KR20100087658A - Radiation sensitive resin composition, and interlayer insulating film and forming method thereof - Google Patents

Abstract

PURPOSE: A radiation sensitive resin composition, an interlayer insulating film, and a method for forming the same are provided to obtain an uniform thickness of a film even when a slit coating method is used, to have high radiation sensitivity, and to form a good pattern even when optimal developing time is over passed. CONSTITUTION: A radiation sensitive resin composition comprises: an alkali soluble resin; a 1,2-quinonediazide compound; and copolymers of polymerizable unsaturated compounds including a compound which is marked by CH2=CR^1COO-C_α H_2α-C_βF_2β+1, a compound which is marked by CH2=CR^2COO-(C_γ H_2γ-O)_a-R^3, and an unsaturated compound having a functional group which is marked by chemical formula 1.

Description

A radiation sensitive resin composition, an interlayer insulation film, and the formation method therefor {RADIATION SENSITIVE RESIN COMPOSITION, AND INTERLAYER INSULATING FILM AND FORMING METHOD THEREOF}

TECHNICAL FIELD This invention relates to a radiation sensitive resin composition, an interlayer insulation film, and its formation method.

Thin film transistors (hereinafter referred to as "TFT") type liquid crystal display elements, magnetic head elements, integrated circuit elements, and solid state imaging elements are generally used to insulate between wirings arranged in layers. An interlayer insulating film is formed. As a material which forms an interlayer insulation film, the radiation sensitive resin composition is widely used by the point that there are few processes for obtaining the required pattern shape, and it is preferable that it has high flatness (refer patent document 1 and patent document 2).

Among the electronic components, for example, a TFT type liquid crystal display element is manufactured through a process of forming a transparent electrode film on the interlayer insulating film and further forming a liquid crystal alignment film thereon. Therefore, since the interlayer insulation film is exposed to high temperature conditions in the step of forming the transparent electrode film or exposed to the stripping solution of the resist used for pattern formation of the electrode, sufficient resistance to these is required.

The interlayer insulating film thus obtained has a developing time in which the developing solution penetrates between the pattern and the substrate and easily peels off when the developing time is excessively shorter than the optimum time in the developing step in forming them. This needs to be strictly controlled, and there is a problem in terms of product yield.

In recent years, in the TFT type liquid crystal display device, there are trends such as large screen, high brightness, high definition, high speed response, and thinning, and the composition for forming an interlayer insulating film used therein is highly sensitive, and the interlayer formed Higher performance is required for the insulating film than in the prior art in terms of low dielectric constant, high transmittance, and the like.

As described above, in forming the interlayer insulating film from the radiation-sensitive resin composition, a high sensitivity is required as the composition, and in the developing step in the forming step, even if the developing time is more than the predetermined time, the pattern is not exfoliated and satisfactory. Although high heat resistance, high solvent resistance, low dielectric constant, high transmittance, and the like are required for the interlayer insulating film formed therefrom and formed therefrom, no radiation-sensitive resin composition that satisfies such a requirement is known.

In addition to these trends, with the recent trend of large-screen TVs and requests for reduction in process costs, there is a tendency for the size of the substrate glass used for the production of substrates with color filters to increase in size. Therefore, in the application | coating process of the radiation sensitive resin composition performed when forming an interlayer insulation film on a board | substrate, it is becoming difficult to employ | adopt the spin coating method conventionally widely performed, and the application | coating method removes a composition from a slit-shaped nozzle. It changes to what is called a slit coating method to apply | coat and apply-discharge (patent document 3). This slit coating method also has the advantage that the amount of the composition required for coating can be reduced as compared with the spin coating method, which also helps to reduce the cost of liquid crystal display device manufacturing. However, in such a slit coating method, the coating nozzle is sweeped in a predetermined direction in a state in which the substrate is in close contact with the vacuum suction, and then applied, and then the support pins stored in the holes for vacuum suction are raised. The substrate is lifted and conveyed to the next step from the coating stage. Therefore, in this series of processes, the coating film may have a nonuniformity caused by a hole for vacuum adsorption, a nonuniformity caused by a support pin, a nonuniformity displayed in a stripe shape in the sweeping direction of the coating nozzle, and the like. There is a problem in achieving such high flatness.

Japanese Patent Laid-Open No. 2001-354822 Japanese Laid-Open Patent Publication No. 2001-343743 Japanese Laid-Open Patent Publication No. 2006-184841

The present invention has been made on the basis of the above circumstances, and an object of the present invention is to exhibit excellent film thickness uniformity and high radiation sensitivity even in the case of employing the slit coating method as the coating method. A radiation-sensitive resin composition having a developing margin that can still form a good pattern shape even after the optimum developing time, and an interlayer insulating film excellent in high performance, high solvent resistance, high transmittance, low dielectric constant, and the like, and a method of forming the same To provide.

The above object and advantages of the present invention, first,

(A) alkali-soluble resin,

(B) 1,2-quinonediazide compound (hereinafter referred to as "compound (B)"),

(C) (c1) A compound represented by the following general formula (1 ⁰ ) (hereinafter referred to as "compound (c1)"), (c2) A compound represented by the following general formula (2 ⁰ ) (hereinafter referred to as "compound ( c2) "and (c3) a copolymer of a polymerizable unsaturated compound containing a polymerizable unsaturated compound having a group represented by the following general formula (3) (hereinafter referred to as" compound (c3) ") (hereinafter, It is achieved by the radiation sensitive resin composition containing "copolymer (C)."

CH ₂ = CR ¹ COO-C _α H _{2 α} -C _β F _{2β + 1} (1 ⁰ )

(In formula (1 ⁰ ), R ¹ is a hydrogen atom or a methyl group, α is an integer of 0 to 6, and β is an integer of 1 to 20.)

CH ₂ = CR ² COO- (C _γ H _{2 γ} -O) _a -R ³ (2 ⁰ )

(In formula (2 ⁰ ), R ² is a hydrogen atom or a methyl group, R ³ is an alkyl group having 1 to 12 carbon atoms, γ is 2 or 3, a is the number of repeating units, and the number average thereof is 1 to 30). .)

(In formula (3), R ⁴ , R ⁵ , R ⁶ , R ⁷ And R ⁸ are each independently an alkyl group having 1 to 20 carbon atoms, a phenyl group or a group represented by the following General Formula (4), and b is an integer of 0 to 3).

(In formula (4), R ⁹ , R ^10. And R ¹¹ Are each independently an alkyl group having 1 to 20 carbon atoms or a phenyl group, and c is an integer of 0 to 3).

The above object and advantages of the present invention are,

Polymeric unsaturation in which the said (C) copolymer contains the polymerizable unsaturated compound which has a (c4) C1-C8 alkyl group other than the said compound (c1), a compound (c2), and a compound (c3) further It is achieved by the radiation sensitive resin composition of the said 1st which is a copolymer of a compound.

The above object and advantages of the present invention are,

In addition to the compound (c1), the compound (c2), the compound (c3) and the compound (c4), the copolymer (C) may further include a polymerizable unsaturated compound having two or more unsaturated bonds in (c5) 1 molecule. It is achieved by the radiation sensitive resin composition of the said 2nd which is a copolymer of the polymerizable unsaturated compound containing.

