KR20120029319A - Radiation-sensitive resin composition, interlayer insulating film, method for forming the interlayer insulating film, and display device - Google Patents

Abstract

PURPOSE: A radiation-sensitive resin composition, an interlayer insulating film, a method for forming the interlayer insulating film, and a display device are provided to improve the transparency, the development adhesion, and the relative permittivity of the interlayer insulating film. CONSTITUTION: A radiation-sensitive resin composition includes copolymer, a polymeric unsaturated compound, a radiation-sensitive polymerization initiator, and an organic solvent. The copolymer includes the following: a structural unit is derived from at least one compound selected from a group including (meta)acrylic acid and unsaturated carbonic anhydride; a structural unit is derived from at least one compound selected from a group including (meta)acrylic acid glycidyl, (meta)acrylic acid 3,4-epoxycyclohexymethyl, 4-hydroxybutyl(meta)acrylateglycidylether, and 3-(meta)acryloyloxymetyl-3-ethyloxetane; a structural unit is derived from at least one compound selected from a group including styrene, alpha-methylstyrene, 4-methystyrene, and 4-hydroxystyrene; and a structural unit is derived from at least one compound selected from a group including acrylic acid methyl, (meta)acrylic acid ethyl, (meta)acrylic acid n-propyl, (meta)acrylic acid isopropyl, n-butyl, (meta)acrylic acid sec-butyl, (meta)acrylic acid isobutyl, and (meta)acrylic acid tert-butyl.

Description

Method of forming radiation-sensitive resin composition, interlayer insulating film, interlayer insulating film and display element

The present invention relates to a method for forming a radiation-sensitive resin composition, an interlayer insulating film, an interlayer insulating film, and a display element.

In an electronic component such as a thin film transistor (TFT) type liquid crystal display element, an interlayer insulating film is formed in order to insulate between wirings generally arranged in a layer shape. For example, a TFT type liquid crystal display element is manufactured through the process of forming a transparent electrode film on an interlayer insulation film, and forming a liquid crystal aligning film on it further. Since such an interlayer insulation film is exposed to the high temperature condition in the transparent electrode film formation process and the resist stripping solution of the resist in the pattern formation process of the electrode, sufficient resistance to these is required.

 Conventionally, a positive radiation sensitive resin composition using a radiation sensitive acid generator has been used as a material for forming an interlayer insulating film (see Japanese Patent Laid-Open No. 2001-354822). In recent years, application of a negative radiation sensitive resin composition is advanced from the viewpoint of high sensitivity, high transparency of the resulting interlayer insulating film, and the like (see Japanese Patent Laid-Open No. 2000-162769).

On the other hand, in view of cost reduction, process time, and the like accompanying the spread of liquid crystal panels, shortening (high sensitivity), high resolution, and the like of irradiation time in the photolithography step are desired. However, when high sensitivity, high resolution, and the like are pursued, there is a problem of deterioration in adhesion to the substrate, transparency, and the like.

From such a situation, development of the radiation sensitive resin composition which is excellent in a sensitivity and the resolution, and the interlayer insulation film which is excellent in transparency, image development adhesiveness, and relative dielectric constant with little nonuniformity is desired.

Japanese Laid-Open Patent Publication No. 2001-354822 Japanese Laid-Open Patent Publication No. 2000-162769

The present invention has been made on the basis of the above circumstances, and an object thereof is to provide a radiation-sensitive resin composition having excellent sensitivity and resolution, and an interlayer insulating film having little unevenness and excellent transparency, developing adhesiveness, and relative dielectric constant.

The invention made to solve the above problems,

[A] copolymer,

[B] a polymerizable unsaturated compound,

[C] a radiation sensitive polymerization initiator, and

[D] organic solvents

≪ / RTI >

[A] The copolymer is

(A1) Structural unit derived from at least 1 compound (Hereinafter, it may be called "(A1) compound") chosen from the group which consists of (meth) acrylic acid and unsaturated carboxylic anhydride,

(A2) (meth) acrylic acid glycidyl, (meth) acrylic acid 3,4-epoxycyclohexylmethyl, 4-hydroxybutyl (meth) acrylate glycidyl ether and 3- (meth) acryloyloxymethyl- A structural unit derived from at least one compound selected from the group consisting of 3-ethyloxetane (hereinafter, sometimes referred to as "(A12) compound"),

(A3) Structural unit derived from at least 1 compound (Hereinafter, it may be called "(A3) compound") chosen from the group which consists of styrene, (alpha) -methylstyrene, 4-methylstyrene, and 4-hydroxystyrene. And,

(A4) methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, and Structural unit derived from at least 1 compound (Hereinafter, it may be called "(A4) compound.") Chosen from the group which consists of (meth) acrylic-acid tert-butyl.

Including,

[A] With respect to the total amount of all structural units in the copolymer,

The content ratio of the structural unit derived from (A1) compound is 1 mol% or more and 40 mol% or less,

The content ratio of the structural unit derived from (A2) compound is 1 mol% or more and 15 mol% or less,

1 mol% or more and 70 mol% or less of the content rate of the structural unit derived from (A3) compound, and

(A4) The content rate of the structural unit derived from a compound is 1 mol% or more and 30 mol% or less

It is a phosphorus radiation sensitive resin composition.

The composition contains the [A] copolymer, the [B] polymerizable unsaturated compound, the [C] radiation sensitive polymerization initiator, and the [D] organic solvent as described above. When the [A] copolymer contains a specific amount of the structural units (A1) to (A4) derived from the specific compound, solubility in the aqueous alkali solution of the [A] copolymer can be optimized, and consequently, the resolution can be improved. have. In addition, development adhesiveness and resistance can be imparted to the interlayer insulating film formed from the composition. Moreover, since the said composition contains a [B] polymerizable unsaturated compound and a [C] radiation sensitive polymerization initiator, the interlayer insulation film excellent in sensitivity is obtained even in the case of low exposure amount.

The copolymer (A) is at least one compound selected from the group consisting of (A5) maleimide, N-phenylmaleimide and N-cyclohexyl maleimide (hereinafter, may be referred to as "(A5) compound"). It is preferable to further contain the structural unit derived from and to contain 1 mol% or more and 40 mol% or less of the content rate of the structural unit derived from the said (A5) compound.

It is preferable that the organic solvent (D) contains the organic solvent represented by following formula (1). [D] The organic solvent is a solvent used for preparation of the composition, and it is preferable to dissolve or disperse the [A] copolymer, the [B] polymerizable unsaturated compound and the [C] radiation sensitive polymerization initiator uniformly. Preferably, by including the organic solvent represented by following formula (1), a heterogeneity can be eliminated, for example:

(In formula (1), R <^1> and R <^2> is respectively independently a C1-C6 alkyl group; n is an integer of 1-6.).

The polymerizable unsaturated compound (B) contains a polymerizable unsaturated compound having a hydroxyl group or a carboxyl group, and the content of the polymerizable unsaturated compound (B) is preferably 10 mol% or more and 60 mol% or less. When the polymerizable unsaturated compound (B) has a specific amount of hydroxyl group or carboxyl group, a more resistant interlayer insulating film is obtained by curing reaction with an epoxy group derived from the compound (A2) of the [A] copolymer. .

The method of forming the interlayer insulating film of the present invention,

(1) forming a coating film of the composition on a substrate;

(2) irradiating at least a part of the coating film with radiation;

(3) developing the coating film irradiated with the radiation;

(4) The process of baking the developed coating film

Respectively.

According to the formation method of this invention, the interlayer insulation film which is few in unevenness and after image development, and excellent in transparency and a dielectric constant can be formed. Therefore, the said composition is suitable for forming the interlayer insulation film for display elements.

This invention also suitably includes the display element provided with the said interlayer insulation film.

