JP4529616B2 - Radiation-sensitive resin composition for forming interlayer insulating film and interlayer insulating film - Google Patents

Description

  The present invention relates to a radiation sensitive resin composition for forming an interlayer insulating film, an interlayer insulating film formed from the radiation sensitive resin composition for forming an interlayer insulating film, a method for forming the interlayer insulating film, and a liquid crystal display including the interlayer insulating film. It relates to an element.

A thin film transistor (hereinafter referred to as “TFT”) type liquid crystal display element, magnetic head element, integrated circuit element, solid-state imaging tube element, and other electronic parts are generally provided with an interlayer for insulating between wirings arranged in layers. An insulating film is provided, and as the material, a material having a small number of steps for obtaining a required pattern shape and having sufficient flatness is preferable, and thus a radiation-sensitive resin composition is widely used. (For example, see Patent Document 1 and Patent Document 2).
Among the electronic components, the TFT type liquid crystal display element is manufactured through a process of forming a transparent electrode film on an interlayer insulating film and further forming a liquid crystal alignment film on the interlayer insulating film. In the process of forming the transparent electrode film, it is exposed to a high temperature condition or exposed to a resist stripping solution used when forming an electrode having a predetermined pattern shape.
In recent years, TFT-type liquid crystal display elements are under various technological trends such as an increase in screen size, high brightness, high definition, and high speed response, and the structure of the liquid crystal display elements has become complicated accordingly. Therefore, the interlayer insulating film to be used is required to have higher performance than the conventional ones in terms of low dielectric constant, high light transmittance, etc., and can be thickened due to the structure of the liquid crystal display element. There are also special requests.
However, it is extremely difficult to achieve a thick film, a high light transmittance, and a high resolution at the same time with the radiation-sensitive resin composition that is usually used for forming the conventional interlayer insulating film. There has been a strong demand for the development of a radiation sensitive resin composition capable of forming an interlayer insulating film having both characteristics.

JP 2001-354822 A JP 2001-343743 A

The present invention has been made in view of the circumstances as described above, and the problem is high resolution, sufficient film thickness, and transparency, heat resistance, adhesion, and solvent resistance. An object of the present invention is to provide a radiation sensitive resin composition for forming an interlayer insulating film capable of forming an interlayer insulating film having excellent physical properties such as the above.
Another object of the present invention is to provide an interlayer insulating film formed from the radiation-sensitive resin composition for forming an interlayer insulating film, a method for forming the interlayer insulating film, and a liquid crystal display device including the interlayer insulating film.
Still other problems and advantages of the present invention will become apparent from the following description.

The present invention, first,
(A) (a) 10 to 50% by weight of a polymerizable unsaturated compound having an acidic functional group, which is a monoesterified product of (meth) acrylic acid and 2-hydroxyethyl (meth) acrylate and hexahydrophthalic acid , b) 20-60% by weight of a polymerizable unsaturated compound having tricyclodecanyl (meth) acrylate as an essential component and having an alicyclic hydrocarbon group and no acidic functional group, and (c) other polymerization An alkali-soluble copolymer obtained by polymerizing 5 to 40% by weight of the unsaturated compound (where (a) + (b) + (c) = 100% by weight), (B) a polymerizable unsaturated compound, C) A photopolymerization initiator, and (D) a radiation-sensitive resin composition for forming an interlayer insulating film, which contains a coupling agent.
The “radiation” as used in the present invention means a substance containing ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ rays, synchrotron radiation, proton beams, and the like.

The present invention secondly,
An interlayer insulating film formed from the radiation-sensitive resin composition for forming the interlayer insulating film.

Third, the present invention
It comprises a method for forming an interlayer insulating film characterized by including at least the following steps (a) to (d) in the order described below.
(A) forming a coating film of the radiation-sensitive resin composition for forming an interlayer insulating film on a substrate;
(B) irradiating at least a part of the coating film with radiation;
(C) developing the coated film after irradiation;
(D) A step of baking the developed coating film.

The present invention fourthly,
A liquid crystal display element having the interlayer insulating film.

Hereinafter, the present invention will be described in detail.
Radiation-sensitive resin composition for forming interlayer insulation film -Copolymer (A)-
The component (A) in the present invention comprises (a) a monoester product of (meth) acrylic acid and 2-hydroxyethyl (meth) acrylate and hexahydrophthalic acid [hereinafter referred to as “hexahydrophthalic acid mono [2- (meta ) Acrylyloxyethyl] ”. 10-50 wt% of a polymerizable unsaturated compound having an acidic functional group (hereinafter referred to as “(a) polymerizable unsaturated compound”), (b) tricyclodecanyl (meth) acrylate as an essential component and has an alicyclic hydrocarbon group, no acidic functional group polymerizable unsaturated compound (hereinafter, referred to as "(b) polymerizable unsaturated compounds".) 20 to 60 wt% and (c) An alkali-soluble copolymer (hereinafter referred to as “(A) copolymer” obtained by polymerizing 5 to 40% by weight of another polymerizable unsaturated compound (where (a) + (b) + (c) = 100% by weight). Polymer)).

In the present invention, (a) the polymerizable unsaturated compound is particularly preferably a mixture of methacrylic acid and mono (2-methacryloyloxyethyl) hexahydrophthalate.

Next, as the polymerizable unsaturated compound (b) other than tricyclodecanyl (meth) acrylate, for example, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl (meth) ) Acrylate, adamantyl (meth) acrylate, 2-cyclopentyloxyethyl (meth) acrylate, 2-cyclohexyloxyethyl (meth) acrylate, 2-isobornyloxyethyl (meth) acrylate, 2-dicyclopentanyloxyethyl ( And (meth) acrylate, 2-adamantyloxyethyl (meth) acrylate, and the like.

In the present invention, (b) a polymerizable unsaturated compound, in particular tricyclodecanyl methacrylate are preferred.
In the present invention, the polymerizable unsaturated compound (b) can be used alone or in admixture of two or more.

Furthermore, other polymerizable unsaturated compounds are mainly used for the purpose of controlling the mechanical properties of the (A) copolymer.
Other polymerizable unsaturated compounds include, for example, (meth) acrylic acid esters, diesters of unsaturated dicarboxylic acids exemplified for the polymerizable unsaturated compound (a), aromatic vinyl compounds, conjugated diolefins, Examples include nitrile group-containing unsaturated compounds, chlorine-containing unsaturated compounds, amide group-containing unsaturated compounds, and aliphatic vinyl esters.

More specifically, as other polymerizable unsaturated compounds,
As (meth) acrylic acid esters, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) ) Acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, 4-i-pentylhexyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl ( (Meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraquinonyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, benzyl (meth) acrylate, fe Til (meth) acrylate, cresyl (meth) acrylate, glycidyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, pentafluoroethyl ( (Meth) acrylate, heptafluoro-n-propyl (meth) acrylate, heptafluoro-i-propyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 3- (N, N-dimethyl) Amino) propyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, α- (meth) acryloyloxy-γ-butyrolactone, β- (meth) acryloyloxy-γ- Butyrora Kuton, etc .;

Diesters of unsaturated dicarboxylic acids include dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl itaconate, diethyl itaconate, etc .; aromatic vinyl compounds such as styrene, α-methylstyrene, o-methyl Styrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, etc .; 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. as conjugated diolefins; nitrile group-containing unsaturated As compounds, (meth) acrylonitrile, vinylidene cyanide, etc .; Chlorine-containing unsaturated compounds, vinyl chloride, vinylidene chloride, etc .; As amide group-containing unsaturated compounds, (meth) acrylamide, maleic acid diamide, fumaric acid diamide, etc .; Acetic acid as an aromatic vinyl ester Alkenyl, and vinyl Puropiron acid.

Of these other polymerizable unsaturated compounds, tetrahydrofurfuryl (meth) acrylate, styrene, 1,3-butadiene, isoprene and the like are preferable.
In the present invention, other polymerizable unsaturated compounds can be used alone or in admixture of two or more, but a mixture of styrene and tetrahydrofurfuryl (meth) acrylate, styrene and 1,3-butadiene. And / or a mixture with isoprene is more preferred, and a mixture of styrene and tetrahydrofurfuryl methacrylate is particularly preferred.

More specific examples of the preferred (A) copolymer in the present invention include:
Preferably, ( a ) a polymerizable unsaturated compound composed of a mixture of (meth) acrylic acid and mono [2- (meth) acryloyloxyethyl] hexahydrophthalic acid, and (b) composed of tricyclodecanyl (meth) acrylate A copolymer of a polymerizable unsaturated compound and another polymerizable unsaturated compound consisting of at least one selected from the group consisting of tetrahydrofurfuryl (meth) acrylate, styrene, 1,3-butadiene and isoprene;

More preferably, ( a ) a polymerizable unsaturated compound composed of a mixture of (meth) acrylic acid and hexahydrophthalic acid mono [2- (meth) acryloyloxyethyl], and tricyclodecanyl (meth) acrylate (b ) Copolymers of polymerizable unsaturated compounds and other polymerizable unsaturated compounds comprising a mixture of styrene and tetrahydrofurfuryl (meth) acrylate, or a mixture of styrene and 1,3-butadiene and / or isoprene. And

Particularly preferably, ( a ) a polymerizable unsaturated compound composed of a mixture of methacrylic acid and mono (2-methacryloyloxyethyl) hexahydrophthalate, ( b ) a polymerizable unsaturated compound composed of tricyclodecanyl methacrylate, and styrene And a copolymer of other polymerizable unsaturated compounds made of a mixture of tetrahydrofurfuryl methacrylate.