The above objects and advantages of the present invention are fourth,

The compound (c1) is a compound represented by the following formula (1),

The compound (c2) is a compound represented by the following general formula (2), further

(C) the copolymer,

25-35 mass% of compound (c1),

20-30 mass% of compound (c2),

15-20 mass% of compound (c3),

25-35 mass% of compound (c4), and

1-5 mass% of compound (c5)

It is achieved by the radiation sensitive resin composition of the said 3rd which is a copolymer of the polymerizable unsaturated compound which consists of.

CH ₂ = CR ¹ COOCH ₂ CH ₂ C ₈ F ₁₇ (1)

(In formula (1), R ¹ is as defined in the formula (1 ⁰ ).)

CH ₂ = CR ² COO (C ₂ H ₄ O) _a R ³ (2)

(Formula (2) of, R ² and R ³ are, respectively, as defined in the formula ^(20), the number average value of a number of repeating units is 4 to 12).

The above object and advantages of the present invention are,

(A) alkali-soluble resin,

(a1) at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and

(a2) Polymerizable unsaturated compound having an epoxy group

It is achieved by the radiation sensitive resin composition of the said 1st-4th which is a copolymer of the monomer containing.

The above objects and advantages of the present invention are sixth,

It is achieved by the interlayer insulation film formed from said radiation sensitive resin composition.

The above object and advantages of the present invention are seventh,

The following steps are included in the order described below, which is achieved by a method for forming an interlayer insulating film.

(1) process of apply | coating said radiation sensitive resin composition on a board | substrate, and forming a coating film,

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

(3) the developing step;

(4) heating step.

The above object and advantages of the present invention, eighth,

It is achieved by an interlayer insulating film formed by the above method.

The above object and advantages of the present invention, the ninth,

(A) alkali-soluble resin,

(a1) at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and

(a2) In addition to the polymerizable unsaturated compound having an epoxy group, further

(a3) It is achieved by the radiation sensitive resin composition of said 1st-4th which is a copolymer of the monomer containing the unsaturated compound which has radical polymerizability.

According to the present invention, even when the slit coating method is adopted as the coating method, it exhibits excellent film thickness uniformity, high radiation sensitivity, and can still form a good pattern shape even after exceeding the optimum developing time in the developing step. Provided are a radiation-sensitive resin composition having a developing margin, and an interlayer insulating film excellent in high performance, such as high heat resistance, high solvent resistance, high transmittance, and low dielectric constant, and a method of forming the same.

(Form to carry out invention)

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.

<(A) alkali-soluble resin>

The (A) alkali-soluble resin contained in the radiation sensitive resin composition of this invention will not be specifically limited if it is alkali-soluble resin which has solubility with respect to the developing solution used for the image development process mentioned later preferably an alkali developing solution. As such (A) alkali-soluble resin, alkali-soluble resin which has at least 1 sort (s) chosen from the group which consists of a carboxyl group and a carbonic anhydride group is preferable, For example,

(a1) at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as "compound (a1)"), and

(a2) A copolymer of a monomer (hereinafter referred to as "copolymer (A)") containing a polymerizable unsaturated compound having an epoxy group (hereinafter referred to as "compound (a2)") can be suitably used.

The copolymer (A) may be a copolymer of a monomer comprising the compound (a1) and the compound (a2), or polymerizable unsaturated compounds other than these compounds (a3) in addition to the compound (a1) and the compound (a2) ( Hereinafter, although the copolymer of the monomer containing "compound (a3)" may be sufficient, it is preferable that it is the latter.

The copolymer (A) can be produced by radically polymerizing the above monomers in a solvent, preferably in the presence of a polymerization initiator.

[Compound (a1)]

The copolymer (A) used in the present invention preferably has a structural unit derived from the compound (a1) based on the sum of the repeating units derived from the compound (a1), (a2) and (a3). It is-40 mass%, Especially preferably, it contains 5-25 mass%. When the ratio of this structural unit is 5-40 mass%, the radiation sensitive resin composition by which the various characteristics, such as radiation sensitivity, developability, and storage stability, were balanced to a higher level is obtained.

The compound (a1) is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. For example, monocarboxylic acid, dicarboxylic acid, anhydrides of dicarboxylic acids, and mono carboxylic acids of polyhydric acid [ (Meth) acryloyloxyalkyl] ester, the mono (meth) acrylate of the polymer which has a carboxyl group and a hydroxyl group at both terminals, the polycyclic compound which has a carboxyl group, its anhydride, etc. are mentioned.

As these specific examples, As monocarboxylic acid, For example, acrylic acid, methacrylic acid, crotonic acid, etc .;

As dicarboxylic acid, For example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .;

As anhydride of dicarboxylic acid, For example, anhydride of the compound illustrated as said dicarboxylic acid;

As mono [(meth) acryloyloxyalkyl] ester of polyhydric carboxylic acid, for example, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] My back;

As mono (meth) acrylate of the polymer which has a carboxyl group and a hydroxyl group in both terminal, For example, (omega)-carboxy polycaprolactone mono (meth) acrylate, etc .;

As a polycyclic compound which has a carboxyl group, and its anhydride, for example, 5-carboxy bicyclo [2.2.1] hept-2-ene, 5,6- dicarboxy bicyclo [2.2.1] hept-2-ene, 5 -Carboxy-5-methyl bicyclo [2.2.1] hept-2-yen, 5-carboxy-5-ethyl bicyclo [2.2.1] hept-2-yen, 5-carboxy-6-methyl bicyclo [2.2 .1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene and these Anhydrides etc. are mentioned, respectively.

Among these, anhydrides of monocarboxylic acid and dicarboxylic acid are preferably used, and acrylic acid, methacrylic acid and maleic anhydride are particularly preferably used in view of copolymerization reactivity, solubility in aqueous alkali solution and ease of obtaining. These compounds (a1) can also be used individually or in combination.

[Compound (a2)]

The copolymer (A) used in the present invention preferably has a structural unit derived from the compound (a2) based on the sum of the repeating units derived from the compound (a1), (a2) and (a3), preferably 10 80 mass%, Especially preferably, it contains 30-80 mass%. When the ratio of this structural unit is 10-80 mass%, the radiation-sensitive resin composition obtained by balancing the heat resistance and solvent resistance of an interlayer insulation film, and the storage stability of a radiation-sensitive resin composition to a higher level is obtained.

Compound (a2) is a polymerizable unsaturated compound having an epoxy group. Here, as an epoxy group, an oxiranyl group (having a 1,2-epoxy structure), an oxetanyl group (having a 1-3-epoxy structure), etc. are mentioned.

As a polymerizable unsaturated compound which has an oxiranyl group, for example, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycidyl (alpha)-n-propyl acrylate, the glycerin (alpha)-n-butylacrylate Cydyl, acrylic acid 3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6, 7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3, 4- epoxy cyclohexyl methacrylate, etc. are mentioned. Of these, methacrylic acid glycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3, 4-epoxycyclohexyl methacrylate etc. can be used preferably.