In addition, "baking" as used in this specification means heating until the surface hardness requested | required of an interlayer insulation film is obtained. In addition, the "radiation radiation" of a "radiation-sensitive resin composition" is a concept containing visible light, an ultraviolet-ray, an ultraviolet-ray, an X-ray, a charged particle beam.

As described above, the present invention can provide a radiation-sensitive resin composition having excellent sensitivity and resolution, and an interlayer insulating film having little unevenness and excellent transparency, development adhesiveness, and relative dielectric constant. Therefore, such an interlayer insulating film is suitably used for a display element.

(Form to carry out invention)

<Radiation Resin Composition>

The radiation sensitive resin composition of this invention contains a [A] copolymer, a [B] polymerizable unsaturated compound, a [C] radiation sensitive polymerization initiator, and an [D] organic solvent, and may further contain arbitrary components. . Hereinafter, each component is explained in full detail.

<[A] copolymer>

[A] The copolymer is

(A1) Structural unit derived from at least 1 compound (Hereinafter, it may be called "(A1) compound") chosen from the group which consists of (meth) acrylic acid and unsaturated carboxylic anhydride,

(A2) (meth) acrylic acid glycidyl, (meth) acrylic acid 3,4-epoxycyclohexylmethyl, 4- (meth) acryloyloxybutylglycidyl ether and 3-ethyl-3-methyl (meth) acrylic The structural unit derived from at least 1 compound (Hereinafter, it may be called "(A2) compound") chosen from the group which consists of a latex oxetane,

(A3) Structural unit derived from at least 1 compound (Hereinafter, it may be called "(A3) compound") chosen from the group which consists of styrene, (alpha) -methylstyrene, 4-methylstyrene, and 4-hydroxystyrene. And,

(A4) methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, 1-methylethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-methacrylate (meth) acrylate A structural unit derived from at least one compound selected from the group consisting of butyl, isobutyl (meth) acrylate and tert-butyl (meth) acrylate (hereinafter sometimes referred to as "(A4) compound"), The content rate of the structural unit originating in the (A2) compound is 1 mol% or more and 40 mol% or less with respect to the total amount of all the structural units in the copolymer (A1). 1 mol% or more and 15 mol% or less, the content rate of the structural unit derived from (A3) compound is 1 mol% or more and 70 mol% or less, and the content rate of the structural unit derived from (A4) compound is 1 mol% or more It is 50 mol% or less.

[(A1) Compound]

The compound (A1) is at least one compound selected from the group consisting of (meth) acrylic acid and unsaturated carboxylic acid anhydride. As unsaturated carboxylic anhydride which is a (A1) compound, unsaturated dicarboxylic acid anhydride is mentioned typically. As unsaturated dicarboxylic anhydride, for example, maleic anhydride, fumaric anhydride, citraconic anhydride, mesaconic anhydride, itaconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, cyclohexene-1,2- Dicarboxylic acid anhydride, 3-butene-1,2-dicarboxylic acid anhydride, and the like.

As the compound (A1), acrylic acid, methacrylic acid and maleic anhydride are more preferable from the copolymerization reactivity, the solubility in the aqueous alkali solution of the [A] copolymer and the availability. These (A1) compounds may be used independently or may be used in mixture of 2 or more type.

The copolymer (A) contains 1 mol% or more and 40 mol% or less of the structural unit derived from the compound (A1). Preferably they are 10 mol% or more and 35 mol% or less. By setting the ratio of the structural unit derived from the compound (A1) to 1 mol% or more and 40 mol% or less, solubility in the aqueous alkali solution of the [A] copolymer can be optimized, and as a result, resolution can be improved.

[(A2) Compound]

(A2) A compound has (meth) acrylic-acid glycidyl, (meth) acrylic-acid 3,4- epoxycyclohexylmethyl, 4- (meth) acryloyloxy butyl glycidyl ether, and 3-ethyl which have radical polymerizability. It is at least 1 compound chosen from the group which consists of 3-methyl (meth) acrylate oxetane. Since the epoxy group derived from these (A2) compounds, and the carboxyl group or acid anhydride group derived from (A1) compound crosslinked, the curability of the said composition can be improved. These (A2) compounds may be used independently or may be used in mixture of 2 or more type.

The copolymer (A) contains 1 mol% or more and 15 mol% or less of the structural unit derived from the compound (A2). Preferably 3 mol% or more and 10 mol% or less are contained. By setting the ratio of the structural units derived from the compound (A2) to 1 mol% or more and 15 mol% or less, an interlayer insulating film capable of balancing developability, resolution and resistance to a high level can be formed.

[(A3) Compound]

The compound (A3) is at least one compound selected from the group consisting of styrene, α-methylstyrene, 4-methylstyrene, and 4-hydroxystyrene. The copolymer (A) contains 1 mol% or more and 70 mol% or less of the structural unit derived from the compound (A3). Preferably they are 40 mol% or more and 65 mol% or less. By setting the ratio of the structural unit derived from the (A3) compound to 1 mol% or more and 70 mol% or less, the radiation sensitive resin composition which can form the interlayer insulation film excellent in image development adhesiveness and tolerance can be obtained.

[(A4) Compound]

(A4) The compound is methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, (meth) acrylic acid At least one compound selected from the group consisting of isobutyl and tert-butyl (meth) acrylate. When methyl acrylate and alkyl having 2 to 4 carbon atoms (meth) acrylate are used as the compound (A4), the development adhesion at the time of interlayer insulation film formation is excellent. On the other hand, when methyl methacrylate is used instead of the (A4) compound, Tg is high and the development adhesiveness of the formed interlayer insulation film may be inferior. The copolymer (A) contains 1 mol% or more and 30 mol% or less of the structural unit derived from the compound (A4). Preferably 5 mol% or more and 25 mol% or less are contained. By setting the ratio of the structural unit derived from the (A4) compound to 1 mol% or more and 30 mol% or less, the radiation sensitive resin composition excellent in the image development adhesiveness and tolerance of the interlayer insulation film formed can be obtained.

[(A5) Compound]

[A] The copolymer is selected from the group consisting of (A5) maleimide, N-phenylmaleimide and N-cyclohexyl maleimide as necessary in addition to the structural unit derived from the above-mentioned (A1)-(A4) compounds. It is preferable to further contain the structural unit derived from the at least 1 compound used, and the content rate of the structural unit derived from the said (A5) compound is 1 mol% or more and 40 mol% or less. Heat resistance transparency can be improved further by containing 1 mol% or more and 40 mol% or less of the structural unit derived from (A5) compound further.

As a synthesis | combining method of the [A] copolymer, the method of radically copolymerizing the (A1)-(A4) compound and the (A5) compound as needed in the presence of a polymerization initiator in a solvent # is mentioned, for example.

As a weight average molecular weight (Mw) of the (A) copolymer, 2x10 <^3> -1 * 10 <^5> is preferable and 5x10 <^3> -5 * 10 <^4> is more preferable. By setting Mw of the copolymer (A) to 2 × 10 ^{3 to} 1 × 10 ⁵ , the radiation sensitivity and developability of the composition can be improved. In addition, Mw and the number average molecular weight (Mn) of the polymer in this specification were measured by the gel permeation chromatography (GPC) by the following conditions.

Device: GPC-101 (Showa Denko KK)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804

Mobile phase: tetrahydrofuran

Column temperature: 40 ℃

Flow rate: 1.0mL / min

Sample concentration: 1.0 mass%

Sample injection volume: 100 μL

Detector: parallax refractometer

Standard material: monodisperse polystyrene

Examples of the solvent used for the polymerization reaction for producing the copolymer (A) include alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, and dipropylene glycol dialkyl. Ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone, ester and the like.