  (A) The copolymer comprises (a) a polymerizable unsaturated compound, (b) a polymerizable unsaturated compound and another polymerizable unsaturated compound, for example, in a suitable solvent in the presence of a radical polymerization initiator. It can be produced by polymerization.

(A) The use ratio of each polymerizable unsaturated compound in producing the copolymer is (a) 10 to 50% by weight, preferably 20 to 40% by weight of the polymerizable unsaturated compound, (b ) The polymerizable unsaturated compound is 20 to 60% by weight, preferably 30 to 50% by weight, and the other polymerizable unsaturated compound is 5 to 40% by weight, preferably 10 to 35% by weight (provided that ( a) + (b) + (c) = 100 wt%).
In this case, if the proportion of the polymerizable unsaturated compound (a) used is less than 10% by weight, the resulting copolymer is difficult to dissolve in an alkaline developer, resulting in a film residue after development and sufficient resolution. On the other hand, if it exceeds 50% by weight, the solubility of the resulting copolymer in an alkaline developer becomes too high, resulting in a large reduction in film thickness at the radiation irradiated portion. Further, when the use ratio of the polymerizable unsaturated compound (b) is less than 20% by weight, the molecular weight of the obtained copolymer is not sufficiently increased, and it becomes difficult to form a coating film having a thickness of 10 μm or more. If it exceeds 60% by weight, the solubility in the solvent used for the polymerization of the resulting copolymer and the organic solvent used in the preparation of the liquid composition to be described later decreases.

As the solvent used for the polymerization, for example,
Alcohols such as methanol, ethanol and diacetone alcohol; ethers such as tetrahydrofuran, tetrahydropyran and dioxane; ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate and ethylene glycol mono Ethylene glycol monoalkyl ether acetates such as ethyl ether acetate; diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol diethyl ether; propylene glycol monomethyl ether Propylene glycol monoalkyl ethers such as ter, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono- Propylene glycol monoalkyl ether acetates such as n-propyl ether acetate and propylene glycol mono-n-butyl ether acetate; propylene glycol monomethyl ether propionate, propylene glycol ethyl monoether propionate, propylene glycol mono-n-propyl ether pro Pionate, propylene glycol mono-n-butyl ether Propylene glycol monoalkyl ether propionates such as terpropionate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone Ketones such as;

Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, methyl lactate, ethyl lactate, n-propyl lactate, n-lactic acid Butyl, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2 -Ethyl methylpropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, n-propyl methoxyacetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, n-propyl ethoxyacetate, Ethoxyacetic acid n- Chill, n-propoxyacetate methyl, n-propoxyacetate ethyl, n-propoxyacetate n-propyl, n-propoxyacetate n-butyl, n-butoxyacetate methyl, n-butoxyacetate, n-butoxyacetate n-propyl, n-Butoxyacetate n-butyl, 2-methoxypropionate methyl, 2-methoxypropionate ethyl, 2-methoxypropionate n-propyl, 2-methoxypropionate n-butyl, 2-ethoxypropionate methyl, 2-ethoxy Ethyl propionate, n-propyl 2-ethoxypropionate, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate N-butyl 2-n-propoxypropionate, -Methyl n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate, 3-methoxypropionate Ethyl acetate, n-propyl 3-methoxypropionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, n-ethoxypropionate n -Butyl, methyl 3-n-propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, 3-n-butoxypropionic acid Methyl, ethyl 3-n-butoxypropionate, 3- Other esters such as n-propyl n-butoxypropionate and n-butyl 3-n-butoxypropionate can be mentioned.
These solvents can be used alone or in admixture of two or more.

  Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis (4- Azo compounds such as methoxy-2,4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane, Hydrogen peroxide etc. can be mentioned. When a peroxide is used as the radical polymerization initiator, a redox initiator may be used in combination with a reducing agent.

(A) The polystyrene equivalent weight average molecular weight (hereinafter referred to as “Mw”) of the copolymer is preferably 2,000 to 100,000, and more preferably 5,000 to 50,000. In this case, if the Mw of the copolymer (A) is less than 2,000, the alkali developability and the residual film ratio may be decreased, and the pattern shape and heat resistance may be impaired. If it exceeds, the sensitivity and pattern shape may be impaired.
Further, the ratio (hereinafter referred to as “Mw / Mn”) of the Mw of the copolymer (A) and the number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) is usually 1.0 to 5.0. , Preferably 1.0 to 3.0.
In the present invention, the (A) copolymer can be used alone or in admixture of two or more.

-(B) polymerizable unsaturated compound-
The polymerizable unsaturated compound in the present invention is a compound that is polymerized by irradiation with radiation in the presence of a photopolymerization initiator.
Examples of the polymerizable unsaturated compound include a compound having one ethylenically unsaturated bond, a compound having two ethylenically unsaturated bonds, and a compound having three or more ethylenically unsaturated bonds. Can do.
Examples of the compound having one ethylenically unsaturated bond include mono (meth) acrylates of monohydric alcohols, preferably compounds represented by the following formula (1).

〔式（１）中、ｎは０〜８の整数であり、Ｒは水素原子または炭素数１〜９の直鎖状、分岐状もしくは環状のアルキル基を示す。〕

[In Formula (1), n is an integer of 0-8, R shows a hydrogen atom or a C1-C9 linear, branched or cyclic alkyl group. ]

Specific examples of the compound represented by the formula (1) include, under the trade names, Aronix M-101 (n = about 2, R = H), M-102 (n = about 4, R = H), M -111 [n = about 1, R = n-C ₉ H ₁₉ (n-nonyl group, the same shall apply hereinafter)]
M-113 (n = about 4, R = n-C ₉ H ₁₉ ),
M-114 (n = about 8, R = n-C ₉ H ₁₉ ),
M-117 (n = 2.5, R = n-C ₉ H ₁₉ ) [above, manufactured by Toa Gosei Chemical Co., Ltd.], KAYARAD R-564 (n = about 2.3, R = H) [ Nippon Kayaku Co., Ltd.].

Specific examples of compounds having one ethylenically unsaturated bond other than the compound represented by the formula (1) include KAYARAD TC-110S, TC-120S [above, Nippon Kayaku Co., Ltd. )], V-158, V-2311 [Osaka Organic Chemical Co., Ltd.] and the like.
Further, as a compound having one ethylenically unsaturated bond other than the above, (a) a polymerizable unsaturated compound in the copolymer (A), such as an unsaturated carboxylic acid diester such as dimethyl maleate and diethyl maleate, (B) The same compounds as those exemplified for the polymerizable unsaturated compound or other polymerizable unsaturated compounds can be used.

  Next, as the compound having two ethylenically unsaturated bonds, for example, di (meth) acrylates of dihydric alcohol, preferably a compound represented by the following formula (2), and the following formula (3): The compound represented, the compound represented by following formula (4), etc. can be mentioned.

〔式（２）中、ｎおよびｍはそれぞれ０〜８の整数であり、各Ｒは相互に独立に水素原子またはメチル基を示す。〕

[In Formula (2), n and m are each an integer of 0-8, and each R shows a hydrogen atom or a methyl group mutually independently. ]

〔式（３）中、Ｒは炭素数２〜８の直鎖状もしくは分岐状のアルキレン基を示し、ｎは１〜１０の整数である。〕

[In Formula (3), R shows a C2-C8 linear or branched alkylene group, and n is an integer of 1-10. ]

〔式（４）中、各Ｒは相互に独立に水素原子またはメチル基を示し、Ｍは２価アルコールの残基を示し、Ｎはジカルボン酸の残基を示し、ｎは０または１である。〕

[In Formula (4), each R independently represents a hydrogen atom or a methyl group, M represents a dihydric alcohol residue, N represents a dicarboxylic acid residue, and n represents 0 or 1. . ]

Specific examples of the compound represented by the formula (2) include, under the trade name, Aronix M-210 (n = about 2, m = about 2, R = CH ₃ ) [manufactured by Toa Gosei Chemical Co., Ltd.], KAYARAD R-551 (n + m = about 4, R = CH ₃ ), R-712 (n + m = about 4, R = H) [above, manufactured by Nippon Kayaku Co., Ltd.] and the like.