As an unsaturated compound which has an oxetanyl group, for example, 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl)- 3-ethyl oxetane, 3- (acryloyloxymethyl) -2-phenyl oxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2- Ethyl oxetane, 3- (2-acryloyloxyethyl) -3-ethyl oxetane, 3- (2-acryloyloxyethyl) -2-phenyl oxetane, 3- (methacryloyloxymethyl) Oxetane, 3- (methacryloyloxymethyl) -2-methyl oxetane, 3- (methacryloyloxymethyl) -3-ethyl oxetane, 3- (methacryloyloxymethyl) -2- Phenyl oxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyl oxetane, 3- (2-methacryloyloxyethyl) -3-ethyl oxetane, 3- (2-methacryloyloxyethyl) -2-phenyl oxetane, etc. are mentioned. have.

These compounds (a2) can also be used individually or in combination.

[Compound (a3)]

The copolymer (A) used in the present invention preferably has a structural unit derived from the compound (a3) based on the sum of the repeating units derived from the compound (a1), (a2) and (a3). -50 mass%, Especially preferably, it contains 5-50 mass%. When the ratio of this structural unit is 1-50 mass%, the radiation sensitive resin composition which balanced the heat resistance and solvent resistance of the interlayer insulation film formed, and the developability with respect to the aqueous alkali solution of a radiation sensitive resin composition to a higher level was carried out. You can get it.

The compound (a3) is not particularly limited as long as it is an unsaturated compound having radical polymerizability. As the compound (a3), for example, methacrylic acid alkyl ester, acrylic acid alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid ester having a hydroxyl group, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated Dicarboxylic acid diesters, bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated dienes;

Unsaturated compounds having a phenolic hydroxyl group represented by the following formula (I);

Unsaturated compounds having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton or a skeleton represented by the following formula (II); And

And other unsaturated compounds.

(In Formula (I), R ^I is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^II to R ^VI are the same or different, and are a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, and B is a A bond, -COO-, or -CONH-, m is an integer of 0-3, provided that at least one of R ^II to R ^VI is a hydroxyl group.)

(In formula (II), R ^VII is a hydrogen atom or a methyl group.)

As these specific examples, as methacrylic acid alkyl ester, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl Methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate and the like;

As acrylic acid alkyl ester, For example, methyl acrylate, isopropyl acrylate, etc .;

As methacrylic acid cyclic alkylester, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, tricyclo [5.2. 1.0 ^2,6 ] decane-8- ^yloxyethyl methacrylate, isoboroyl methacrylate, etc .;

As methacrylic acid ester which has a hydroxyl group, For example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol mono Methacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethyl glycoside, 4-hydroxybenzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, and the like;

As acrylic acid cyclic alkylester, For example, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] Decan-8-yloxyethyl acrylate, isoboroyl acrylate, and the like;

As methacrylic acid aryl ester, For example, phenyl methacrylate, benzyl methacrylate, etc .;

As acrylic acid aryl ester, For example, phenyl acrylate, benzyl acrylate, etc .;

As unsaturated dicarboxylic acid diester, For example, diethyl maleate, diethyl fumarate, diethyl itaconic acid;

As a bicyclo unsaturated compound, it is a bicyclo [2.2.1] hept-2-ene, 5-methyl bicyclo [2.2.1] hept-2-ene, 5-ethyl bicyclo [2.2.1] hept-, for example. 2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept -2 yen, etc .;

As the maleimide compound, for example, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide , N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide pro Cypionate, N- (9-acridinyl) maleimide, etc .;

As an unsaturated aromatic compound, For example, styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy styrene etc .;

Examples of conjugated dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like;

As an unsaturated compound which has a phenolic hydroxyl group represented by said Formula (I), For example, the compound etc. which are represented by each of following formula (I-1)-formula (I-5);

(Formula (I-1) and formula (I-3) in the n each, an integer from 1 to 3, formula (I-1) ~ formula (I-5) of the ^{R I, R II, R III} , R The definitions of ^IV , R ^V and R ^VI are the same as in the above formula (I).)

As an unsaturated compound containing a tetrahydrofuran skeleton, it is tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloyloxy propionate tetrahydrofurfuryl ester, 3- (meth) acryloyloxy, for example. Tetrahydrofuran-2-one, etc .;

As an unsaturated compound containing a furan skeleton, for example, 2-methyl-5- (3-furyl) -1-pentene-3-one, furfuryl (meth) acrylate, and 1-furan-2-butyl-3- Yen-2-one, 1-furan-2-butyl-3-methox-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexene-3-one, 6-furan -2-yl-hex-1-en-3-one, (meth) acrylic acid- 2-furan-2-yl- 1-methyl-ethylester, 6- (2-furyl) -6-methyl- 1-heptene -3-warm etc .;

As an unsaturated compound containing a tetrahydropyran, it is (tetrahydropyran-2-yl) methyl (meth) acrylate, 2,6- dimethyl- 8- (tetrahydropyran-2-yloxy) -oct, for example. -1 -en-3 -one, 2- (meth) acrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, etc .; pyran skeleton As an unsaturated compound containing, for example, 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran and 4- (1,5-dioxane-6- Oxo-7-octenyl) -6-methyl-2-pyran and the like;

As an unsaturated compound containing the skeleton represented by said Formula (II), For example, polyethyleneglycol mono (meth) acrylate of the polymerization degree 2-10, polypropyleneglycol mono (meth) acrylate etc. of the polymerization degree 2-10;

As other unsaturated compounds, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, etc. are mentioned, for example.

Among these, methacrylic acid alkyl esters, methacrylic acid cyclic alkyl esters, acrylic acid cyclic alkyl esters, maleimide compounds and unsaturated aromatic compounds;

Unsaturated compounds having a phenolic hydroxyl group represented by the above formula (I);

An unsaturated compound having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton or a skeleton represented by the formula (II) is preferably used, and in particular, styrene, t-butyl methacrylate, tricyclo [5.2. 1.0 ^2,6 ] decane-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexyl maleimide, tetrahydrofurfuryl (meth) acrylate , Polyethylene glycol (n = 2-10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydrofuran-2-one, 4-hydroxybenzyl (meth) acrylate, 4-hydroxyphenyl Copolymerization reactivity and at least 1 sort (s) chosen from the group which consists of a (meth) acrylate, o-hydroxy styrene, p-hydroxy styrene, and (alpha) -methyl- p-hydroxy styrene are used. It is preferred in view of solubility in an aqueous solution of potassium.

These compounds (a3) can also be used individually or in combination.

As a preferable specific example of the copolymer (A) used by this invention, methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / 2-methylcyclohexyl acrylate / meth Glycidyl glycidyl / styrene copolymer, methacrylic acid / tetrahydrofurfuryl methacrylate / methacrylate glycidyl / N-cyclohexyl maleimide / n-lauryl methacrylate / alpha -methyl-p- Hydroxystyrene copolymer,

Styrene / methacrylic acid / glycidyl methacrylate / 3- (methacryloyloxymethyl) -3-ethyloxetanyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate air Coalescence, etc. are mentioned.