As alcohol, For example, benzyl alcohol;

As glycol ether, For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc .;

As ethylene glycol alkyl ether acetate, For example, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc .;

As diethylene glycol monoalkyl ether, For example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc .;

As diethylene glycol dialkyl ether, For example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As dipropylene glycol dialkyl ether, For example, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, etc .;

As propylene glycol monoalkyl ether, For example, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, etc .;

As propylene glycol alkyl ether acetate, For example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, etc .;

As a propylene glycol monoalkyl ether propionate, For example, propylene glycol methyl ether propionate, a propylene glycol ethyl ether propionate, a propylene glycol propyl ether propionate, etc .;

As a ketone, For example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl- 2-pentanone, methyl isoamyl ketone, etc .;

Examples of the ester include ethyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, butyl hydroxyacetate, methyl lactate and lactic acid. Ethyl, propyl lactic acid, butyl lactate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, ethyl 2-butoxypropionate, Butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3 Propyl ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, and the like.

Among these solvents, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether and propylene glycol alkyl ether acetate are preferable, and diethylene glycol dimethyl ether and diethylene glycol ethylmethyl Ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are more preferable.

As a polymerization initiator used for the polymerization reaction for manufacturing [A] copolymer, what is generally known as a radical polymerization initiator can be used. As a radical polymerization initiator, 2,2'- azobisisobutyronitrile (AIBN), 2,2'- azobis- (2, 4- dimethylvaleronitrile), 2,2'- azobis-, for example Azo compounds such as (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides, such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, 1,1'-bis- (t-butyl peroxy) cyclohexane, and hydrogen peroxide are mentioned. When using a peroxide as a radical polymerization initiator, you may use a peroxide together with a reducing agent as a redox type initiator.

In the polymerization reaction for manufacturing the copolymer (A), in order to adjust the molecular weight, a molecular weight modifier can be used. As a molecular weight modifier, For example, Halogenated hydrocarbons, such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid; Xanthogens, such as dimethyl xanthogen sulfide and diisopropyl xanthogen disulfide; Terpinolene, (alpha) -methylstyrene dimer, etc. are mentioned.

<[B] polymerizable unsaturated compound>

Examples of the polymerizable unsaturated compound [B] contained in the composition include ω-carboxypolycaprolactone mono (meth) acrylate, ethylene glycol mono (meth) acrylate, ethylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) Acrylate, bisphenoxyethanol fluorenedi (meth) acrylate, dimethylol tricyclodecanedi (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate, 2- (2'-vinyloxyethoxy) ethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol pen (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloxyethyl) phosphate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, succinic acid modified pentaerythritol tree In addition to (meth) acrylate, succinic acid-modified dipentaerythritol pentaacrylate, and the like, a compound having a linear alkylene group and an alicyclic structure, and having at least two isocyanate groups, at least one hydroxyl group in the molecule, and three The urethane (meth) acrylate compound etc. which are obtained by making the compound which has five (meth) acryloyl groups react are mentioned.

As a commercial item of the said [B] polymerizable unsaturated compound, for example,

Aronix M-400, M-402, M-405, M-450, M-1310, M-1600, M-1960, M-7100, M- 8030, M-8060, M-8100, M-8530, M-8560, M-9050, Aronix TO-1450, and TO-1382 (above, Toagosei Co., Ltd.);

KAYARAD DPHA, copper DPCA-20, copper DPCA-30, copper DPCA-60, copper DPCA-120, copper MAX-3510 (above, Nippon Kayaku Co., Ltd.);

Biscot 295, East 300, East 360, East GPT, East 3PA, East 400 (above, Osaka Yuki Kagaku Kogyo Co., Ltd.);

As a urethane acrylate compound, New Frontier R-1150 (Daiichi Kogyo Seyaku Co., Ltd.);

KAYARAD DPHA-40H, UX-5000 (above, Nippon Kayaku Co., Ltd.);

UN-9000H (Negami Kogyo Co., Ltd.);

Aronix M-5300, M-5600, M-5700, M-210, M-220, M-240, M-270, M-6200, M-305, M-309 , M-310, M-315 (above, Toagose Co., Ltd.);

KAYARAD HDDA, KAYARAD HX-220, East HX-620, East R-526, East R-167, East R-604, East R-684, East R-551, East R-712, East UX-2201, East UX -2301, East UX-3204, East UX-3301, East UX-4101, East UX-6101, East UX-7101, East UX-8101, East UX-0937, East MU-2100, East MU-4001 Nippon Kayaku Co., Ltd .;

Atresin UN-9000PEP, East UN-9200A, East UN-7600, East UN-333, East UN-1003, East UN-1255, East UN-6060PTM, East UN-6060P, East SH-500B Bridges);

Biscot 260, 312, 335HP (above, Osaka Yuki Kagaku Kogyo Co., Ltd.) etc. are mentioned. These can be used individually or in mixture of 2 or more types.

[B] As a polymerizable unsaturated compound, it is preferable that the polymerizable unsaturated compound which has a hydroxyl group or a carboxyl group is included, and content of the said [B] polymerizable unsaturated compound is 10 mol% or more and 60 mol% or less. When the polymerizable unsaturated compound (B) has a specific amount of hydroxyl group or carboxyl group, a more resistant interlayer insulating film can be obtained by curing reaction with an epoxy group derived from the compound (A2) of the [A] copolymer. have. As a content rate of the [B] polymerizable unsaturated compound in the said composition, 20 mass parts-150 mass parts are preferable with respect to 100 mass parts of [A] copolymers, and 40 mass parts-100 mass parts are more preferable. By making the content rate of the polymerizable unsaturated compound (B) into the said range, the said composition is excellent in image development adhesiveness and can obtain the interlayer insulation film which has sufficient hardness even in low exposure amount.

<[C] radiation sensitive polymerization initiator>

[C] radiation sensitive polymerization initiator contained in the said composition is a component which produces the active species which can start superposition | polymerization of a [B] polymerizable unsaturated compound in response to radiation. As such a [C] radiation sensitive polymerization initiator, an O-acyl oxime compound, an acetophenone compound, a biimidazole compound, etc. are mentioned.

As the O-acyl oxime compound, for example, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1-onoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1- Onoxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyl Oxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone -1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9 -Ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) Etc. can be mentioned. Among them, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl -6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- { Preference is given to 2-methyl-4- (2,2-dimethyl-1,3-dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime). These O-acyl oxime compounds may be used independently or may be used in mixture of 2 or more type.

As an acetophenone compound, the (alpha)-amino ketone compound and the (alpha)-hydroxy ketone compound are mentioned, for example.

As an α-amino ketone compound, for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4-methylbenzyl)- 1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, etc. are mentioned. .

As an alpha-hydroxy ketone compound, it is 1-phenyl- 2-hydroxy-2- methyl propane- 1-one, and 1- (4-i-propylphenyl) -2-hydroxy- 2-methyl propane-, for example. 1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, etc. are mentioned.

Of these acetophenone compounds, α-aminoketone compounds are preferable, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-dimethylamino-2- (4- Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one is more preferred.

As a biimidazole compound, it is a 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetrakis (4-ethoxycarbonylphenyl) -1,2' ratio, for example. Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichloro Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole etc. are mentioned. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichloro Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole is preferred, and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2' -Biimidazole is more preferred.

[C] As a radiation sensitive polymerization initiator, a commercial item may be used, for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure) 907), 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (irgacure 379), ethanone-1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (irgacure OXE02), 1,2-octanedione-1- [4- (phenyl Thio) -2- (O-benzoyl oxime)] (irgacure OXE01), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (irgacure 819) (above, Chiba? Specialty? Chemicals) Etc.) are mentioned.