Further, specific examples of the compound represented by the formula (3) include, under the trade name, Aronix M-240 [R = —CH ₂ CH ₂ —, n = about 4], M-245 [R = —CH _2]. CH ₂ −, n = about 9] [above, manufactured by Toa Gosei Chemical Co., Ltd.]
KAYARAD HDDA [R = − (CH ₂ ) ₆ −, n = 1],
NPGDA [R = —CH ₂ C (CH ₃ ) ₂ CH ₂ —, n = 1],
TPGDA [R = —CH ₂ CH (CH ₃ ) —, n = 1],
PEG400DA [R = —CH ₂ CH ₂ —, n = about 8],
MANDA [R = —CH ₂ C (CH ₃ ) ₂ CH ₂ —, n = 1] [Nippon Kayaku Co., Ltd.], light acrylate 1.9-NDA [R = — (CH ₂ ) ₈ -, N = 1] and the like.

  Moreover, as a specific example of the compound represented by Formula (4), it is a brand name, Aronix M-6100, M-6200, M-6250, M-6300, M-6400, M-6500 [ As mentioned above, Toa Gosei Chemical Co., Ltd.] can be mentioned.

  Furthermore, as a compound having two ethylenically unsaturated bonds other than those described above, a compound represented by the following formula (5-1) [trade name KAYARAD HX-220, manufactured by Nippon Kayaku Co., Ltd.], formula (5 -2) [trade name KAYARAD HX-620, manufactured by Nippon Kayaku Co., Ltd.] and trade names R-604 [manufactured by Nippon Kayaku Co., Ltd.], V-260, V-312 V-335HP [Osaka Organic Chemical Industry Co., Ltd.] and the like.

〔式（５−１）中、ｐおよびｑはそれぞれ０〜２の整数で、ｐ＋ｑ＝２である。〕
〔式（５−２）中、ｐおよびｑはそれぞれ０〜４の整数で、ｐ＋ｑ＝４である。〕

[In Formula (5-1), p and q are each an integer of 0 to 2, and p + q = 2. ]
[In Formula (5-2), p and q are integers of 0 to 4, respectively, and p + q = 4. ]

  Next, examples of the compound having three or more ethylenically unsaturated bonds include poly (meth) acrylates of trivalent or higher alcohols, preferably compounds represented by the following formula (6), 7), a compound represented by the following formula (8), a compound represented by the following formula (9), and the like.

〔式（６）中、ｎは０〜８の整数であり、Ｒは水素原子、メチル基またはヒドロキシル基を示す。〕

[In Formula (6), n is an integer of 0-8, R shows a hydrogen atom, a methyl group, or a hydroxyl group. ]

〔式（７）中、Ｒは酸素原子またはメチレン基を示す。〕

[In Formula (7), R shows an oxygen atom or a methylene group. ]

〔式（８）中、各Ｒは相互に独立に水素原子またはメチル基を示し、Ｘは３価アルコールの残基を示し、Ｙはジカルボン酸の残基を示し、ｎは０〜１５の整数である。〕

[In the formula (8), each R independently represents a hydrogen atom or a methyl group, X represents a trihydric alcohol residue, Y represents a dicarboxylic acid residue, and n represents an integer of 0 to 15. It is. ]

〔式（９）中、ＡはＣＨ₂ ＝ＣＨＣＯ−を示し、ｎは１または２であり、ａは２〜６の整数、ｂは０〜４の整数で、ａ＋ｂ＝６である。〕

Wherein (9), A represents a CH ₂ = CHCO-, n is 1 or 2, a is an integer of from 2 to 6, b is an integer of 0 to 4, which is a + b = 6. ]

Specific examples of the compound represented by the formula (6) include, under trade names, Aronix M-309 (n = 0, R = CH ₃ ), M-310 (n = about 1, R = CH ₃ ) , Manufactured by Toa Gosei Chemical Industry Co., Ltd.], KAYARAD TMPTA (n = 0, R = CH ₃ ) [manufactured by Nippon Kayaku Co., Ltd.], V-295 (n = 0, R = CH ₃ ), V-300 (N = 0, R = OH) [Osaka Organic Chemical Co., Ltd.] etc. can be mentioned.

  Moreover, as a specific example of the compound represented by Formula (7), Aronix M-400 [made by Toa Gosei Chemical Co., Ltd.] etc. can be mentioned by a brand name.

  Further, specific examples of the compound represented by the formula (8) include, under trade names, Aronix M-7100, M-8030, M-8060, M-8100, M-9050 [above, Toa Gosei Chemical Co., Ltd. Manufactured by Kogyo Co., Ltd.].

  Further, specific examples of the compound represented by the formula (9) include KAYARAD DPCA-20 (n = about 1, a = about 2, b = about 4) and DPCA-30 (n = about 1) as trade names. , A = about 3, b = about 3), DPCA-60 (n = about 1, a = about 6, b = about 0), DPCA-120 (m = about 2, a = about 6, b = About 0) [Nippon Kayaku Co., Ltd.], V-360, V-GPT, V-3PA, V-400 [Osaka Organic Chemical Co., Ltd.], and the like.

Of these polymerizable unsaturated compounds, a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds are preferred, and more preferably a compound represented by formula (4), A compound represented by formula (8).
In this invention, a polymerizable unsaturated compound can be used individually or in mixture of 2 or more types.

  The amount of the polymerizable unsaturated compound used in the radiation-sensitive resin composition for forming an interlayer insulating film of the present invention is preferably 30 to 150 parts by weight, more preferably 50, relative to 100 parts by weight of the copolymer (A). ~ 100 parts by weight. In this case, if the amount of the polymerizable unsaturated compound used is less than 30 parts by weight, the sensitivity tends to decrease. On the other hand, if it exceeds 150 parts by weight, the compatibility with the copolymer (A) decreases. There is a risk of film roughness on the coating surface.

-(C) Photopolymerization initiator-
The photopolymerization initiator in the present invention is a compound that generates an active species (for example, a radical or the like) capable of initiating polymerization of the polymerizable unsaturated compound (B) upon irradiation with radiation.
Examples of such a photopolymerization initiator include α-diketones such as benzyl and diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2, Thioxanthones such as 4-diethylthioxanthone and thioxanthone-4-sulfonic acid; Benzophenones such as benzophenone, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone; acetophenone, p-dimethyl Aminoacetophenone, α, α′-dimethoxyacetoxybenzophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1 Acetophenones such as ON, 2-methyl [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one Quinones such as anthraquinone and 1,4-naphthoquinone; halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone, tris (trichloromethyl) -s-triazine, peroxides such as di-t-butyl peroxide; Examples include acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Commercially available photopolymerization initiators are trade names such as Irgacure 184, 500, 651, 907, CGI369, CG24-61 (above, manufactured by Ciba Geigy), Lucirin LR8728, TPO (above. , BASF Corp.), Darocur 1116, 1173 (above, Merck Corp.), Ubekrill p36 (UCB Corp.) and the like.

Of these photopolymerization initiators, 2,2-dimethoxy-1,2-diphenylethane-1-one and 2-methyl [4- (methylthio) phenyl] -2-morpholinopropan-1-one are preferable. Acetophenones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, phenacyl chloride, tribromomethylphenylsulfone, 2,4,6-trimethylbenzoyldiphenylphos Such as fin oxide.
In this invention, a photoinitiator can be used individually or in mixture of 2 or more types, and can also be used together with a photosensitizer.

  The usage-amount of the photoinitiator in the radiation sensitive resin composition for interlayer insulation film formation of this invention becomes like this. Preferably it is 1-50 weight part with respect to 100 weight part of (B) polymerizable unsaturated compounds, Furthermore, 10- 40 parts by weight. In this case, if the amount of the photopolymerization initiator used is less than 1 part by weight, it is easily affected by radical deactivation (reduction in sensitivity) due to oxygen, while if it exceeds 50 parts by weight, the copolymer (A) And the compatibility with the polymerizable unsaturated compound, the storage stability of the resulting resin composition, etc. tend to decrease.