About the copolymer (A) used by this invention, the weight average molecular weight (henceforth "Mw") of polystyrene conversion measured by the gel permeation chromatography, Preferably it is 2 * 10 <^3> -1 * 10 <^5>. More preferably, they are 5 * 10 <^3> -5 * 10 <^4> . When Mw is less than 2x10 <^3> , developing margin may become inadequate, the residual film rate etc. of a film obtained may fall, and also the pattern shape, heat resistance, etc. of an interlayer insulation film obtained may fall, and it may be 1x10. ^When it exceeds ⁵ , the sensitivity may decrease or the pattern shape may fall. In addition, molecular weight distribution (henceforth "Mw / Mn" is called. However, Mn is the number average molecular weight of polystyrene conversion measured by the gel permeation chromatography with respect to the copolymer (A).) Preferably it is 5.0 or less It is more preferably 3.0 or less. When Mw / Mn exceeds 5.0, the pattern shape of the obtained interlayer insulation film may fall.

As mentioned above, the radiation sensitive resin composition containing a copolymer (A) can form a predetermined pattern shape easily, without developing developing residue when developing.

As a solvent used for manufacture of a copolymer (A), for example, diethylene glycol dialkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, propylene glycol ethyl ether, ketone, 3-methoxypropionic acid Methyl, alcohol, glycol ether, ethylene glycol alkyl ether acetate, ester, diethylene glycol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate And propylene glycol monomethyl ether, ethyl ethoxypropionate and the like.

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

As propylene glycol alkyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc. are mentioned, for example.

Among these, diethylene glycol dialkyl ether and propylene glycol alkyl ether acetate are preferable, and especially diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate, and 3-methoxypropionate methyl Preference is given to using.

As a polymerization initiator used for manufacture of a copolymer (A), what is generally known as a radical polymerization initiator can be used. For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvaleronitrile), 2,2'- azobis- (4-methoxy-2, Azo compounds, such as 4-dimethylvaleronitrile), are mentioned.

In manufacture of a copolymer (A), in order to adjust molecular weight, a molecular weight modifier can be used. Specific examples thereof include mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan and thioglycolic acid; dimethyl xanthogen sulfide, diisopropyl xanthogen disulfide and the like. Xanthogens; terpinolene, α-methylstyrene dimer and the like.

<Compound (B)>

Compound (B) used in the present invention is a 1,2-quinonediazide compound which generates a carboxylic acid upon irradiation with a phenolic compound or an alcoholic compound (hereinafter referred to as "nucleus"). Condensates of 1,2-naphthoquinone diazide sulfonic acid halide can be used.

As said mother nucleus, trihydroxy benzophenone, tetrahydroxy benzophenone, pentahydroxy benzophenone, hexahydroxy benzophenone, (polyhydroxyphenyl) alkane, etc. are mentioned, for example.

As these specific examples, as trihydroxy benzophenone, 2,3,4- trihydroxy benzophenone, 2,4,6- trihydroxy benzophenone etc. are mentioned, for example;

2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzo as tetrahydroxybenzophenone Phenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc .;

As pentahydroxy benzophenone, 2,3,4,2 ', 6'- pentahydroxy benzophenone etc. are mentioned, for example;

As hexahydroxy benzophenone, for example, 2,4,6,3 ', 4', 5'-hexahydroxy benzophenone, 3,4,5,3 ', 4', 5'-hexahydroxy benzo Phenone, etc .;

As the (polyhydroxyphenyl) alkane, for example, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1 -Tri (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3 -Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [4-hydroxyphenyl] -1-methylethyl] phenyl] Ethylidene] bisphenol, bis (2,5-dimethyl- 4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'- tetramethyl- 1,1'-spirobiindene-5 Examples of the above-mentioned examples include, but are not limited to, 6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavane, and the like. 1,2-naphthoquinone diazide sulfonic acid amide which changed the ester bond of one mother core to an amide bond, for example, 2,3,4-triha Etc. de hydroxy benzophenone-1,2-naphthoquinonediazide-4-sulfonic acid amide may be suitably used.

Of these mother cores, 2,3,4,4'-tetrahydroxybenzophenone, 4,4 '-[1-[4- [1-[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene Bisphenol is preferable.

As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable, and the specific examples thereof include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-. Naphthoquinone diazide-5-sulfonic acid chloride is mentioned, It is preferable to use a 1, 2- naphthoquinone diazide- 5-sulfonic acid chloride among these.

In the condensation reaction, 1,2-naphthoquinone diazide sulfonic acid halide corresponding to the number of hydroxyl groups in the mother nucleus is preferably 30 to 85 mol%, more preferably 50 to 70 mol%. Condensation reaction can be performed by a well-known method.

These compounds (B) can be used individually or in combination of 2 or more types.

The use ratio of a compound (B) becomes like this. Preferably it is 5-100 mass parts with respect to 100 mass parts of (A) alkali-soluble resin, More preferably, it is 10-50 mass parts. When the ratio is 5 to 100 parts by mass, the solubility difference between the irradiated part and the unirradiated part of the alkaline aqueous solution serving as the developing solution is large, so that the patterning is good, and the heat resistance and solvent resistance of the resulting interlayer insulating film are also good.

<Copolymer (C)>

The copolymer (C) in the present invention is a copolymer of a polymerizable unsaturated compound containing the compound (c1), the compound (c2) and the compound (c3), and in the resin composition for forming an interlayer insulation film of the present invention. The surface smoothness of the coating film can be improved even when used in a small proportion, and the film thickness uniformity of the formed interlayer insulating film can be significantly improved. have.

The copolymer (C) is preferably a polymerizable unsaturated compound having an alkyl group having 1 to 8 carbon atoms in addition to the compound (c1), the compound (c2) and the compound (c3). Compound (c4) "), and more preferably (c5) in addition to the compound (c1), the compound (c2), the compound (c3) and the compound (c4). A copolymer of a polymerizable unsaturated compound containing a polymerizable unsaturated compound having two or more unsaturated bonds (hereinafter referred to as "compound (c5)") in one molecule, and particularly preferably the compound (c1) and a compound It is a copolymer of the polymerizable unsaturated compound which consists of (c2), a compound (c3), a compound (c4), and a compound (c5).

The group -C _α H _{2 α} -in the formula (1 ⁰ ) is a methylene group, an alkylmethylene group, or a linear or branched alkylene group. When the group —C _α H _{2 α} − is asymmetric, the bonding direction is irrespective. Carbon number ( _{alpha) of} group -C ( _alpha) H2 _{( alpha)} -becomes like this. Preferably it is 2-4. Specific examples of the group -C _α H _{2 α} -include 1,2-ethylene groups, 1,2-propylene groups, 1,3-propylene groups, 1,4-butylene groups, and the like. A 1, 2- ethylene group or a 1, 3- propylene group is preferable, and a 1, 2- ethylene group is especially preferable.

The group -C _β F _{2β + 1} in the formula (1 ⁰ ) is a linear or branched fluoroalkylene group, the carbon number β is 1 to 20, preferably 4 to 12, and particularly preferably 8 to be. It is preferable that group -C ( _beta) F2 ( _{beta ) +1} is a linear fluoroalkylene group.