(C) A radiation sensitive polymerization initiator can be used individually or in mixture of 2 or more types. As a content rate of the [C] radiation sensitive polymerization initiator in the said composition, 1 mass part-25 mass parts are preferable with respect to 100 mass parts of [A] copolymers, and 1 mass part-20 mass parts are more preferable. By making the content rate of the (C) radiation sensitive polymerization initiator into 1 mass part-25 mass parts, even if it is a low exposure amount, the said composition can form the interlayer insulation film which has high adhesiveness.

<[D] organic solvent>

As a solvent used for preparation of the said composition, a [A] copolymer, a [B] polymerizable unsaturated compound, a [C] radiation sensitive polymerization initiator, a [D] organic solvent, and arbitrary components are melt | dissolved or disperse | distributed uniformly, and each Those that do not react with the ingredients are used. As such a solvent, the same thing as what was illustrated as a solvent which can be used for synthesize | combining the above-mentioned [A] copolymer is mentioned. A solvent can be used individually or in mixture of 2 or more types.

It is preferable that the organic solvent [D] contains the organic solvent represented by said formula (1) from a viewpoint of solubility of each component, reactivity with each component, the ease of coating film formation, etc. [D] The organic solvent is a solvent used for preparation of the composition, preferably dissolving or dispersing the [A] copolymer, the [B] polymerizable unsaturated compound and the [C] radiation sensitive polymerization initiator uniformly, By including the organic solvent represented by said formula (1), a heterogeneity can be eliminated, for example.

In said formula (1), R <^1> and R <^2> is a C1-C6 alkyl group each independently. n is an integer of 1-6. As a C1-C6 alkyl group, either linear or branched form may be sufficient, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc. are mentioned. As these [D] organic solvent represented by Formula (1), 3-methoxy propionate methyl and 3-methoxy ethylpropionate are more preferable.

<Optional component>

In addition to the above-mentioned [A] copolymer, the [B] polymerizable unsaturated compound, the [C] radiation sensitive polymerization initiator, and the [D] organic solvent, the said composition is [E] in the range which does not impair the effect of this invention. ] Optional components, such as an adhesion | attachment adjuvant, a [F] surfactant, and a [G] polymerization inhibitor, can be contained. These arbitrary components may be used independently, or may mix and use 2 or more types. Hereinafter, arbitrary components are explained in full detail.

[[E] Close Preparation

[E] Adhesion aids can be used to further improve the adhesion between the resulting interlayer insulating film and the substrate. As such [E] adhesion | attachment adjuvant, the functional silane coupling agent which has reactive functional groups, such as a carboxyl group, a methacryloyloxy group, a vinyl group, an isocyanate group, an oxiranyl group, is preferable, For example, a trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4- Epoxy cyclohexyl) ethyl trimethoxysilane, 2- (2-vinyloxyethoxy) ethyl acrylate, etc. are mentioned.

As the usage-amount of [E] adhesion | attachment adjuvant, 15 mass parts or less are preferable with respect to 100 mass parts of [A] copolymers, and 10 mass parts or less are more preferable. When the usage-amount of an adhesion | attachment adjuvant exceeds 15 mass parts, there exists a tendency which develops a developing residue easily.

[[G] surfactants]

[G] Surfactant can be used in order to improve the film formability of the said composition further. As surfactant, a fluorochemical surfactant, silicone type surfactant, and other surfactant are mentioned, for example. As said fluorine-type surfactant, the compound which has a fluoroalkyl group and / or a fluoroalkylene group in at least any part of a terminal, a main chain, and a side chain is preferable, For example, 1,1,2,2- tetrafluoro-n- Octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycoldi (1,1 , 2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1 , 2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycoldi (1,1,2,2-tetrafluoro-n-butyl) ether, perfluoro-n-dodecane Sodium sulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dode Canna, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkyl phosphate, sodium fluoroalkyl carbonate, diglycerin tetrakis (fluoroalkyl Polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, other fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, carboxylic acid fluoroalkyl ester Etc. can be mentioned.

As a commercial item of a fluorine-type surfactant, BM-1000, BM-1100 (above, BM CHEMIE Corporation), Megaface F142D, copper F172, copper F173, copper F183, copper F178, copper F191, copper F471, F476 (above, Dai Nippon Inkika Chemicals Co., Ltd.), Fluorad FC-170C, C-171, C-430, C-431 (above, Sumitomo 3M Co., Ltd.), Suplon (Surflon) S-112, East-113, East-131, East-141, East-145, East-382, Suflon SC-101, East-102, East-103, East-104, East-105, East -106 (above, Asahi Glass Co., Ltd.), Ftop EF301, East 303, East 352 (above, Shin Akita Kasei Co., Ltd.), Fgentgent FT-100, East-110, East -140A, copper-150, copper-250, copper-251, copper-300, copper-310, copper-400S, aftergent FTX-218, east-251, aftergent 710F (or above) Can be mentioned.

As a commercial item of a silicone type surfactant, Toray Silicone DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ-6032 , SF-8428, DC-57, DC-190 (above, Dow Corning Silicon Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF And -4452 (above, GE Toshiba Silicone Co., Ltd.) and organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.).

As other surfactant, For example, polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene-n-octylphenyl ether and polyoxyethylene-n-nonylphenyl ether; Nonionic surfactants, such as polyoxyethylene dialkyl ester, such as polyoxyethylene dilaurate and polyoxyethylene distearate, (meth) acrylic-acid copolymer polyflow No.57, copper No.95 ( The Kyoeisha Chemicals Co., Ltd. is mentioned above.

As the usage-amount of surfactant, 1.0 mass part or less is preferable with respect to 100 mass parts of [A] copolymers, and 0.8 mass part or less is more preferable. When the usage-amount of surfactant exceeds 1.0 mass part, it will become easy to produce a film nonuniformity.

[[G] polymerization inhibitor]

Examples of the polymerization inhibitor [G] include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitroso compounds, and the like, and more specifically, p-methoxyphenol and N-nitroso. -N-phenylhydroxylamine aluminum etc. are mentioned.

As the usage-amount of the [G] polymerization inhibitor, 3.0 mass parts or less are preferable with respect to 100 mass parts of [A] copolymers, and 1.0 mass part or less is more preferable. When the usage-amount of the [G] polymerization inhibitor exceeds 3.0 mass parts, the sensitivity of the said composition may fall and a pattern shape may deteriorate.

<Preparation method of this composition>

In addition to the [A] copolymer, the [B] polymerizable unsaturated compound, the [C] radiation sensitive polymerization initiator, and the [D] organic solvent, the said composition is prepared by mixing arbitrary components in a predetermined ratio as needed. This radiation sensitive resin composition is preferably dissolved in a suitable solvent and used in a solution state.

When preparing the composition in a solution state, the solid content concentration (components other than the solvent occupied in the composition solution) may be any concentration (for example, 5% by mass to 50% by mass) depending on the purpose of use or the value of the desired film thickness. ) Can be set. As a more preferable solid content concentration, although it changes with the formation method of the film on a board | substrate, it mentions later. About the composition solution prepared in this way, it can provide for use, after filtering using a Millipore filter etc. about 0.5 micrometer of pore diameters.

<Interlayer Insulating Film and Formation Method>

The said composition is suitable for forming the interlayer insulation film for display elements.

The method for forming the interlayer insulating film is

(1) forming a coating film of the composition on a substrate;

(2) irradiating at least a part of the coating film with radiation;

(3) developing the coating film irradiated with the radiation;

(4) The process of baking the developed coating film

Respectively.

According to the formation method of this invention, an interlayer insulation film with little nonuniformity and residue, and excellent in transparency and relative dielectric constant can be formed. Hereinafter, each process is explained in full detail.

[Step (1)]

In this step, a transparent conductive film is formed on one surface of the transparent substrate, and a film of the composition is formed on the transparent conductive film. As a transparent substrate, the resin substrate which consists of plastics, such as glass substrates, such as a soda lime glass and an alkali free glass, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and polyimide, etc. are mentioned, for example. .