-(D) Coupling agent-
Examples of the coupling agent in the present invention include a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent.
Examples of the silane coupling agent include:
3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri (n-propoxy) silane, 3- (meth) acryloyloxypropyltri ( i-propoxy) silane, 3- (meth) acryloyloxypropyltriacetoxysilane, 3- (meth) acryloyloxypropyltris (2-methoxyethoxy) silane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- ( (Meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldi (n-propoxy) silane, 3- (meth) acryloyloxypropylmethyldi (i-propoxy) silane, 3- (meta Acryloyloxypropyl methyl diacetoxy silane, 3- (meth) acryloyloxy propyl methyl bis (2-methoxyethoxy) (meth) acryloyl group-containing silane coupling agent such as a silane;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (n-propoxy) silane, vinyltri (i-propoxy) silane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, 1,3-divinyltetramethyldisilazane, etc. Vinyl group-containing silane coupling agent of

5- (bicycloheptenyl) trimethoxysilane, 5- (bicycloheptenyl) triethoxysilane, 5- (bicycloheptenyl) tri (n-propoxy) silane, 5- (bicycloheptenyl) tri (i-propoxy) Bicycloheptenyl group-containing silane coupling agents such as silane, 5- (bicycloheptenyl) triacetoxysilane, 5- (bicycloheptenyl) tris (2-methoxyethoxy) silane;
[2- (3-cyclohexenyl) ethyl] trimethoxysilane, [2- (3-cyclohexenyl) ethyl] triethoxysilane, [2- (3-cyclohexenyl) ethyl] tri (n-propoxy) silane, [ 2- (3-cyclohexenyl) ethyl] tri (i-propoxy) silane, [2- (3-cyclohexenyl) ethyl] triacetoxysilane, [2- (3-cyclohexenyl) ethyl] tris (2-methoxyethoxy) ) Cyclohexenyl group-containing silane coupling agents such as silane;

3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltri (n-propoxy) silane, 3-glycidoxypropyltri (i-propoxy) silane, 3- Glycidoxypropyltriacetoxysilane, 3-glycidoxypropyltris (2-methoxyethoxy) silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Methyldi (n-propoxy) silane, 3-glycidoxypropylmethyldi (i-propoxy) silane, 3-glycidoxypropylmethyldiacetoxysilane, 3-glycidoxypropylmethylbis (2-methoxyethoxy) silane 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri (n-propoxy) silane, 2- (3,4-epoxycyclohexyl) ethyltri Epoxy group-containing silane coupling agents such as (i-propoxy) silane, 2- (3,4-epoxycyclohexyl) ethyltriacetoxysilane, 2- (3,4-epoxycyclohexyl) ethyltris (2-methoxyethoxy) silane ;

3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltri (n-propoxy) silane, 3-isocyanatopropyltri (i-propoxy) silane, 3-isocyanatopropyltri Isocyanate group-containing silane coupling agents such as acetoxysilane and 3-isocyanatopropyltris (2-methoxyethoxy) silane;
3-diallylaminopropyltrimethoxysilane, 3-diallylaminopropyltriethoxysilane, 3-diallylaminopropyltri (n-propoxy) silane, 3-diallylaminopropyltri (i-propoxy) silane, 3-diallylaminopropyltri Acetoxysilane, 3-diallylaminopropyltris (2-methoxyethoxy) silane, 3- (3-aminopropoxy) -3,3-dimethyl-1-propenyltrimethoxysilane, 3- (3-aminopropoxy) -3, 3-dimethyl-1-propenyltriethoxysilane, 3- (3-aminopropoxy) -3,3-dimethyl-1-propenyltri (n-propoxy) silane, 3- (3-aminopropoxy) -3,3- Dimethyl-1-propenyltri (i-propoxy) silane, 3 Amino groups such as (3-aminopropoxy) -3,3-dimethyl-1-propenyltriacetoxysilane, 3- (3-aminopropoxy) -3,3-dimethyl-1-propenyltris (2-methoxyethoxy) silane Containing silane coupling agents;

N- [2- (p-vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane / hydrochloride, N- [2- (p-vinylbenzylamino) ethyl] -3-aminopropyltriethoxysilane / hydrochloric acid Salt, N- [2- (p-vinylbenzylamino) ethyl] -3-aminopropyltri (n-propoxy) silane / hydrochloride, N- [2- (p-vinylbenzylamino) ethyl] -3-amino Propyltri (i-propoxy) silane · hydrochloride, N- [2- (p-vinylbenzylamino) ethyl] -3-aminopropyltriacetoxysilane · hydrochloride, N- [2- (p-vinylbenzylamino) Ethyl] -3-aminopropyltris (2-methoxyethoxy) silane / hydrochloride containing amine hydrochloride base-containing silane coupling agents;
2- (chloromethyl) allyltrimethoxysilane, 2- (chloromethyl) allyltriethoxysilane, 2- (chloromethyl) allyltri (n-propoxy) silane, 2- (chloromethyl) allyltri (i-propoxy) silane, Examples thereof include halogen-containing silane coupling agents such as 2- (chloromethyl) allyltriacetoxysilane and 2- (chloromethyl) allyltris (2-methoxyethoxy) silane.

Examples of the titanium coupling agent include:
3- (meth) acryloyloxypropyltrimethoxytitanium, 3- (meth) acryloyloxypropyltriethoxytitanium, 3- (meth) acryloyloxypropyltri (n-propoxy) titanium, 3- (meth) acryloyloxypropyltri ( i-propoxy) titanium, 3- (meth) acryloyloxypropyltriacetoxytitanium, 3- (meth) acryloyloxypropyltris (2-methoxyethoxy) titanium, 3- (meth) acryloyloxypropylmethyldimethoxytitanium, 3- ( (Meth) acryloyloxypropylmethyldiethoxytitanium, 3- (meth) acryloyloxypropylmethyldi (n-propoxy) titanium, 3- (meth) acryloyloxypropylmethyldi (i-propoxy) titanium, 3- (meta Acryloyloxypropyl methyl diacetoxy titanium, 3- (meth) acryloyloxy propyl methyl bis (2-methoxyethoxy) (meth) acryloyl group-containing titanium-based coupling agents such as titanium;
Vinyl group-containing titanium-based coupling agents such as vinyltrimethoxytitanium, vinyltriethoxytitanium, vinyltri (n-propoxy) titanium, vinyltri (i-propoxy) titanium, vinyltriacetoxytitanium, vinyltris (2-methoxyethoxy) titanium;

5- (bicycloheptenyl) trimethoxytitanium, 5- (bicycloheptenyl) triethoxytitanium, 5- (bicycloheptenyl) tri (n-propoxy) titanium, 5- (bicycloheptenyl) tri (i-propoxy) Bicycloheptenyl group-containing titanium-based coupling agents such as titanium, 5- (bicycloheptenyl) triacetoxy titanium, 5- (bicycloheptenyl) tris (2-methoxyethoxy) titanium;
[2- (3-cyclohexenyl) ethyl] trimethoxytitanium, [2- (3-cyclohexenyl) ethyl] triethoxytitanium, [2- (3-cyclohexenyl) ethyl] tri (n-propoxy) titanium, [ 2- (3-Cyclohexenyl) ethyl] tri (i-propoxy) titanium, [2- (3-cyclohexenyl) ethyl] triacetoxytitanium, [2- (3-cyclohexenyl) ethyl] tris (2-methoxyethoxy) ) Titanium coupling agent containing cyclohexenyl group such as titanium;

3-glycidoxypropyltrimethoxytitanium, 3-glycidoxypropyltriethoxytitanium, 3-glycidoxypropyltri (n-propoxy) titanium, 3-glycidoxypropyltri (i-propoxy) titanium, 3- Glycidoxypropyltriacetoxytitanium, 3-glycidoxypropyltris (2-methoxyethoxy) titanium, 3-glycidoxypropylmethyldimethoxytitanium, 3-glycidoxypropylmethyldiethoxytitanium, 3-glycidoxypropyl Methyldi (n-propoxy) titanium, 3-glycidoxypropylmethyldi (i-propoxy) titanium, 3-glycidoxypropylmethyldiacetoxytitanium, 3-glycidoxypropylmethylbis (2-methoxyethoxy) titanium 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxytitanium, 2- (3,4-epoxycyclohexyl) ethyltriethoxytitanium, 2- (3,4-epoxycyclohexyl) ethyltri (n-propoxy) titanium, 2- (3,4-epoxycyclohexyl) ethyltri Epoxy group-containing titanium-based coupling agents such as (i-propoxy) titanium, 2- (3,4-epoxycyclohexyl) ethyltriacetoxytitanium, 2- (3,4-epoxycyclohexyl) ethyltris (2-methoxyethoxy) titanium ;

3-isocyanatopropyltrimethoxytitanium, 3-isocyanatopropyltriethoxytitanium, 3-isocyanatopropyltri (n-propoxy) titanium, 3-isocyanatopropyltri (i-propoxy) titanium, 3-isocyanatopropyltri Isocyanate group-containing titanium-based coupling agents such as acetoxytitanium and 3-isocyanatopropyltris (2-methoxyethoxy) titanium;
3-diallylaminopropyltrimethoxytitanium, 3-diallylaminopropyltriethoxytitanium, 3-diallylaminopropyltri (n-propoxy) titanium, 3-diallylaminopropyltri (i-propoxy) titanium, 3-diallylaminopropyltri Acetoxytitanium, 3-diallylaminopropyltris (2-methoxyethoxy) titanium, 3- (3-aminopropoxy) -3,3-dimethyl-1-propenyltrimethoxytitanium, 3- (3-aminopropoxy) -3, 3-dimethyl-1-propenyltriethoxytitanium, 3- (3-aminopropoxy) -3,3-dimethyl-1-propenyltri (n-propoxy) titanium, 3- (3-aminopropoxy) -3,3- Dimethyl-1-propenyltri (i-propoxy) titanium, 3 Amino groups such as (3-aminopropoxy) -3,3-dimethyl-1-propenyltriacetoxytitanium, 3- (3-aminopropoxy) -3,3-dimethyl-1-propenyltris (2-methoxyethoxy) titanium Containing titanium coupling agent;

N- [2- (p-vinylbenzylamino) ethyl] -3-aminopropyltrimethoxytitanium / hydrochloride, N- [2- (p-vinylbenzylamino) ethyl] -3-aminopropyltriethoxytitanium / hydrochloric acid Salt, N- [2- (p-vinylbenzylamino) ethyl] -3-aminopropyltri (n-propoxy) titanium / hydrochloride, N- [2- (p-vinylbenzylamino) ethyl] -3-amino Propyltri (i-propoxy) titanium / hydrochloride, N- [2- (p-vinylbenzylamino) ethyl] -3-aminopropyltriacetoxytitanium / hydrochloride, N- [2- (p-vinylbenzylamino) Ethyl] -3-aminopropyltris (2-methoxyethoxy) titanium / hydrochloride-containing titanium coupling agent containing amine hydrochloride base;
2- (chloromethyl) allyltrimethoxytitanium, 2- (chloromethyl) allyltriethoxytitanium, 2- (chloromethyl) allyltri (n-propoxy) titanium, 2- (chloromethyl) allyltri (i-propoxy) titanium, Mention may be made of halogen-containing titanium-based coupling agents such as 2- (chloromethyl) allyltriacetoxytitanium and 2- (chloromethyl) allyltris (2-methoxyethoxy) titanium.