As a compound (c1) in this invention, it is preferable that it is a compound represented by following formula (1), and the compound represented by each of following formula (c1-1) and (c1-2) as the specific example is mentioned. Can be.

CH ₂ = CR ¹ COOCH ₂ CH ₂ C ₈ F ₁₇ (1)

(In formula (1), R ¹ is as defined in the formula (1 ⁰ ).)

CH ₂ = CHCOOCH ₂ CH ₂ (CF ₂ ) ₇ CF ₃ (c1-1)

CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₇ CF ₃ (c1-2)

The group -C _γ H _{2 γ} -in the formula (2 ⁰ ) is a linear or branched alkylene group. When the group -C _γ H _{2 γ} -is asymmetric, the direction of bonding thereof is irrespective. As a specific example of group -C ( _gamma) H2 _{( gamma)} -, a 1,2-ethylene group and a 1,2-propylene group are mentioned, for example, It is preferable that it is a 1,2-ethylene group.

Compound (c2) is used as a mixture of compounds in which the value of the repeating unit number a in General Formula (2 ⁰ ) is different. The number average value of a is 1-30, Preferably it is 2-20, It is especially preferable that it is 4-12. The value of this a can be calculated | required by calculation from the number average molecular weight of polystyrene conversion measured by the gel permeation chromatography with respect to the compound (c2).

As a compound (c2) in this invention, it is preferable that it is a compound represented by following formula (2).

CH ₂ = CR ² COO (C ₂ H ₄ O) _a R ³ (2)

(Formula (2) of, R ² and R ³ are, respectively, the same meanings as defined in the formula ^(20), the number average value of a number of repeating units is 4 to 12).

As such a compound (c2), a commercial item can be used suitably, For example, NK-ester M-40G, M-90G, AM-90G by Shin-Nakamura Chemical Industries Co., Ltd .; Niche oil company BLEMMER PME-200, PME-400, PME-550 etc. are mentioned.

In the general formula (3), when a plurality of R ⁵ and R ⁶ are each present, each R ⁵ may be the same or different, and each R ⁶ may be the same or different. In addition, in the said General formula (4), when there exist two or more R <^10> and R <^11> , each R <^10> may be the same or different, and each R <^11> may be the same or different.

As said compound (c3), in said General formula (3), R <^4> , R <^5> and R <^6> are respectively a C1-C20 alkyl group or a phenyl group, and R <^7> and R <^8> are respectively said It is preferable that it is a polymerizable unsaturated compound which has group represented by General formula (4). As compound (c3), it is preferably a compound represented by the following general formula (c3-1).

(In formula (c3-1), R ^Si is a group represented by the general formula (3), R ¹² is a hydrogen atom or a methyl group, and d is an integer of 1 to 3.)

As a more specific example of a compound (c3), the compound represented by each of following General formula (c3-1-1)-(c3-1-3) is mentioned.

(In said formula, Me is a methyl group, Ph is a phenyl group, and r, s, and t are the integers of 0-3, respectively.)

As said compound (c4), the alkyl (meth) acrylate etc. which have a C1-C8 alkyl group are mentioned, for example, Specifically, methyl methacrylate and 2-ethylhexyl acrylate, for example. Etc. can be mentioned.

As a specific example of the said compound (c5), the compound which methacrylated the both ends of tetramethylene glycol, the polyethyleneglycol of the polymerization degrees 1-20, the polypropylene glycol of the polymerization degrees 1-20, etc. are mentioned, for example. As said compound (c5), a commercial item can be used suitably, As a specific example, NK ester 1G, Copper 2G, Copper 3G, Copper 4G, Copper 9G, by Shin-Nakamura Chemical Co., Ltd., for example. Copper 14G, and the like.

The copolymer (C) in the present invention is a copolymer of a polymerizable unsaturated compound containing a compound (c1), a compound (c2) and a compound (c3) as described above. Here, the use ratio of each compound with respect to all of a polymerizable unsaturated compound is 10-50 mass% in the case of a compound (c1), 10-50 mass% in the case of a compound (c2), and a compound (c3) It is 5-45 mass%.

Copolymer (C), Preferably, it is a copolymer of the polymerizable unsaturated compound containing compound (c4) other than a compound (c1), a compound (c2), and a compound (c3). At this time, the use ratio of each compound with respect to all of a polymerizable unsaturated compound is 20-50 mass% in the case of a compound (c1), 15-40 mass% in the case of a compound (c2), and a compound (c3) It is 10-30 mass%, and in the case of a compound (c4), it is 20-35 mass%. Copolymer (C) is more preferably a copolymer of a polymerizable unsaturated compound containing compound (c5) in addition to compound (c1), compound (c2), compound (c3) and compound (c4), and particularly Preferably, it is a copolymer of the polymerizable unsaturated compound which consists of a compound (c1), a compound (c2), a compound (c3), a compound (c4), and a compound (c5). The use ratio of each compound with respect to all the polymerizable unsaturated compounds at this time is 25-35 mass% in the case of a compound (c1), 20-30 mass% in the case of a compound (c2), and in the case of a compound (c3) 15 It is -20 mass%, in the case of a compound (c4), it is 25-35 mass%, and in the case of a compound (c5), it is 1-5 mass%.

The weight average molecular weight (Mw) of the copolymer (C) is preferably 5,000 to 25,000, more preferably 10,000 to 25,000, and particularly preferably 15,000 to 25,000. The molecular weight distribution (Mw / Mn) of the copolymer (C) is preferably 1 to 10, more preferably 2 to 4.

There is no restriction | limiting in particular about the manufacturing method of such a copolymer (C), Based on well-known methods, for example, polymerization mechanisms, such as a radical polymerization method, a cation polymerization method, and an anion polymerization method, a solution polymerization method and a block shape I) Although it can manufacture by a polymerization method, an emulsion polymerization method, etc., since it is simple by the radical polymerization method in a solution, it is industrially preferable.

As a polymerization initiator used when manufacturing a copolymer (C), For example, Peroxides, such as benzoyl peroxide and diacyl peroxide; Azo compounds, such as 2,2'- azobisisobutyronitrile and phenyl azo triphenylmethane, etc. are mentioned.

Although manufacture of a copolymer (C) can be performed in the presence or absence of a solvent, it is preferable to carry out in presence of a solvent from a viewpoint of workability. Examples of the solvent include alcohols, ketones, esters, alkyl esters of monocarboxylic acids, polar solvents, ethers, propylene glycol and esters thereof, halogenated hydrocarbons, aromatic hydrocarbons, fluorinated inert liquids, and the like. . As said alcohol, For example, ethanol, isopropyl alcohol, n-butanol, iso-butanol, tert-butanol, etc .;

As said ketone, For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amino ketone, etc .;

As said ester, For example, methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate etc .;

Examples of the alkyl ester of the monocarboxylic acid include methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate and ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, butyl 2-methoxypropionate, etc .;

As said polar solvent, For example, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc .;

As said ether, For example, methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, ethyl cellosolve acetate, tetrahydrofuran, dioxane, etc .; As said propylene glycol and its ester, For example, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, a propylene glycol monobutyl ether acetate, etc .;

Examples of the halogenated hydrocarbons include 1,1,1-trichloroethane, chloroform and the like;

As said aromatic hydrocarbon, For example, benzene, toluene, xylene, etc .; Examples of the fluorinated inert liquid include perfluorooctane, perfluoro tri-n-butylamine, and the like, and any of these can be used.