Examples of the transparent conductive film formed on one surface of the transparent substrate include an NESA film made of tin oxide (SnO ₂ ) (registered trademark of US PPG), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), and the like. Can be mentioned.

When forming a film by the apply | coating method, after apply | coating the solution of the said composition on the said transparent conductive film, Preferably, a film can be formed by heating (prebaking) an application surface. As solid content concentration of the composition solution used for a coating method, 5 mass%-50 mass% are preferable, 10 mass%-40 mass% are more preferable, 15 mass%-35 mass% are especially preferable. As a coating method of the composition, for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slit coating method (slit die coating method), a bar coating method, or an inkjet coating method may be adopted. Can be. Among these, a spin coating method or a slit coating method is preferable.

As conditions of the said prebaking, although it changes with kinds, compounding ratio, etc. of each component, 70 degreeC-120 degreeC is preferable and it is about 1 minute-about 15 minutes. 0.5 micrometer-10 micrometers are preferable, and, as for the film thickness after the prebaking of a film, about 1.0 micrometer-7.0 micrometers are more preferable.

[Step (2)]

In this step, at least part of the formed film is irradiated with radiation. At this time, when irradiating only a part of film, it can be based on the method of irradiating through the photomask which has a predetermined pattern, for example.

As radiation used for irradiation, visible light, an ultraviolet-ray, an ultraviolet ray, etc. are mentioned. Among these, the radiation whose wavelength is 250 nm-550 nm is preferable, and the radiation containing 365 nm ultraviolet-ray is more preferable.

The radiation dose (exposure dose) is a value measured by an illuminometer (OAI model 356, manufactured by Optical Associates Inc.) at a wavelength of 365 nm of radiation to be irradiated, and preferably 100 J / m 2 to 5,000 J / m 2, 200 J / m <2> -3,000 J / m <2> is more preferable.

The composition has a higher radiation sensitivity than a conventionally known composition, and even if the radiation dose is 850 J / m 2 or less, it is possible to obtain an interlayer insulating film having a desired film thickness, good shape, excellent adhesion and high hardness.

[Step (3)]

In this step, by developing the film after irradiation, unnecessary portions are removed to form a predetermined pattern. As a developing solution used for image development, aqueous solution of alkaline compounds, such as inorganic alkali, such as sodium hydroxide, potassium hydroxide, sodium carbonate, quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, is mentioned, for example. have. You may add a suitable amount of water-soluble organic solvents, such as methanol and ethanol, and / or surfactant to the aqueous solution of the said alkaline compound.

The developing method may be any of a puddle method, a dipping method, a shower method, and the like, and the developing time is preferably about 10 seconds to 180 seconds at normal temperature. After the development treatment, for example, flowing water is washed for 30 seconds to 90 seconds, and then the desired pattern can be obtained by air drying with compressed air or compressed nitrogen.

[Step (4)]

In this step, an interlayer insulating film is obtained by baking (postbaking) the obtained patterned film by a suitable heating apparatus such as a hot plate or an oven. As baking temperature, 100 degreeC-250 degreeC is preferable, and 150 degreeC-230 degreeC is more preferable. As baking time, for example, 5 minutes-30 minutes on a hot plate, 30 minutes-180 minutes in an oven are preferable. Since the said composition contains the organic solvent [D] as mentioned above, such low low temperature baking can be implement | achieved and it is suitable as a formation material of the interlayer insulation film used for the flexible display etc. for which low temperature baking is desired.

<Display element and its manufacturing method>

This invention also suitably includes the display element provided with the said interlayer insulation film. The display element of this invention can be manufactured by the following method, for example.

First, a pair (two sheets) of transparent substrates having a transparent conductive film (electrode) on one side were prepared, and an interlayer insulating film was prepared on the transparent conductive film of one of the substrates according to the above-described method using the composition. In addition, a spacer, a protective film, etc. are formed as needed. Subsequently, an alignment film having liquid crystal alignment capability is formed and overlapped. These substrates are disposed to face each other with the surface on the side on which the alignment film is formed to face each other via a constant gap (cell gap) so that the liquid crystal alignment direction of each alignment film is perpendicular or antiparallel, and the surface (alignment film) of the substrate and The liquid crystal is filled in the cell gap partitioned by the spacer, and the filling hole is sealed to form a liquid crystal cell. And the display element of this invention can be obtained by bonding a polarizing plate to both outer surfaces of a liquid crystal cell so that the polarization direction may coincide with or perpendicular to the liquid crystal aligning direction of the alignment film formed in one surface of the said board | substrate.

As another method, a pair of transparent substrates having a transparent conductive film, an interlayer insulating film, and an alignment film formed in the same manner as the above method are prepared. Then, the ultraviolet curable sealing compound is apply | coated using a dispenser along the edge part of one board | substrate, liquid crystal is dripped in the shape of a microdroplet using a liquid crystal dispenser, and both board | substrates are bonded under vacuum. And the said sealing agent is irradiated with an ultraviolet-ray using a high pressure mercury lamp, and both board | substrates are sealed. Finally, the display element of this invention can be obtained by bonding a polarizing plate to both outer surfaces of a liquid crystal cell.

As a liquid crystal used in each said method, a nematic liquid crystal, a smectic liquid crystal, etc. are mentioned, for example. Moreover, as a polarizing plate used on the outer side of a liquid crystal cell, the polarizing plate which sandwiched the polyvinyl alcohol, the polarizing film called "H film | membrane" which absorbed iodine between the cellulose acetate protective film, or the polarizing plate which consists of H film itself, etc. Can be mentioned.

(Example)

Hereinafter, although this invention is explained based on an Example, this invention is not limitedly interpreted by this Example.

<Synthesis of Copolymer of [A]>

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate were placed. Next, 20 parts by mass of (A1) methacrylic acid, (10 parts by mass of glycidyl methacrylate), 60 parts by mass of (A3) styrene, 10 parts by mass of (A4) ethyl methacrylate and α-methylstyrene dimer 1 After mass parts were added and nitrogen was substituted, stirring was started gently. The temperature of the solution was raised to 70 ° C., and the polymer solution containing the copolymer (A-1) was obtained by maintaining the temperature for 4 hours (solid content concentration = 34.4 mass%, Mw = 10,000, Mw / Mn = 2.4). . ^As a result of ¹³ C-NMR analysis, the content of the structural unit derived from the (A1) compound, the structural unit derived from the (A2) compound, the structural unit derived from the (A3) compound, and the structural unit derived from the (A4) compound 23 mol%, 7 mol%, 60 mol%, and 10 mol%, respectively. Further, by ^{1 H-NMR, 13 C-} NMR, FT-IR, pyrolysis gas chromatography-mass spectrometry, the content was determined.

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate were placed. Next, 20 parts by mass of (A1) methacrylic acid, (10 parts by mass of glycidyl methacrylate), 50 parts by mass of (A3) styrene, 20 parts by mass of (A4) ethyl methacrylate and α-methylstyrene dimer 1 After mass parts were added and nitrogen was substituted, stirring was started gently. The temperature of the solution was raised to 70 ° C., and the polymer solution containing the copolymer (A-2) was obtained by maintaining the temperature for 4 hours (solid content concentration = 34.3 mass%, Mw = 10,000, Mw / Mn = 2.3). . As a result of the analysis in the same manner as in Synthesis example 1, the structural unit derived from the compound (A1), the structural unit derived from the compound (A2), the structural unit derived from the compound (A3), and the structural unit derived from the compound (A4) Content was 24 mol%, 7 mol%, 50 mol%, and 19 mol%, respectively.

Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate were placed. Subsequently, (A1) 30 mass parts of methacrylic acid, (A2) glycidyl methacrylate 10 mass parts, (A3) 50 mass parts of styrene, (A4) 10 mass parts of ethyl methacrylate, and (alpha) -methylstyrene dimer 1 After mass parts were added and nitrogen was substituted, stirring was started gently. The temperature of the solution was raised to 70 ° C., and the polymer solution containing the copolymer (A-3) was obtained by maintaining the temperature for 4 hours (solid content concentration = 33.3 mass%, Mw = 11,000, Mw / Mn = 2.4). . As a result of the analysis in the same manner as in Synthesis example 1, the structural unit derived from the compound (A1), the structural unit derived from the compound (A2), the structural unit derived from the compound (A3), and the structural unit derived from the compound (A4) Content was 35 mol%, 7 mol%, 50 mol%, and 8 mol%, respectively.

Synthesis Example 4

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate were placed. Next, 25 parts by mass of (A1) methacrylic acid, (5 parts by mass of glycidyl methacrylate), 50 parts by mass of (A3) styrene, 20 parts by mass of (A4) ethyl acrylate and 1 part by mass of α-methylstyrene dimer After adding and replacing with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and the polymer solution containing the copolymer (A-4) was obtained by storing the temperature for 4 hours (solid content concentration = 34.0 mass%, Mw = 9,000, Mw / Mn = 2.3). . As a result of the analysis in the same manner as in Synthesis example 1, the structural unit derived from the compound (A1), the structural unit derived from the compound (A2), the structural unit derived from the compound (A3), and the structural unit derived from the compound (A4) Content was 28 mol%, 4 mol%, 48 mol%, and 20 mol%, respectively.

Synthesis Example 5

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate were placed. Subsequently, (A1) 25 parts by mass of methacrylic acid, (5 parts by mass of glycidyl methacrylate), 50 parts by mass of (A3) styrene, 20 parts by mass of (A4) isopropyl methacrylic acid and α-methylstyrene dimer 1 mass part was substituted and nitrogen-substituted, and stirring was started gently. The temperature of the solution was raised to 70 ° C., and the polymer solution containing the copolymer (A-5) was obtained by maintaining the temperature for 4 hours (solid content concentration = 34.0 mass%, Mw = 9,000, Mw / Mn = 2.3). . As a result of the analysis in the same manner as in Synthesis example 1, the structural unit derived from the compound (A1), the structural unit derived from the compound (A2), the structural unit derived from the compound (A3), and the structural unit derived from the compound (A4) Content was 30 mol%, 4 mol%, 51 mol%, 16 mol%, respectively.

[Synthesis Example 6]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate were placed. Subsequently, (A1) 20 parts by mass of methacrylic acid, (A2) 10 parts by mass of 3-ethyl-3-methylmethacrylate oxetane, (A3) 50 parts by mass of styrene, (A4) 20 parts by mass of ethyl methacrylate, and After 1 mass part of (alpha) -methylstyrene dimers were substituted for nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and the polymer solution containing the copolymer (A-6) was obtained by preserving this temperature for 4 hours (solid content concentration = 32.3% by mass, Mw = 9,000, Mw / Mn = 2.3). . As a result of the analysis in the same manner as in Synthesis example 1, the structural unit derived from the compound (A1), the structural unit derived from the compound (A2), the structural unit derived from the compound (A3), and the structural unit derived from the compound (A4) Content was 25 mol%, 6 mol%, 50 mol%, and 19 mol%, respectively.

[Synthesis Example 7]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate were placed. Next, 18 parts by mass of (A1) acrylic acid, (A2) 12 parts by mass of 3,4-epoxycyclohexylmethyl methacrylic acid, (A3) 50 parts by mass of styrene, (A4) 20 parts by mass of ethyl methacrylate and α-methyl After 1 mass part of styrene dimers were substituted for nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and the polymer solution containing the copolymer (A-7) was obtained by preserving this temperature for 4 hours (solid content concentration = 32.3% by mass, Mw = 8,000, Mw / Mn = 2.3). . As a result of the analysis in the same manner as in Synthesis example 1, the structural unit derived from the compound (A1), the structural unit derived from the compound (A2), the structural unit derived from the compound (A3), and the structural unit derived from the compound (A4) Content was 29 mol%, 9 mol%, 38 mol%, and 24 mol%, respectively.

[Synthesis Example 8]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate were placed. Subsequently, (A1) 20 mass parts of methacrylic acid, (A2) glycidyl methacrylate 10 mass parts, (A3) styrene 30 mass parts, (A4) 20 mass parts of ethyl methacrylate, (A5) N-phenyl 20 mass parts of maleimide and 1 mass part of (alpha) -methylstyrene dimers were put, and it substituted for nitrogen, and stirring was started gently. The temperature of the solution was raised to 70 ° C., and the polymer solution containing the copolymer (A-8) was obtained by maintaining the temperature for 4 hours (solid content concentration = 34.0 mass%, Mw = 9,000, Mw / Mn = 2.1). . As a result of the same analysis as in Synthesis Example 1, the structural unit derived from the compound (A1), the structural unit derived from the compound (A2), the structural unit derived from the compound (A3), the structural unit derived from the compound (A4), Content of the structural unit derived from (A5) compound was 26 mol%, 8 mol%, 33 mol%, 20 mol%, and 13 mol%, respectively.

Synthesis Example 9

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate were placed. Subsequently, (A1) methacrylic acid 30 mass parts, (A2) methacrylic acid glycidyl 10 mass parts, (A3) styrene 40 mass parts, (A4) ethyl methacrylate 10 mass parts, methacrylic as other components 10 mass parts of acid methyl, and 1 mass part of (alpha) -methylstyrene dimers were put, and nitrogen substitution was carried out, and stirring was started gently. The temperature of the solution was raised to 70 ° C, and the polymer solution containing the copolymer (A-9) was obtained by preserving this temperature for 4 hours (solid content concentration = 33.3 mass%, Mw = 12,000, Mw / Mn = 2.5). . As a result of analysis in the same manner as in Synthesis example 1, the structural unit derived from the compound (A1), the structural unit derived from the compound (A2), the structural unit derived from the compound (A3), and the structural unit derived from the compound (A4) Content of the structural unit derived from methyl methacrylate was 35 mol%, 7 mol%, 40 mol%, 9 mol%, 10 mol%, respectively.

Comparative Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were placed. Subsequently, 30 mass parts of (A1) methacrylic acid, 60 mass parts of (A3) styrene, 10 mass parts of (A4) ethyl methacrylate, and 1 mass part of (alpha) -methylstyrene dimer are substituted, and it is nitrogen-substituted, and it starts stirring gently. did. The temperature of the solution was raised to 70 ° C., and the polymer solution containing the copolymer (CA-1) was obtained by maintaining the temperature for 4 hours (solid content concentration = 34.5 mass%, Mw = 9,000, Mw / Mn = 2.3). . As a result of the analysis in the same manner as in Synthesis example 1, the content of the structural unit derived from the compound (A1), the structural unit derived from the compound (A3), and the structural unit derived from the compound (A4) were 34 mol% and 57 mol%, respectively. , 9 mol%.

Comparative Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate were placed. Then, 25 parts by mass of (A1) methacrylic acid, 5 parts by mass of glycidyl (A2), 50 parts by mass of (A3) styrene, 20 parts by mass of methyl methacrylate, and 1 part by mass of α-methylstyrene dimer were added thereto. After nitrogen substitution, stirring was started gently. The temperature of the solution was raised to 70 ° C., and the polymer solution containing the copolymer (CA-2) was obtained by maintaining the temperature for 4 hours (solid content concentration = 35.4 mass%, Mw = 15,000, Mw / Mn = 2.4). . As a result of analysis in the same manner as in Synthesis example 1, the structural unit derived from the compound (A1), the structural unit derived from the compound (A2), the structural unit derived from the compound (A3), and the structural unit derived from methyl methacrylate. The content of was 30 mol%, 4 mol%, 49 mol%, 17 mol%, respectively.