Moreover, as an aluminum coupling agent, for example,
3- (meth) acryloyloxypropyldimethoxyaluminum, 3- (meth) acryloyloxypropyldiethoxyaluminum, 3- (meth) acryloyloxypropyldi (n-propoxy) aluminum, 3- (meth) acryloyloxypropyldi (i -Propoxy) aluminum, 3- (meth) acryloyloxypropyldiacetoxyaluminum, 3- (meth) acryloyloxypropylbis (2-methoxyethoxy) aluminum, 3- (meth) acryloyloxypropylmethylmethoxyaluminum, 3- (meta ) Acryloyloxypropylmethylethoxyaluminum, 3- (meth) acryloyloxypropylmethyl (n-propoxy) aluminum, 3- (meth) acryloyloxypropylmethyl ( - propoxy) aluminum, 3- (meth) acryloyloxy propyl methyl acetoxy aluminum, 3- (meth) acryloyloxy propyl methyl (2-methoxyethoxy) aluminum etc. (meth) acryloyl group-containing aluminum-based coupling agent;
Vinyl group-containing aluminum-based coupling agents such as vinyldimethoxyaluminum, vinyldiethoxyaluminum, vinyldi (n-propoxy) aluminum, vinyldi (i-propoxy) aluminum, vinyldiacetoxyaluminum, vinylbis (2-methoxyethoxy) aluminum;

5- (bicycloheptenyl) dimethoxyaluminum, 5- (bicycloheptenyl) diethoxyaluminum, 5- (bicycloheptenyl) di (n-propoxy) aluminum, 5- (bicycloheptenyl) di (i-propoxy) aluminum , Bicycloheptenyl group-containing aluminum-based coupling agents such as 5- (bicycloheptenyl) diacetoxyaluminum and 5- (bicycloheptenyl) bis (2-methoxyethoxy) aluminum;
[2- (3-cyclohexenyl) ethyl] dimethoxyaluminum, [2- (3-cyclohexenyl) ethyl] diethoxyaluminum, [2- (3-cyclohexenyl) ethyl] di (n-propoxy) aluminum, [2 -(3-Cyclohexenyl) ethyl] di (i-propoxy) aluminum, [2- (3-cyclohexenyl) ethyl] diacetoxyaluminum, [2- (3-cyclohexenyl) ethyl] bis (2-methoxyethoxy) An aluminum-based coupling agent containing a cyclohexenyl group such as aluminum;

3-glycidoxypropyldimethoxyaluminum, γ-glycidoxypropyldiethoxyaluminum, 3-glycidoxypropyldi (n-propoxy) aluminum, 3-glycidoxypropyldi (i-propoxy) aluminum, 3-glycidyl Sidoxypropyldiacetoxyaluminum, 3-glycidoxypropylbis (2-methoxyethoxy) aluminum, 3-glycidoxypropylmethylmethoxyaluminum, 3-glycidoxypropylmethylethoxyaluminum, 3-glycidoxypropylmethyl ( n-propoxy) aluminum, 3-glycidoxypropylmethyl (i-propoxy) aluminum, 3-glycidoxypropylmethylacetoxyaluminum, 3-glycidoxypropylmethyl (2-methoxyethoxy) a Minium, 2- (3,4-epoxycyclohexyl) ethyldimethoxyaluminum, 2- (3,4-epoxycyclohexyl) ethyldiethoxyaluminum, 2- (3,4-epoxycyclohexyl) ethyldi (n-propoxy) aluminum, 2 -(3,4-epoxycyclohexyl) ethyldi (i-propoxy) aluminum, 2- (3,4-epoxycyclohexyl) ethyldiacetoxyaluminum, 2- (3,4-epoxycyclohexyl) ethylbis (2-methoxyethoxy) aluminum Epoxy group-containing aluminum-based coupling agents such as

3-isocyanatopropyldimethoxyaluminum, 3-isocyanatopropyldiethoxyaluminum, 3-isocyanatopropyldi (n-propoxy) aluminum, 3-isocyanatopropyldi (i-propoxy) aluminum, 3-isocyanatopropyldiacetoxy An aluminum group-containing coupling agent containing an isocyanate group such as aluminum and 3-isocyanatopropylbis (2-methoxyethoxy) aluminum;
3-diallylaminopropyldimethoxyaluminum, 3-diallylaminopropyldiethoxyaluminum, γ-diallylaminopropyldi (n-propoxy) aluminum, γ-diallylaminopropyldi (i-propoxy) aluminum, 3-diallylaminopropyldiacetoxy Aluminum, 3-diallylaminopropylbis (2-methoxyethoxy) aluminum, 3- (3-aminopropoxy) -3,3-dimethyl-1-propenyldimethoxyaluminum, 3- (3-aminopropoxy) -3,3- Dimethyl-1-propenyldiethoxyaluminum, 3- (3-aminopropoxy) -3,3-dimethyl-1-propenyldi (n-propoxy) aluminum, 3- (3-aminopropoxy) -3,3-dimethyl-1 -Propeni Rudi (i-propoxy) aluminum, 3- (3-aminopropoxy) -3,3-dimethyl-1-propenyldiacetoxyaluminum, 3- (3-aminopropoxy) -3,3-dimethyl-1-propenylbis ( Amino group-containing aluminum-based coupling agents such as 2-methoxyethoxy) aluminum;

N- [2- (p-vinylbenzylamino) ethyl] -3-aminopropyldimethoxyaluminum hydrochloride, N- [2- (p-vinylbenzylamino) ethyl] -3-aminopropyldiethoxyaluminum hydrochloride N- [2- (p-vinylbenzylamino) ethyl] -3-aminopropyldi (n-propoxy) aluminum hydrochloride, N- [2- (p-vinylbenzylamino) ethyl] -3-aminopropyl Di (i-propoxy) aluminum hydrochloride, N- [2- (p-vinylbenzylamino) ethyl] -3-aminopropyldiacetoxyaluminum hydrochloride, N- [2- (p-vinylbenzylamino) ethyl ] 3-aminopropylbis (2-methoxyethoxy) aluminum / hydrochloride containing amine hydrochloride base containing aluminum Coupling agent;
2- (chloromethyl) allyldimethoxyaluminum, 2- (chloromethyl) allyldiethoxyaluminum, 2- (chloromethyl) allyldi (n-propoxy) aluminum, 2- (chloromethyl) allyldi (i-propoxy) aluminum, 2 Halogen-containing aluminum-based coupling agents such as-(chloromethyl) allyldiacetoxyaluminum and 2- (chloromethyl) allylbis (2-methoxyethoxy) aluminum;
Examples include 9-octadecenyl acetoacetate aluminum di-i-propoxide.

Among these coupling agents, 3- (meth) acryloyloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 1,3-divinyl Tetramethyldisilazane, 3- (meth) acryloyloxypropyltri (i-propoxy) titanium, 9-octadecenylacetoacetate aluminum di-i-propoxide and the like are preferable.
In this invention, a coupling agent can be used individually or in mixture of 2 or more types.

  The amount of the coupling agent used in the radiation-sensitive resin composition for forming an interlayer insulating film of the present invention is preferably 0.5 to 20 parts by weight, more preferably 2 with respect to 100 parts by weight of the copolymer (A). -10 parts by weight. In this case, when the amount of the coupling agent used is less than 1 part by weight, the adhesion between the obtained interlayer insulating film and the interlayer insulating film of the transparent electrode such as ITO (tin-doped indium oxide) or the like There is a possibility that the adhesiveness may be lowered. On the other hand, if it exceeds 20 parts by weight, the developability of the resulting composition tends to be lowered, and the development residue tends to remain.