When manufacturing a copolymer (C), you may further use chain transfer agents, such as lauryl mercaptan, 2-mercaptoethanol, ethyl thioglycolic acid, and octyl thioglycolic acid, as needed.

The use ratio of the copolymer (C) in the radiation-sensitive resin composition of the present invention is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2 with respect to 100 parts by mass of the (A) alkali-soluble resin. It is a mass part. Here, if the use ratio of a copolymer (C) is 0.01-3 mass parts, the film thickness uniformity of the coating film formed by application | coating by the slit coating method will become favorable. When this value exceeds 3 parts by mass, film roughness may easily occur, and the film thickness uniformity of the interlayer insulating film to be formed may be impaired.

<Other components>

Although the radiation sensitive resin composition of this invention contains the above-mentioned copolymer (A), a compound (B), and a copolymer (C) as an essential component, in addition, if necessary, (D) a thermosensitive acid production compound, (E) Epoxy resins other than a polymeric compound (henceforth "(E) component") and (F) copolymer (A) which have at least 1 ethylenically unsaturated double bond (hereinafter, "(F) component" And (G) adhesion adjuvant, (H) radical scavenging agent, and the like.

[(D) Thermosensitive Acid Generating Compound]

(D) A thermosensitive acid generating compound is a compound which generate | occur | produces an acid by heating, and can be contained in the radiation sensitive resin composition of this invention in order to improve heat resistance and hardness. Specific examples thereof include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts and phosphonium salts.

Specific examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts, and the like.

Of these, sulfonium salts and benzothiazonium salts are preferably used, and 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate and benzyl-4 are particularly preferred. -Hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acet The oxyphenyl benzylsulfonium hexafluoro antimonate and 3-benzyl benzothiazonium hexafluoro antimonate are used preferably.

Examples of such commercially available products include San-Aid SI-L85, SI-L110, SI-L145, SI-L150, and SI-L160 (manufactured by Sanshin Kagaku Kogyo Co., Ltd.).

The use ratio of the (D) thermosensitive acid generating compound is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. When this amount is 0.1 to 10 parts by mass, precipitates do not precipitate in the coating film forming step, and an interlayer insulating film having good hardness can be formed.

[(E) component]

As a polymeric compound which has at least 1 ethylenically unsaturated double bond which is the said (E) component, For example, monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional or more (meth) acrylate, etc. are mentioned. It may be mentioned suitably.

As said monofunctional (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate etc. are mentioned, for example. As these commercial items, for example, ARONIX M-101, M-111, M-114 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, and TC-120S (above, Nippon Kayaku Co., Ltd.) Kavisa Co., Ltd., VISCOAT 158, East 2311 (above, Osaka Yuki Kagaku Kogyo Co., Ltd.), etc. are mentioned.

As said bifunctional (meth) acrylate, ethylene glycol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, 1, 9- nonane diol di (meth) acrylate, polypropylene is mentioned, for example. Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, bisphenoxy ethanol fluorene diacrylate, and the like. As these commercial items, for example, ARONIX M-210, M-240, M-6200 (above, Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (above, Nippon Kaya) KUCO, Ltd.), VISCOAT 260, 312, 335HP (above, Osaka Yuki Kagaku Kogyo Co., Ltd.), etc. are mentioned.

As said trifunctional or more than (meth) acrylate, a trimethylol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a tri ((meth) acryloyloxyethyl) phosphate, a pentaerythritol tetra ( Meta) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Examples of the commercially available products include ARONIX M-309, copper M-400, copper M- and the like. 405, East M-450, East M-7100, East M-8030, East M-8050 (above, Toagosei Co., Ltd.), KAYARAD TMPTA, East DPHA, East DPCA-20, East DPCA-30, East DPCA -60, East DPCA-120 (above, Nippon Kayaku Co., Ltd.), VISCOAT 295, East 300, East 360, East GPT, East 3PA, East 400 (above, Osaka Yuki Kagaku Kogyo Co., Ltd.) Can be mentioned.

Of these, trifunctional or higher (meth) acrylates are preferably used, and trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are particularly preferred. Do.

These monofunctional, bifunctional or trifunctional or more (meth) acrylates may be used alone or in combination. The use ratio of (E) component is 50 mass parts or less with respect to 100 mass parts of (A) alkali-soluble resin, More preferably, it is 1-50 mass parts, More preferably, it is 3-30 mass parts. to be. When the use ratio of (E) component is 1-50 mass parts, the heat resistance, surface hardness, etc. of the interlayer insulation film obtained can be raised more.

[(F) component]

As epoxy resins other than the copolymer (A) which is said (F) component, it is resin which has an epoxy group (preferably oxiranyl group), and is compatible with the other component contained in the radiation sensitive resin composition of this invention ( It does not restrict | limit unless there is an effect on phase. As preferable (F) component, a bisphenol A epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, a cyclic aliphatic epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, for example And resins (co) polymerized with a heterocyclic epoxy resin and glycidyl methacrylate. Among these, bisphenol-A epoxy resin, cresol novolak-type epoxy resin, glycidyl ester type epoxy resin, etc. are especially preferable.

The use ratio of (F) component is 30 mass parts or less with respect to 100 mass parts of (A) alkali-soluble resin, More preferably, it is 1-30 mass parts. By containing (F) component in the ratio of 1-30 mass parts, heat resistance, surface hardness, etc. of an interlayer insulation film can be improved further.

In addition, although copolymer (A) can also be called "epoxy resin", a copolymer (A) differs from (F) component in the point which has alkali solubility. (F) component is alkali insoluble.

[(G) Adhesive Aids]

In the radiation sensitive resin composition of this invention, in order to improve the adhesiveness with a base | substrate more, (G) adhesion | attachment adjuvant can also be used. As such (G) adhesion | attachment adjuvant, a functional silane coupling agent is used preferably, For example, the silane couple which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group (preferably an oxiranyl group), etc. A ring agent is mentioned. Specifically, for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ -Glycidoxy propyl trimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyl trimethoxysilane, etc. are mentioned.

Such (G) adhesion | attachment adjuvant is used with respect to 100 mass parts of (A) alkali-soluble resin, Preferably it is 20 mass parts or less, More preferably, it is 1-20 mass parts, More preferably, it is used in the quantity of 3-15 mass parts. do. (G) When the use ratio of an adhesive adjuvant is 1-20 mass parts, adhesiveness with a base becomes the best.

[(H) radical scavenger]

The said (H) radical scavenger can be used for the purpose of making the film thickness of the interlayer insulation film formed more uniform, while improving the storage stability of the radiation sensitive resin composition obtained. As such a (H) radical scavenger, a hindered phenol compound, a hindered amine compound, an alkyl phosphate compound, a compound containing a sulfur atom (except an alkyl phosphate compound), etc. can be used, for example.

