resistance The thin film pattern formed in the above (I) was placed in an oven for 22 hours.
Heat at 0 ° C. for 60 minutes. Table 1 shows the change rate of the film thickness. When the film reduction rate is within 5% before and after heating, it can be said that the heat resistance is good.

(IV) Evaluation of Transparency Spectrophotometer (150-20 double beam (Hitachi, Ltd.)
The transmittance of the patterned thin film at 400 nm was measured by using the method described in (1). Table 1 shows the results. At this time, the transmittance is 9
When it exceeds 0%, it can be said that the transparency is good.

(V) Evaluation of heat discoloration resistance The pattern-like thin film obtained in the above (I) was evaluated for 220
The composition was heated in an oven at a temperature of 1 ° C. for 1 hour, and the heat-resistant discoloration was evaluated based on the change in transmittance of the patterned thin film before and after heating.
The results are shown in Table 1. At this time, the transmittance reduction rate is 5%.
When it is within, it can be said that the heat discoloration resistance is good. The transmittance at this time was determined in the same manner as in (IV) Evaluation of transparency.

(VI) Evaluation of Storage Stability The composition solution was heated in an oven at 40 ° C. for one week, and storage stability was evaluated by a change in viscosity before and after heating. Table 1 shows the increase rate at this time. The rate of increase in viscosity is 5
%, It can be said that the storage stability is good.

(VII) Evaluation of Solvent Resistance The glass substrate on which the patterned thin film was formed
It was immersed in methylpyrrolidone and the change in film thickness was evaluated.
Table 1 shows the rate of change at this time. When the rate of change of swelling and dissolution is within ± 5%, it can be said that the solvent resistance is good.

Example 2 In Example 1, a solution containing the copolymer [A-2] obtained in Synthesis Example 2 was used instead of the solution containing the copolymer [A-1]. A composition solution (S-2) was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 3 In Example 1, a solution containing the copolymer [A-3] obtained in Synthesis Example 3 was used instead of the solution containing the copolymer [A-1]. A composition solution (S-3) was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 4 In Example 1, a solution containing the copolymer [A-4] obtained in Synthesis Example 4 was used instead of the solution containing the copolymer [A-1]. A composition solution (S-4) was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 5 The procedure of Example 1 was repeated, except that the solution containing the copolymer [A-5] obtained in Synthesis Example 5 was used instead of the solution containing the copolymer [A-1]. A composition solution (S-5) was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 In Example 1, the copolymer [A-1R] obtained in Comparative Synthesis Example 1 was used instead of the solution containing the copolymer [A-1].
A composition solution (S-1R) was prepared and evaluated in the same manner as in Example 1, except that a solution containing was used. Table 1 shows the results.

Comparative Example 2 A solution containing the copolymer [A-2R] obtained in Comparative Synthesis Example 2 (corresponding to 100 parts by weight (solid content) of the copolymer [A-2R]) and the component [B] 4,4 ′-[1- [4- [1
-[4-hydroxyphenyl] -1-methylethyl]
Phenyl] ethylidene] bisphenol (1 mol)
Of a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2 mol), 25 parts by weight of hexamethylolmelamine, and 5 parts by weight of γ-methacryloxypropyltrimethoxysilane were mixed. After dissolving in propylene glycol monomethyl ether acetate so that the concentration becomes 30% by weight, the pore size is 0.5 μm.
The solution (S-2R) of the radiation-sensitive resin composition was prepared by filtration through a Millipore filter of m and evaluated. Table 1 shows the results.

[0081]

[Table 1]

[0082]

According to the present invention, a sufficient process margin can be obtained, and the heat resistance, solvent resistance, transparency, adhesion to a base, and storage stability required for an interlayer insulating film and a microlens can be obtained. A radiation-sensitive resin composition having the same can be obtained. Further, an interlayer insulating film and a microlens having excellent physical properties are formed from the radiation-sensitive resin composition.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/033 G03F 7/033 7/039 7/039 H01L 21/312 H01L 21/312 DF term (reference) ) 2H025 AA00 AA06 AA10 AA14 AB14 AB16 AB17 AC01 AC04 AC05 AC06 AC07 AD03 BE01 CB08 CB14 CB30 4J002 BC021 BD031 BD101 BF021 BG071 BG101 BG131 BL011 CM041 EQ036 EV246 EV266 GP01 GP03 G0401A04 AB02 AB04 AB02 AL08Q AL09R AL34R AL62R AL66R AM02R AM15R AM48R AS02R AS03R BA02Q BA03Q BA03R BA04R BA05R BC04Q BC04R BC07R BC08R BC43R BC54Q CA05 JA33 JA37 JA39 5F058 AA05 AA08 AC07 AF04 AG01 AG09 AH02

Claims (5)

[Claims] [A] (a) (a1) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, (a2) a compound represented by the following formula (1): In the formula, R is a hydrogen atom or a methyl group, R ¹ is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6,
And / or the following formula (2): In the formula, R ² is a hydrogen atom or a methyl group, and p is 1 to
And q is an integer of 1 to 6, and (a3) a copolymer obtained by copolymerizing an olefinically unsaturated compound other than (a1) and (a2). A radiation-sensitive resin composition comprising a polymer and [B] a 1,2-quinonediazide compound. 2. Use of the radiation-sensitive resin composition according to claim 1 for an interlayer insulating film. 3. Use of the radiation-sensitive resin composition according to claim 1 for a microlens. 4. An interlayer insulating film formed from the radiation-sensitive resin composition according to claim 1. 5. A microlens formed from the radiation-sensitive resin composition according to claim 1.