-Other additives-
Other additives such as an epoxy compound, a thermal polymerization inhibitor, a surfactant, and a carboxylic acid additive can be blended with the radiation-sensitive resin composition for forming an interlayer insulating film of the present invention.
The epoxy compound is a component used for the purpose of further improving the heat resistance and hardness of the interlayer insulating film.
Such an epoxy compound is not particularly limited as long as there is no problem in compatibility with the constituents of the radiation-sensitive resin composition. For example, bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol Examples thereof include novolak type epoxy resins, cycloaliphatic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, heterocyclic epoxy resins, poly (glycidyl methacrylate) and the like.
Of these epoxy compounds, bisphenol A type epoxy resin, cresol novolac type epoxy resin, glycidyl ester type epoxy resin and the like are preferable.
The said epoxy compound can be used individually or in mixture of 2 or more types.
The compounding amount of the epoxy compound is preferably 100 parts by weight or less with respect to 100 parts by weight of the copolymer (A).

The thermal polymerization inhibitor is a component used for the purpose of suppressing a decrease in developability due to hot fog during pre-baking when forming an interlayer insulating film.
Examples of such thermal polymerization inhibitors include pyrogallol, benzoquinone, hydroquinone, methylene blue, t-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4 , 4 ′-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] diphenol, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) ) -3-phenylpropane and the like.
These thermal polymerization inhibitors can be used alone or in admixture of two or more.
The blending amount of the thermal polymerization inhibitor is preferably 5 parts by weight or less with respect to 100 parts by weight of the copolymer (A).

Moreover, the said surfactant is a component used in order to improve the applicability | paintability of the liquid composition mentioned later, defoaming property, leveling property, etc.
Examples of such surfactants include fluorine surfactants, silicone surfactants, nonionic surfactants, and the like.
Examples of the fluorine-based surfactant include BM-1000, BM-1100 (manufactured by BM CHIMIE), MegaFack F142D, F172, F173, and F183 (all Dainippon Ink Chemicals, Inc.). Industrial Co., Ltd.), Florard FC-135, FC-170C, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S- 131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (above, Asahi Glass For example).

  Examples of the silicone surfactant include trade names such as SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, and DC-190 (above, Toray Dow Corning Silicone Co., Ltd.), KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), F-top EF301, EF303, EF352 (above, Shin-Akita Kasei Co., Ltd.).

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene dialkyl esters, and the like.
Examples of the polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether. Examples of the polyoxyethylene aryl ethers include polyoxyethylene n-octyl. Examples of the polyoxyethylene dialkyl esters include phenyl ether and polyoxyethylene n-nonyl phenyl ether, and examples thereof include polyoxyethylene dilaurate and polyoxyethylene distearate.
Furthermore, as surfactants other than those described above, for example, (meth) acrylic acid copolymer polyflow No. 57, no. 90 (manufactured by Kyoeisha Chemical Co., Ltd.).
These surfactants can be used alone or in admixture of two or more.

  The blending amount of the surfactant is preferably 5 parts by weight or less, more preferably 2 parts by weight or less with respect to 100 parts by weight of the copolymer (A). In this case, when the compounding amount of the surfactant exceeds 5 parts by weight, the coating film tends to be rough.

The carboxylic acid additive is a component made of a compound having a carboxyl group and / or a carboxylic anhydride group, and used for the purpose of finely adjusting the solubility in an alkali developer.
Examples of such carboxylic acid-based additives include monocarboxylic acids such as acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; lactic acid, 2-hydroxybutyric acid, 3 Hydroxy such as hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, o-hydroxycinnamic acid, m-hydroxycinnamic acid, p-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic acid Monocarboxylic acids; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4- Cyclohexanetricarboxylic acid, trimellitic acid, pyromellitic acid, 1,2,3,4-butanetetracarboxylic acid Polyvalent carboxylic acids such as 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, Tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, 1,2,3,4-butanetetracarboxylic acid Dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, ethylene glycol bis (trimellitate) dianhydride, glycerin Examples thereof include carboxylic acid anhydrides such as tris (trimellitate) dianhydride.
These carboxylic acid-based additives can be used alone or in admixture of two or more.
The blending amount of the carboxylic acid-based additive is preferably 10 parts by weight or less with respect to 100 parts by weight of the (A) copolymer.

Further, in the radiation sensitive resin composition for forming an interlayer insulating film of the present invention, a filler, a colorant, a viscosity modifier and the like are added in a range that does not impair the original characteristics of the radiation sensitive resin composition, preferably in total. The amount can be blended within a range of 50% by weight or less of the total composition to be obtained.
Examples of the filler include silica, alumina, talc, bentonite, zirconium silicate, and powdered glass.
These fillers can be used alone or in admixture of two or more.
Examples of the colorant include extender pigments such as alumina white, clay, barium carbonate, barium sulfate; zinc white, lead white, yellow lead, red lead, ultramarine, bitumen, titanium oxide, zinc chromate, bengara, Inorganic pigments such as carbon black; organic pigments such as brilliant carmine 6B, permanent red 6B, permanent red R, benzidine yellow, phthalocyanine blue, and phthalocyanine green; basic dyes such as magenta and rhodamine; direct dyes such as direct scarlet and direct orange And acid dyes such as roserine and metanyl yellow.
These colorants can be used alone or in admixture of two or more.
Examples of the viscosity modifier include bentonite, silica gel, and aluminum powder.
These viscosity modifiers can be used alone or in admixture of two or more.

Liquid Composition The radiation-sensitive resin composition for forming an interlayer insulating film of the present invention comprises (A) a copolymer, (B) a polymerizable unsaturated compound, (C) a photopolymerization initiator, (D) a coupling agent, and It is preferable to dilute with an organic solvent to obtain a liquid composition for the purpose of uniformly mixing other additives blended as necessary and facilitating the coating operation on the substrate.
The organic solvent is preferably one that can uniformly dissolve or disperse the constituent components of the radiation-sensitive resin composition, does not react with the constituent components, and has appropriate volatility.
Examples of such an organic solvent include those similar to the solvents exemplified for the polymerization for producing the copolymer (A), N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N -Methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, di (n-hexyl) ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol And high-boiling solvents such as benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate.

Among these organic solvents, polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether and diethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, due to solubility, reactivity with constituents and ease of coating formation. Alkyl ether acetates of polyhydric alcohols such as, other esters such as ethyl lactate, methyl 3-methoxypropionate and ethyl 3-ethoxypropionate, and ketones such as diacetone alcohol are preferred.
The said organic solvent can be used individually or in mixture of 2 or more types.
The amount of the organic solvent used can be appropriately selected according to the specific use of the radiation-sensitive resin composition for forming an interlayer insulating film, the coating method, and the like.

  When preparing the radiation-sensitive resin composition and the liquid composition in the present invention, when a filler or pigment is not blended, it is only necessary to stir and mix by a usual method. When adding a filler or pigment, And a disperser such as a dissolver, a homogenizer, and a three roll mill. In addition, the liquid composition may be subjected to use after preparation by filtration through a mesh, a membrane filter or the like after preparation.

Method for Forming Interlayer Insulating Film The method for forming an interlayer insulating film of the present invention includes at least the following steps (a) to (d) in the order described below.
(A) a step of forming a coating film of the radiation-sensitive resin composition for forming an interlayer insulating film of the present invention (hereinafter simply referred to as “radiation-sensitive resin composition”) on a substrate;
(B) A step of irradiating at least a part of the coating film (hereinafter referred to as “exposure”), (c) a step of developing the coating film after exposure,
(D) A step of baking (hereinafter referred to as “baking”) the developed coating film.

Hereinafter, these steps will be described.
-(I) Process-
In step (a), the radiation-sensitive resin composition is preferably applied as a liquid composition to the substrate surface, and the solvent is removed by pre-baking to form a coating film of the radiation-sensitive resin composition. To do.
Examples of the types of substrates that can be used include glass substrates, silicon wafers, and substrates on which various metals are formed.
The coating method of the composition solution is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, an ink jet method or the like may be adopted. Can do.
The pre-baking conditions vary depending on the types of constituents of the radiation-sensitive resin composition, the use ratio, and the like, but can be set at, for example, 60 to 130 ° C. for 30 seconds to 15 minutes.
As a film thickness of the coating film formed, 5-20 micrometers is preferable as a value after prebaking, for example.

-(B) Process-
In the step (b), at least a part of the formed coating film is exposed. In this case, when only a part of the coating film is exposed, the exposure is usually performed through a photomask having a pattern of a predetermined shape.
Examples of radiation used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm), far ultraviolet rays such as KrF excimer laser and ArF excimer laser, X-rays such as synchrotron radiation, and electron beams. And charged particle beams.
Of these radiations, ultraviolet rays are preferable, and ultraviolet rays including g-line and / or i-line are particularly preferable.
The exposure dose is preferably set to 50~10,000J / m ² approximately.

-(C) Process-
In step (c), the exposed coating film is developed to remove unexposed portions, thereby forming a pattern with a predetermined shape.
Examples of the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine. , Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5- An aqueous solution of an alkaline compound such as diazabicyclo [4,3,0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the aqueous solution of the alkaline compound.