As these specific examples, as said hindered phenolic compound, for example, pentaerythritol tetrakis [3- (3,5-di-tert- butyl- 4-hydroxyphenyl) propionate], thiodiethylene bis [3] -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1 , 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N'-hexane-1,6-diylbis [3- ( 3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 3,3 ', 3 ", 5', 5" -hexa-tert-butyl- alpha, alpha ', alpha "-(mesitylene -2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis ( Oxyethylene) bis [3- (5-tert- butyl- 4-hydroxy-m-tolyl) propionate, hexamethylene bis [3- (3,5-di) -Tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine- 2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris ((4-tert-butyl-3-hydroxy-2,6-xyllin) methyl] -1,3, 5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5- And triazine-2-ylamine) phenol and 1,3,5-tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) isocyanuric acid.

As these commercial items, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330 (above, manufactured by ADEKA); sumilizer GM, sumilizer GS, sumilizer MDP-S, sumilizer BBM-S, sumilizer WX-R, sumilizer GA-80 (above, manufactured by Sumitomo Chemical Co., Ltd.); IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1098, IRGANOX 1135, IRGANOX 1330, IRGANOX 1726, IRGANOX 1425WL, IRGANOX 1520L, IRGANOX 245, IRGANOX 259, IRGANOX 3114, IRGANOX 565, IRGAMOD 2 ;

YOSHINOX BHT, YOSHINOX BB, YOSHINOX 2246G, YOSHINOX 425, YOSHINOX 250, YOSHINOX 930, YOSHINOX SS, YOSHINOX TT, YOSHINOX 917, YOSHINOX 314 (or more)

As said hindered amine compound, for example, tetrakis (2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate and bis (1-octyloxy-) 2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1 , 1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, and the like, and examples of commercially available products thereof include ADK STAB LA-52, ADK STAB LA57, ADK STAB LA-62, and ADK STAB. LA-67, ADK STAB LA-63P, ADK STAB LA-68LD, ADK STAB LA-77, ADK STAB LA-82, and ADK STAB LA-87 (above, manufactured by ADEKA);

sumilizer 9A (manufactured by Sumitomo Chemical Co., Ltd.);

CHIMASSORB 119FL, CHIMASSORB 2020FDL, CHIMASSORB 944FDL, TINUVIN 622LD, TINUVIN 123, TINUVIN 144, TINUVIN 765, and TINUVIN 770DF (above, manufactured by Chiba Specialty Chemicals Co., Ltd.).

As said alkyl phosphate compound, for example, butylidenebis {2-tert- butyl- 5-methyl- p-phenylene} -P, P, P, P, P- tetratridecylbis (phosphine), distea Ryl pentaerythritol diphosphite, 2,2'- methylenebis (4,6-di-tert- butyl- phenyloxy) (2-ethylhexyloxy) phosphorus, tris (2, 4-di-tert- Butylphenyl) phosphite, 3, 9-bis (2, 6- di-tert- butyl- 4-methylphenoxy)-2, 4, 8, 10- tetraoxa-3, 9- diphosphaspiro [5.5] Undecane etc. are mentioned, As these commercial items, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP- 10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, ADK STAB TPP (above, manufactured by ADEKA); IRGAFOS 168 (made by Chiba Specialty Chemicals Co., Ltd.), etc. are mentioned.

Examples of the compound containing the sulfur atom include pentaerythritol tetrakis (3-laurylthiopropionate), di (propionic acid-n-tridecanyl) sulfide, thiodiethylenebis [3- (3,5) -Di-tert-butyl-4-hydroxyphenyl) propionate] and the like, and thioethers can be used. As a commercial item of a thioether, For example, ADK STAB AO-412S and ADK STAB AO-503 (above, ADEKA make); sumilizer TPL-R, sumilizer TPM, sumilizer TPS, sumilizer TP-D, sumilizer MB (above, Sumitomo Chemical Co., Ltd. make); IRGANOX PS800FD, IRGANOX PS802FD, and IRGANOX 1035 (above, Chiba Specialty Chemicals Co., Ltd. product); DLTP, DSTP, DMTP, DTTP (above, Apia Corporation) etc. are mentioned.

These (H) radical scavengers can be used individually or in combination of 2 or more types.

The (H) radical scavenger can be used in a proportion of 15 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin, preferably in the range of 0.01 to 15 parts by mass, and more preferably 1 to 10 parts by mass. By using in the range, the effect of the (H) radical scavenger can be exhibited effectively, without impairing the radiation sensitivity of the radiation sensitive resin composition obtained, and it is preferable.

<Preparation of a radiation sensitive resin composition>

The radiation sensitive resin composition of this invention is said (A) alkali-soluble resin, a compound (B), and a copolymer (C), or (A) alkali-soluble resin, a compound (B), and a copolymer (C), and the said It is prepared by uniformly mixing other ingredients such as. The radiation-sensitive resin composition of the present invention is preferably dissolved in a suitable solvent and used in a solution state. For example, the radiation sensitive resin composition of a solution state can be prepared by mixing (A) alkali-soluble resin, a compound (B), a copolymer (C), and the other component added arbitrarily at a predetermined ratio.

As a solvent used for preparation of the radiation sensitive resin composition of this invention, (A) alkali-soluble resin, a compound (B), a copolymer (C), and each component of the other component mix | blended arbitrarily are melt | dissolved uniformly, 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 manufacturing the above-mentioned copolymer (A) is mentioned.

Among these solvents, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycol are preferably used in view of solubility of each component, reactivity with each component, ease of coating film formation, and the like. Among these, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, di Ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxy propionate, and ethoxy propionate can be used especially preferably.

Moreover, in order to raise the in-plane uniformity of a film thickness with the said solvent, you may use together a high boiling point solvent. As a high boiling point solvent which can be used together, N-methylformamide, N, N- dimethylformamide, N-methylformanilide, N-methylacetamide, N, N- dimethylacetamide, N-methylpi Ralidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, male Diethyl acid, gamma -butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like. Among them, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

When using a high boiling point solvent together as a solvent of the radiation sensitive resin composition of this invention, the usage-amount is 1-40 mass% with respect to solvent whole quantity, More preferably, it can be 3-30 mass%. . When the usage-amount of a high boiling point solvent is 1-40 mass%, the film thickness uniformity of a coating film becomes favorable and patterning becomes favorable.

When preparing the radiation-sensitive resin composition of the present invention in a solution state, components other than the solvent occupied in the solution (that is, (A) alkali-soluble resin, compound (B) and copolymer (C), and others optionally added) Although the ratio of the total amount of components) can be arbitrarily set according to a purpose of use, the value of a desired film thickness, etc., Preferably it is 5-50 mass%, More preferably, it is 10-40 mass%, More preferably, it is 15- It is 35 mass%.

The composition solution thus prepared may be used for use after being filtered using a Millipore filter or the like having a pore size of about 0.2 μm.

<Method of Forming Interlayer Insulating Film>

Next, the method of forming an interlayer insulation film is described using the radiation sensitive resin composition of this invention. The method for forming the interlayer insulating film of the present invention is characterized by including the following steps in the order described below.