Comparative Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were placed. Subsequently, (A1) 45 mass parts of methacrylic acid, (A2) 5 mass parts of glycidyl methacrylate, (A3) 40 mass parts of styrene, (A4) 10 mass parts of ethyl methacrylate, and (alpha) -methylstyrene dimer 1 After mass parts were added and nitrogen was substituted, stirring was started gently. The temperature of the solution was raised to 70 ° C., and the polymer solution containing the copolymer (CA-3) was obtained by maintaining the temperature for 4 hours (solid content concentration = 34.4 mass%, Mw = 20,000, Mw / Mn = 2.6). . As a result of analysis in the same manner as in Synthesis example 1, the structural unit derived from the compound (A1), the structural unit derived from the compound (A2), the structural unit derived from the compound (A3), and the structural unit derived from the compound (A4) The content of was 51 mol%, 3 mol%, 37 mol%, 9 mol%, respectively.

Comparative Synthesis Example 4

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methylethyl ether were placed. Subsequently, (A1) 12 parts by mass of methacrylic acid, (A2) 5 parts by mass of glycidyl methacrylate, (A3) 78 parts by mass of styrene, (A4) 5 parts by mass of ethyl methacrylate and α-methylstyrene dimer 1 After mass parts were added and nitrogen was substituted, stirring was started gently. The temperature of the solution was raised to 70 ° C., and the polymer solution containing the copolymer (CA-4) was obtained by maintaining the temperature for 4 hours (solid content concentration = 35.0 mass%, Mw = 9,000, Mw / Mn = 2.1). . As a result of analysis in the same manner as in Synthesis example 1, the structural unit derived from the compound (A1), the structural unit derived from the compound (A2), the structural unit derived from the compound (A3), and the structural unit derived from the compound (A4) The content of was 14 mol%, 4 mol%, 77 mol%, and 5 mol%, respectively.

Comparative Synthesis Example 5

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate were placed. Next, 20 parts by mass of (A1) methacrylic acid, (5 parts by mass of glycidyl methacrylate), 30 parts by mass of (A3) styrene, 45 parts by mass of (A4) ethyl methacrylate and α-methylstyrene dimer 1 After mass parts were added and nitrogen was substituted, stirring was started gently. The temperature of the solution was raised to 70 ° C., and the polymer solution containing the copolymer (CA-5) was obtained by preserving this temperature for 4 hours (solid content concentration = 35.1 mass%, Mw = 17,000, Mw / Mn = 2.2). . As a result of analysis in the same manner as in Synthesis example 1, the structural unit derived from the compound (A1), the structural unit derived from the compound (A2), the structural unit derived from the compound (A3), and the structural unit derived from the compound (A4) The content of was 24 mol%, 4 mol%, 30 mol%, and 42 mol%, respectively.

<Preparation of a radiation sensitive resin composition>

Example 1

[A] 25 mass of (B-1) as a polymerizable unsaturated compound with respect to the quantity containing (A-1) 100 mass parts (solid content) in the solution containing (A-1) as a copolymer. 25 parts by mass of (B-8), 5 parts by mass of (C-1) as the radiation-sensitive polymerization initiator, 1 part by mass of the [E] adhesion aid (E-1) as an optional component, and (E-2 ) 1 mass part, 0.10 mass part of [F] surfactants (F-1), and 0.1 mass part of [G] polymerization inhibitors (G-1) p-methoxyphenol, are mixed so that solid content concentration may be 30 mass% [ D] After dissolving in methyl-3-methoxypropionate as an organic solvent, it filtered with the membrane filter of 0.2 micrometer of pore diameters, and prepared the radiation sensitive resin composition (S-1).

[Examples 2 to 23 and Comparative Examples 1 to 6]

It is the same as that of Example 1 except having used the kind, quantity [A] copolymer, [B] polymerizable unsaturated compound, [C] radiation sensitive polymerization initiator, [D] organic solvent, and arbitrary components which are shown in Table 1. It operated and prepared the radiation sensitive resin composition (S-2)-(S-23) and (CS-1)-(CS-6).

The detail of each component used by the Example and the comparative example is shown.

<[B] polymerizable unsaturated compound>

(B-1)? (B-5) A polymerizable unsaturated compound having a hydroxyl group or a carboxyl group

B-1: succinic acid modified pentaerythritol triacrylate (Toagose Co., Ltd., Aaronics TO-756)

B-2: succinic acid modified dipentaerythritol pentaacrylate (Toagose Corporation, Aaronics M-520)

B-3: ω-carboxy-polycaprolactone monoacrylate

B-4: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (approximately 60% of pentaerythritol triacrylate content) (Shin Nakamura Kagaku Kogyo Co., Ltd., NK ester A-TMM-3LM- N)

B-5: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (50% dipentaerythritol pentaacrylate content) (Shin-Nakamura Kagaku Kogyo Co., Ltd. NK ester A-9550)

(B-6)? (B-9) A polymerizable unsaturated compound having neither a hydroxyl group nor a carboxyl group

B-6: trimethylol propane triacrylate (Shin-Nakamura Chemical Co., Ltd., NK ester A-TMPT)

B-7: pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., Ltd., NK ester A-TMMT)

B-8: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (content of dipentaerythritol hexaacrylate content of 90%) (Shin-Nakamura Kagaku Kogyo Co., Ltd., NK ester A-DPH)

B-9: Polymerizable unsaturated monomer containing polyfunctional urethane acrylate type compound (Nippon Kayaku Co., Ltd., KAYARAD DPHA-40H)

<[C] radiation sensitive polymerization initiator>

C-1: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Chiba-Specialty-Chemicals Co., Ltd.) Kaisha, Irgacure OXE02)

C-2: 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyl oxime)] (Chiba specialty chemicals, Irgacure OXE01)

C-3: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty Chemicals, Irgacure 819)

C-4: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (Chiba-Specialty-Chemicals, Irgacure 907)

<[D] organic solvent>

D-1: 3-methoxypropionate methyl

D-2: 3-methoxy ethylpropionate

D-3: Propylene Glycol Monomethoxy Acetate

D-4: diethylene glycol methyl ethyl ether

In addition, the mixing ratio of the solvent in Examples 18, 19, and 20 is as showing below, respectively.

Example 18 D-1 / D-3 = 50/50

Example 19 D-2 / D-4 = 60/40

Example 20 D-1 / D-3 = 50/50

<[E] adhesion preparation>

E-1: (gamma)-glycidoxy propyl trimethoxysilane (Tosoh Co., S-510)

E-2: 2- (2-vinyloxyethoxy) ethyl acrylate (Nippon Shokubai, VEEA)

<[F] surfactant>

F-1: Silicone Surfactant (Torre Dow Corning Silicon Co., Ltd., SH28PA)

F-2: fluorine-based surfactant (Neo, Pgentent 710F)

<[G] polymerization inhibitor>

G-1: p-methoxy phenol (Wako Junyaku Co., Ltd., p-methoxy phenol)

<Evaluation of Physical Properties of Interlayer Insulating Film>

The interlayer insulation film was formed as follows with the radiation sensitive resin composition prepared as mentioned above, and the physical property was evaluated. The results are shown in Table 1 below.