Moreover, in this invention, when the radiation sensitive resin composition does not contain insoluble components, such as a filler and a pigment, the various organic solvent which melt | dissolves a structural component can also be used as a developing solution.
As a developing method, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method or the like can be employed.
The development time varies depending on the composition of the radiation sensitive resin composition, but can be, for example, 30 to 300 seconds.
In addition, since the radiation sensitive resin composition conventionally used for the formation of the interlayer insulating film causes a defect such as peeling in the formed pattern when the development time exceeds about 20 to 25 seconds or more from the optimum condition, Although it was necessary to strictly control the development time, in the case of the radiation-sensitive resin composition of the present invention, a good pattern can be formed even if the excess time from the optimal development time is 30 seconds or more, and the product yield There are the above advantages.

-(D) Process-
In the step (d), the developed coating film is post-exposed as necessary, and then, for example, is baked by a heating device such as a hot plate or oven to cure the coating film. Examples of radiation used for the post-exposure include ultraviolet rays such as g-ray (wavelength 436 nm) and i-ray (wavelength 365 nm), far-ultraviolet rays such as KrF excimer laser and ArF excimer laser, X-rays such as synchrotron radiation, and electron beams. And the like.
Of these radiations, ultraviolet rays are preferable, and ultraviolet rays including g-line and / or i-line are particularly preferable.
Exposure of post-exposure, it is preferable that the 50~10,000J / m ² approximately.
The baking conditions vary depending on the types and use ratios of the components of the radiation-sensitive resin composition, the desired pattern shape, the heating device used, etc., but in the case of a hot plate, for example, 10 to 150 to 240 ° C. It is about 30 minutes, and in the case of an oven, for example, it is about 150 to 240 ° C. for about 30 to 90 minutes. Moreover, in baking, the step baking method etc. which heat-process twice or more can also be employ | adopted.
In this way, a desired interlayer insulating film can be formed on the substrate.

The radiation-sensitive resin composition for forming an interlayer insulating film of the present invention can be formed into an interlayer insulating film having high resolution and sufficient thickness and having excellent characteristics.
The interlayer insulating film of the present invention is excellent in various physical properties such as transparency, heat resistance, heat discoloration, adhesion, and solvent resistance. For example, various liquid crystal display elements including TFT type liquid crystal display elements, It can be used very suitably for electronic components such as magnetic head elements, integrated circuit elements, and solid-state imaging elements.
Further, according to the method of forming an interlayer insulating film of the present invention, an interlayer insulating film having excellent characteristics can be easily formed with a high product yield.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
Synthesis example 1
After replacing the flask equipped with a dry ice / methanol system reflux with nitrogen, 4 g of 2,2′-azobisisobutyronitrile as a radical polymerization initiator, 100 g of diethylene glycol dimethyl ether and 50 g of diethylene glycol monomethyl ether as an organic solvent, and radical Stir until the polymerization initiator is dissolved. Subsequently, 15 g of methacrylic acid, 15 g of mono (2-methacryloyloxyethyl) hexahydrophthalate, 40 g of tricyclodecanyl methacrylate, 15 g of styrene and 15 g of tetrahydrofurfuryl methacrylate were charged, and the temperature of the solution was adjusted to 80 with stirring. The polymerization was carried out at this temperature for 4 hours. Thereafter, the reaction product was dropped into a large amount of methanol to solidify the reaction product, and the coagulated product was washed with water. Thereafter, redissolving in the same weight of tetrahydrofuran as the obtained coagulated material and re-coagulation with a large amount of methanol was performed three times in total, and then the obtained coagulated material was vacuumed at 40 ° C. for 48 hours. The copolymer was obtained by drying.
This copolymer had Mw of 13,000. This copolymer is referred to as “copolymer (A-1)”.

Synthesis example 2
After substituting a flask equipped with a dry ice / methanol reflux with nitrogen, 4 g of 2,2′-azobis-2,4-dimethylvaleronitrile as a radical polymerization initiator and 100 g of diethylene glycol diethyl ether and 150 g of ethyl lactate as an organic solvent were charged. The mixture was stirred until the radical polymerization initiator was dissolved. Subsequently, 10 g of methacrylic acid, 15 g of mono (2-methacryloyloxyethyl) hexahydrophthalate, 40 g of tricyclodecanyl methacrylate, 15 g of styrene and 20 g of tetrahydrofurfuryl methacrylate were charged, and the temperature of the solution was adjusted while stirring. The temperature was raised to 80 ° C., and polymerization was carried out at this temperature for 4 hours. Thereafter, the reaction product was dropped into a large amount of methanol to solidify the reaction product, and the coagulated product was washed with water. Thereafter, redissolving in the same weight of tetrahydrofuran as the obtained coagulated material and re-coagulation with a large amount of methanol was performed three times in total, and then the obtained coagulated material was vacuumed at 40 ° C. for 48 hours. The copolymer was obtained by drying.
This copolymer had a Mw of 15,000. This copolymer is referred to as “copolymer (A-2)”.

Synthesis example 3
After replacing the flask equipped with a dry ice / methanol reflux with nitrogen, 4 g of 2,2′-azobisisobutyronitrile as a radical polymerization initiator and 150 g of diacetone alcohol as an organic solvent were dissolved, and the radical polymerization initiator was dissolved. Stir until Subsequently, 20 g of acrylic acid, 15 g of mono (2-methacryloyloxyethyl) hexahydrophthalate, 45 g of tricyclodecanyl methacrylate, 15 g of styrene and 5 g of isoprene were added, and the temperature of the solution was raised to 80 ° C. while stirring. Polymerization was carried out at this temperature for 4 hours. Thereafter, the reaction product was dropped into a large amount of methanol to solidify the reaction product, and the coagulated product was washed with water. Then, after redissolving in the same weight of tetrahydrofuran as the obtained coagulated product and re-dissolving and coagulating with a large amount of methanol three times in total, the obtained coagulated product was vacuum-dried at 40 ° C. for 48 hours. Thus, a copolymer was obtained.
This copolymer had a Mw of 14,000. This copolymer is referred to as “copolymer (A-3)”.

Synthesis example 4
After substituting a flask equipped with a dry ice / methanol reflux with nitrogen, 4 g of 2,2′-azobis-2,4-dimethylvaleronitrile as a radical polymerization initiator and 150 g of ethyl 3-ethoxypropionate as an organic solvent were charged. Stir until the radical polymerization initiator is dissolved. Subsequently, 15 g of methacrylic acid, 15 g of mono (2-methacryloyloxyethyl) hexahydrophthalate, 45 g of tricyclodecanyl methacrylate, 15 g of styrene and 10 g of isoprene were added, and the temperature of the solution was raised to 80 ° C. while stirring. Polymerization was carried out at this temperature for 4 hours. Thereafter, the reaction product was dropped into a large amount of methanol to solidify the reaction product, and the coagulated product was washed with water. Then, after redissolving in the same weight of tetrahydrofuran as the obtained coagulated product and re-dissolving and coagulating with a large amount of methanol three times in total, the obtained coagulated product was vacuum-dried at 40 ° C. for 48 hours. Thus, a copolymer was obtained.
This copolymer had Mw of 16,000. This copolymer is referred to as “copolymer (A-4)”.

Synthesis example 5
After substituting a flask equipped with a dry ice / methanol reflux with nitrogen, 4 g of 2,2′-azobisisobutyronitrile as a radical polymerization initiator and 150 g of methyl 3-methoxypropionate as an organic solvent were added to start radical polymerization. Stir until the agent is dissolved. Subsequently, 20 g of methacrylic acid, 15 g of mono (2-methacryloyloxyethyl) hexahydrophthalate, 45 g of tricyclodecanyl methacrylate, 15.0 g of styrene and 5 g of 1,3-butadiene were added to the solution while stirring. The temperature was raised to 80 ° C., and polymerization was carried out at this temperature for 4 hours. Thereafter, the reaction product was dropped into a large amount of methanol to solidify the reaction product, and the coagulated product was washed with water. Then, after redissolving in the same weight of tetrahydrofuran as the obtained coagulated product and re-dissolving and coagulating with a large amount of methanol three times in total, the obtained coagulated product was vacuum-dried at 40 ° C. for 48 hours. Thus, a copolymer was obtained.
This copolymer had a Mw of 12,000. This copolymer is referred to as “copolymer (A-5)”.

Synthesis Example 6
After substituting a flask equipped with a dry ice / methanol reflux with nitrogen, 4 g of 2,2′-azobisisobutyronitrile as a radical polymerization initiator and 150 g of methyl 3-methoxypropionate as an organic solvent were added to start radical polymerization. Stir until the agent is dissolved. Subsequently, 15 g of methacrylic acid, 15 g of mono (2-methacryloyloxyethyl) hexahydrophthalate, 45 g of tricyclodecanyl methacrylate, 15 g of styrene and 10 g of 1,3-butadiene were charged, and the temperature of the solution was adjusted while stirring. The temperature was raised to 80 ° C., and polymerization was carried out at this temperature for 4 hours. Thereafter, the reaction product was dropped into a large amount of methanol to solidify the reaction product, and the coagulated product was washed with water. Then, after redissolving in the same weight of tetrahydrofuran as the obtained coagulated product and re-dissolving and coagulating with a large amount of methanol three times in total, the obtained coagulated product was vacuum-dried at 40 ° C. for 48 hours. Thus, a copolymer was obtained.
This copolymer had a Mw of 12,000. This copolymer is referred to as “copolymer (A-6)”.

Example 1
Preparation of liquid composition 10 g of copolymer (A-1) was dissolved in 10 g of 3-methoxypropionate, (B) 5 g of Aronics M-8060 as a polymerizable unsaturated compound, and (C) as a photopolymerization initiator. 2.0 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name Lucillin TPO) and 1.0 g of 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name Irgacure 651), (D ) Add 0.2g of 3-acryloyloxypropyltrimethoxysilane as a coupling agent, dissolve in methyl 3-methoxypropionate so that the total solid concentration is 45% by weight, and filter through a membrane filter with a pore size of 5μm Thus, a liquid composition (S-1) was prepared.

Formation of Interlayer Insulating Film The liquid composition (S-1) was applied on a glass substrate using a spinner and then pre-baked on a hot plate at 100 ° C. for 5 minutes to form a coating film.
Next, ultraviolet light having a wavelength of 365 nm and an intensity of 200 W / m ² was exposed to the coating film through a photomask having a pattern of a predetermined shape for 5 seconds. Then, using a 0.5 wt% tetramethylammonium hydroxide aqueous solution, shower development was performed at 25 ° C. for 2 minutes, and then washed with pure water for 1 minute to remove unnecessary portions and obtain a patterned thin film. .
Next, the obtained patterned thin film is post-exposed with ultraviolet rays having a wavelength of 365 nm and an intensity of 200 W / m ² for 10 seconds, and then baked in an oven at 220 ° C. for 60 minutes to be cured, thereby obtaining a predetermined pattern shape. An interlayer insulating film having a thickness of 10.5 μm was obtained.

Evaluation Subsequently, evaluation was performed in the following manner. The evaluation results are shown in Table 1 together with the thickness of the interlayer insulating film (the same applies hereinafter).
-Evaluation of resolution-
In the obtained interlayer insulating film, a case where a 15 μm square hole pattern can be resolved is ◯, a case where a 15 μm square hole pattern cannot be resolved, a case where a 20 μm square hole pattern can be resolved, and a 20 μm square hole pattern. The case where it was not resolvable was evaluated as x.
-Evaluation of transparency-
About the continuous film part of the obtained interlayer insulation film, the transmittance | permeability in wavelength 400nm was measured and evaluated using the spectrophotometer 150-20 type | mold double beam (brand name, Hitachi, Ltd. product). When this transmittance exceeds 90%, it can be said that the transparency is good.

-Evaluation of heat resistance-
The obtained interlayer insulating film was heated in an oven at 220 ° C. for 60 minutes, and the rate of change in film thickness before and after heating (%) [= (film thickness before heating−film thickness after heating) × 100 / heating The previous film thickness] was measured and evaluated. When this change rate is within 5%, it can be said that the heat resistance is good.
-Evaluation of heat discoloration-
The obtained interlayer insulating film was heated in an oven at 220 ° C. for 60 minutes, and the transmittance at a wavelength of 400 nm was measured for a continuous film portion of the interlayer insulating film using a spectrophotometer 150-20 type double beam (trade name, ) Manufactured by Hitachi, Ltd.)), and change rate of transmittance before and after heating (%) [= (transmittance before heating−transmittance after heating) × 100 / transmittance before heating] evaluated. When this rate of change is within 5%, it can be said that the heat discoloration is good.

-Evaluation of adhesion-
On the obtained interlayer insulation film, sputtering was performed at 100 ° C. using a sputtering apparatus SH-550-C12 (trade name, manufactured by ULVAC, Inc.) to form an ITO film having a thickness of 1,300 mm. Later, using an adhesive tape (cellophane adhesive tape N.29, manufactured by Nitto Denko Corporation) compliant with the JIS Z-1552 standard, the peeling test was performed three times at the same location, and the ITO film could be performed three times. The case where the film was not peeled off from the interlayer insulating film was evaluated as ◯, the case where it was peeled off twice or the third time was evaluated as Δ, and the case where it was peeled off once.
-Evaluation of solvent resistance-
The glass substrate on which the interlayer insulating film is formed is immersed in N-methylpyrrolidone at 50 ° C. for 15 minutes, and the change rate (%) of the film thickness of the interlayer insulating film before and after the immersion [= (film thickness after immersion−before immersion) Film thickness) × 100 / film thickness before immersion]. When this rate of change is within ± 5%, it can be said that the solvent resistance is good.

Example 2
In Example 1, a composition solution (S--) was used in the same manner as in Example 1 except that 0.3 g of 3-methacryloyloxypropyltrimethoxysilane was used instead of 0.2 g of 3-acryloyloxypropyltrimethoxysilane. 2) was prepared and evaluated. The evaluation results are shown in Table 1.

Example 3
In Example 1, 10 g of copolymer (A-2) was used instead of 10 g of copolymer (A-1), and 3-glycidoxypropyltrimethyl was replaced with 0.2 g of 3-acryloyloxypropyltrimethoxysilane. A composition solution (S-3) was prepared and evaluated in the same manner as in Example 1 except that 0.5 g of methoxysilane was used. The evaluation results are shown in Table 1.

Example 4
In Example 1, 10 g of copolymer (A-3) was used instead of 10 g of copolymer (A-1), and 2- (3,4-) was used instead of 0.2 g of 3-acryloyloxypropyltrimethoxysilane. A composition solution (S-4) was prepared and evaluated in the same manner as in Example 1 except that 0.5 g of (epoxycyclohexyl) ethyltrimethoxysilane was used. The evaluation results are shown in Table 1.

Example 5
In Example 1, 10 g of copolymer (A-4) was used instead of 10 g of copolymer (A-1), and 1,3-divinyltetramethyl was used instead of 0.2 g of 3-acryloyloxypropyltrimethoxysilane. A composition solution (S-5) was prepared and evaluated in the same manner as in Example 1 except that 0.5 g of disilazane was used. The evaluation results are shown in Table 1.

Example 6
In Example 1, 10 g of copolymer (A-5) was used instead of 10 g of copolymer (A-1), and 3-methacryloyloxypropyltri ( i-propoxy) A composition solution (S-6) was prepared and evaluated in the same manner as in Example 1 except that 0.5 g of titanium was used. The evaluation results are shown in Table 1.

Example 7
In Example 1, 10 g of copolymer (A-6) was used instead of 10 g of copolymer (A-1), and 9-octadecenylacetate was used instead of 0.2 g of 3-acryloyloxypropyltrimethoxysilane. A composition solution (S-7) was prepared and evaluated in the same manner as in Example 1 except that 0.5 g of aluminum acetate di-i-propoxide was used. The evaluation results are shown in Table 1.

Comparative Example 1
In Example 1, a composition solution (s-1) was prepared and evaluated in the same manner as in Example 1 except that 3-acryloyloxypropyltrimethoxysilane was not added. The evaluation results are shown in Table 1.

Comparative Example 2
In Example 3, a liquid composition (s-2) of the radiation sensitive resin composition was prepared in the same manner as in Example 3 except that 3-glycidoxypropyltrimethoxysilane was not added. Evaluation was performed in the same manner as in 1. The evaluation results are shown in Table 1.

Claims (4)

(A) (a) 10 to 50% by weight of a polymerizable unsaturated compound having an acidic functional group, which is a monoesterified product of (meth) acrylic acid and 2-hydroxyethyl (meth) acrylate and hexahydrophthalic acid , b) 20-60% by weight of a polymerizable unsaturated compound having tricyclodecanyl (meth) acrylate as an essential component and having an alicyclic hydrocarbon group and no acidic functional group, and (c) other polymerization An alkali-soluble copolymer obtained by polymerizing 5 to 40% by weight of the unsaturated compound (where (a) + (b) + (c) = 100% by weight), (B) a polymerizable unsaturated compound, C) A radiation-sensitive resin composition for forming an interlayer insulating film, comprising a photopolymerization initiator and (D) a coupling agent.   The interlayer insulation film formed from the radiation sensitive resin composition for interlayer insulation film formation of Claim 1. A method for forming an interlayer insulating film, comprising at least the following steps (a) to (d) in the order described below.
(A) forming a coating film of the radiation-sensitive resin composition for forming an interlayer insulating film according to claim 1 on a substrate;
(B) irradiating at least a part of the coating film with radiation;
(C) developing the coated film after irradiation;
(D) A step of baking the developed coating film.   A liquid crystal display device comprising the interlayer insulating film according to claim 2.