[Sensitivity]

After applying the radiation-sensitive resin compositions (S-1) to (S-23) and (CS-1) to (CS-6), respectively, on the silicon substrate by using a spinner, on a hot plate at 100 ° C for 2 minutes. It prebaked and the coating film of 4.0 micrometers in thickness was formed. Subsequently, exposure time was changed using the exposure machine (ultra high pressure mercury lamp, Canon Corporation, PLA-501F), and exposure was performed to the coating film through the pattern mask which has a predetermined pattern. Next, the image development process was performed at 25 degreeC by the puddle method using the tetramethylammonium hydroxide aqueous solution (developer) of 0.4 mass%. The development processing time was 100 seconds. After the development treatment, the coating film was washed with ultrapure water for 1 minute, dried, and a pattern was formed on the wafer. This silicon substrate was heated in a clean oven at 220 degreeC for 1 hour, and the interlayer insulation film was obtained. The film thickness of the obtained cured film was measured using the stylus type film thickness meter.

The exposure amount at which the residual film ratio (the ratio of the pattern-shaped thin film remaining properly) represented by the following formula is 85% or more is determined as the sensitivity, and the case of less than 800 J / m 2 is used in the case of A, 800 J / m 2 or more and less than 1,000 J / m 2. And C, 1,200 J / m <2> or more as the case of 1,000 J / m <2> or more and less than 1,200 J / m <2> as D.

[Resolution]

The minimum diameter of the penetrating hole formed in the interlayer insulating film formed as described above was observed with an optical microscope, and the minimum diameter was A in the case of 5-10 μm, B in the case of 10-20 μm, The case where a hole does not arise was made into D.

[Residue]

The hole of 10x10 micrometers of the interlayer insulation film formed as mentioned above was observed with the optical microscope, and the grade of the residue was evaluated. A was the case where the residue could not be confirmed, B was the case where the residue could be confirmed slightly, C was the case where the residue could be clearly identified, and D was the case where the residue could be confirmed in large quantities.

[Unique]

The external appearance of the interlayer insulation film formed as above was visually observed. A was the case where nonuniformity could not be confirmed, and the case where nonuniformity could be confirmed in C and the whole surface was D as the case where A and the nonuniformity could be confirmed a little, and the case where many nonuniformity could be confirmed.

[Transparency]

In the formation of the interlayer insulating film, the same operation was performed except that a glass substrate (Corning 7059, Corning Corporation) was used instead of the silicon substrate, thereby forming an interlayer insulating film on the glass substrate. The light transmittance (%) of the glass substrate which has an interlayer insulation film was measured with the wavelength of 400-800 nm using the spectrophotometer (150-20 type double beam, Hitachi Seisakusho). A, 90% or more and 95% or less of B and C and less than 85% or less of C and less than 85% of the case where the minimum light transmittance exceeded 95% were made into D.

[Heat resistant transparency]

The board | substrate created by the said evaluation of transparency was further heated at 250 degreeC in clean oven for 1 hour, and the light transmittance before and behind heating was measured and operated similarly to the said transparency evaluation. Heat resistance transparency (%) is computed according to a following formula, and when this value is 4% or less, it can be judged that the heat resistance transparency of a protective film is favorable.

Heat resistance transparency (%) = light transmittance (%) before heating-light transmittance (%) after heating

[Adhesiveness of phenomenon]

The coating film was formed similarly to the formation of the said interlayer insulation film, and it exposed at 2,000J / m <2>, and observed the minimum size which does not peel after image development with the optical microscope in the pattern of L / S = 1: 1. The minimum size of D was less than 30 micrometers A, and 30 micrometers or more and 50 micrometers or less and B and 50 micrometers or more peeled.

Relative permittivity

After apply | coating radiation sensitive resin composition (S-1)-(S-23) and (CS-1)-(CS-6), respectively, using the spinner on the polished SUS304 manufacture board | substrate, it is 2 minutes at 100 degreeC. Prebaking was carried out on a hot plate to form a coating film having a film thickness of 3.0 mu m. Subsequently, an exposure machine (ultra-high pressure mercury lamp, Canon Inc., PLA-501F) was used to expose the coating film so that the total irradiation amount was 3,000 J / m 2, and the silicon substrate was heated at 220 ° C. for 1 hour in a clean oven. Thus, an interlayer insulating film of 3.0 mu m thickness was formed. By the vapor deposition method, the Pt / Pd electrode pattern with respect to this interlayer insulation film was created, and it was set as the sample for dielectric constant measurement. The dielectric constant of the board | substrate was measured by CV method at the frequency of 10 Hz using the electrode (Yokogawa-Hewlett-Packard Co., Ltd., HP16451B) and HP4284A fresh LCR meter. A with a relative dielectric constant of less than 3.5 was A, 3.5 or more was less than 3.8, B, 3.8 or more was less than 4.1, and C and 4.1 were more than D.

As is apparent from Table 1, the composition of the present invention was found to have good sensitivity and resolution. In addition, it was found that the interlayer insulating film formed from the composition had few residues and unevenness, and was excellent in transparency, heat resistance transparency, development adhesiveness, and relative dielectric constant.

The present invention can provide a radiation-sensitive resin composition having excellent sensitivity and resolution, and an interlayer insulating film having little unevenness and excellent transparency, development adhesiveness, relative dielectric constant, and the like. Therefore, such an interlayer insulating film is suitably used for a display element.

Claims (7)

[A] copolymer,
[B] a polymerizable unsaturated compound,
[C] a radiation sensitive polymerization initiator, and
[D] organic solvents
&Lt; / RTI &gt;
[A] The copolymer is
(A1) a structural unit derived from at least one compound selected from the group consisting of (meth) acrylic acid and unsaturated carboxylic anhydride,
(A2) (meth) acrylic acid glycidyl, (meth) acrylic acid 3,4-epoxycyclohexylmethyl, 4-hydroxybutyl (meth) acrylate glycidyl ether and 3- (meth) acryloyloxymethyl- A structural unit derived from at least one compound selected from the group consisting of 3-ethyloxetane,
(A3) structural units derived from at least one compound selected from the group consisting of styrene, α-methylstyrene, 4-methylstyrene and 4-hydroxystyrene, and
(A4) methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, and Structural units derived from at least one compound selected from the group consisting of tert-butyl (meth) acrylate
Including,
[A] With respect to the total amount of all structural units in the copolymer,
The content ratio of the structural unit derived from (A1) compound is 1 mol% or more and 40 mol% or less,
The content ratio of the structural unit derived from (A2) compound is 1 mol% or more and 15 mol% or less,
1 mol% or more and 70 mol% or less of the content rate of the structural unit derived from (A3) compound, and
(A4) The content rate of the structural unit derived from a compound is 1 mol% or more and 30 mol% or less
Phosphorus radiation sensitive resin composition. The method of claim 1,
[A] The copolymer further contains a structural unit derived from at least one compound selected from the group consisting of (A5) maleimide, N-phenylmaleimide and N-cyclohexyl maleimide,
The radiation sensitive resin composition whose content rate of the structural unit derived from the said (A5) compound contains 1 mol% or more and 40 mol% or less. The method of claim 1,
The radiation sensitive resin composition in which an organic solvent (D) contains the organic solvent represented by following formula (1):

(In formula (1), R <^1> and R <^2> is respectively independently a C1-C6 alkyl group; n is an integer of 1-6.). The method of claim 1,
(B) A radiation sensitive resin composition in which a polymerizable unsaturated compound contains the polymerizable unsaturated compound which has a hydroxyl group or a carboxyl group, and whose content of the said [B] polymerizable unsaturated compound is 10 mol% or more and 60 mol% or less. The interlayer insulation film for display elements formed from the radiation sensitive resin composition of any one of Claims 1-4. (1) Process of forming the coating film of the radiation sensitive resin composition in any one of Claims 1-4 on a board | substrate,
(2) irradiating at least a part of the coating film with radiation;
(3) developing the coating film irradiated with the radiation;
(4) The process of baking the developed coating film
The formation method of the interlayer insulation film for display elements which has this. The display element provided with the interlayer insulation film for display elements of Claim 5.