(1) process of forming the coating film of the radiation sensitive resin composition of this invention on a board | substrate,

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

(3) the developing step;

(4) heating step.

[(1) Step of Forming Coating Film of Radiation-Resistant Composition of the Present Invention on Substrate]

In the process of said (1), the radiation-sensitive resin composition of this invention is apply | coated to the surface of a board | substrate, Preferably it carries out prebaking, removes a solvent, forms a coating film, and performs a postbaking further, a coating film To cure.

As a kind of board | substrate which can be used for formation of an interlayer insulation film, a glass substrate, a silicon wafer, and the board | substrate with which various metal was formed in these surfaces are mentioned, for example.

It does not specifically limit as a coating method of a resin composition solution, For example, appropriate methods, such as a spray method, a roll coating method, a spin coating method (spin coating method), the slit coating method, the bar coating method, the inkjet method, can be employ | adopted. The spin coating method and the slit coating method are preferable. In particular, when the slit coating method is adopted, the advantageous effect of the present invention can be exhibited to the maximum, which is preferable.

The conditions of prebaking and postbaking should be appropriately set according to the kind, usage ratio, etc. of each component, respectively. Prebaking can be performed, for example at 70-90 degreeC on conditions for about 1 to 15 minutes. Post-baking can be performed by appropriate heating apparatuses, such as a hotplate and a clean oven. As temperature of a postbaking, 120-250 degreeC is preferable. As a time of postbaking, it is preferable to carry out for 30 to 90 minutes each when it uses a hot oven as a heating apparatus for 5 to 30 minutes, and when using a clean oven as a heating apparatus.

The film thickness of the coating film formed in this way becomes like this. Preferably it is 0.1-8 micrometers, More preferably, it is 0.1-6 micrometers, More preferably, it is 0.1-4 micrometers.

[(2) Step of irradiating at least part of the coating film with radiation]

In the process of said (2), radiation is irradiated to the formed coating film through the mask which has a predetermined | prescribed pattern. As radiation used at this time, an ultraviolet-ray, an ultraviolet-ray, etc. are mentioned, for example.

As said ultraviolet-ray, g line | wire (wavelength 436 nm), i line | wire (wavelength 365 nm), etc. are mentioned, for example. As far ultraviolet rays, KrF excimer laser etc. are mentioned, for example. Among these, ultraviolet rays are preferable, and among them, radiation containing at least one kind of bright lines selected from the group consisting of g rays and i rays is particularly preferable.

As an irradiation amount of radiation, it is preferable to set it as 1,500-3,000 J / m <2>. Moreover, if the radiation sensitive resin composition of this invention is used, even if the irradiation amount of this radiation is 2,000 J / m <2> or less, a desired pattern can be formed, Furthermore, even if this value is 1,700 J / m <2> or less It has the advantage of forming a desired pattern.

[(3) Developing Step]

Subsequently, in the process of (3), it develops using a developing solution with respect to the coating film after said irradiation, and patterning is performed by removing the irradiation part of radiation.

As a developing solution used for the developing process, aqueous solution of alkali (basic compound), such as sodium hydroxide, potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, can be used, for example. Moreover, the aqueous solution which added water-soluble organic solvents, such as methanol and ethanol, and surfactant in an appropriate amount in the said aqueous alkali solution, or the various organic solvent which melt | dissolves the composition of this invention can be used as a developing solution.

As the developing method, for example, a suitable method such as a puddle method, a dipping method, a rocking dipping method or a shower method can be used. Although image development time changes with the composition of a radiation sensitive resin composition, it can be set as 30 to 120 second, for example.

In addition, since the peeling occurs in the pattern formed when the developing time exceeds about 20-25 second from the optimal value, the radiation-sensitive resin of the present invention was required to strictly control the developing time. In the case of the composition, even if the excess time from the optimum developing time is 30 seconds or more, good pattern formation is possible, and there is an advantage in product yield.

(3) After the developing step, it is preferable to perform a rinse treatment by, for example, running water washing, and further irradiate the entire surface of the patterned coating film with a high pressure mercury lamp or the like (after exposure). It is preferable to perform the decomposition | disassembly process of the (B) 1, 2- quinonediazide compound which remains in a patterned coating film by this. The radiation dose in this post-exposure process becomes like this. Preferably it is about 2,000-5,000 J / m <2>.

[(4) heating process]

In the process of (4), the hardening process of a patterned coating film is performed by heat processing (post-baking process) by heating apparatuses, such as a hotplate and oven. The heating temperature in this process (4) is 120-250 degreeC, for example. Although heating time changes with kinds of heating apparatus, it can be set as 5 to 30 minutes, for example, when carrying out heat processing on a hotplate, and 30 to 90 minutes when carrying out heat processing in an oven. At this time, the step baking method etc. which perform two or more heating processes can also be used.

In this manner, a patterned thin film corresponding to the target interlayer insulating film can be formed on the surface of the substrate.

<Interlayer Insulation Film>

The interlayer insulating film formed as described above has excellent adhesion to the substrate, excellent heat resistance, solvent resistance, transparency, and the like, and has a low dielectric constant, as is apparent from the examples below. It can be used suitably as.

(Example)

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. In addition, below, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured by the gel permeation chromatography (GPC) by the following conditions.

Measuring device: Toso Corporation, "HLC8220 system"

Separation column: Tosoh Co., Ltd. make and use four TSK gel GMH _HR- N connected in series

Column temperature: 40 degrees Celsius

Elution solvent: Tetrahydrofuran (made by Wako Pure Chemical Industries, Ltd.)

Flow rate: 1.0mL / minute

Sample concentration: 1.0 mass%

Sample injection volume: 100 μm

Detector: parallax refractometer

Standard material: Monodisperse polystyrene

In addition, the solution viscosity of the radiation sensitive resin composition was measured at 30 degreeC using the E-type viscosity meter by Tokyo Keiki Co., Ltd. make.

<Synthesis of Copolymer (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 diethylene glycol ethylmethyl ether were placed. 16 parts by mass of methacrylic acid, 16 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 20 parts by mass of 2-methylcyclohexyl acrylate, and 40 parts by mass of glycidyl methacrylate 10 mass parts of styrene and 3 mass parts of (alpha) -methylstyrene dimers were added, and nitrogen was substituted, and stirring was started slowly. The polymer solution containing a copolymer (A-1) was obtained by raising the temperature of a solution to 70 degreeC and holding this temperature for 4 hours.

The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A-1) was 8,000, and molecular weight distribution (Mw / Mn) was 2.3. In addition, the solid content concentration (The ratio which the mass of the polymer contained in a polymer solution occupies in the total mass of a polymer solution. Hereafter the same) of the polymer solution obtained here was 34.4 mass%.

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethylmethyl ether were placed. Then, 11 parts by mass of methacrylic acid, 12 parts by mass of tetrahydrofurfuryl methacrylate, 40 parts by mass of glycidyl methacrylate, 15 parts by mass of N-cyclohexylmaleimide, 10 parts by mass of n-lauryl methacrylate, 10 mass parts of (alpha) -methyl- p-hydroxy styrenes, and 3 mass parts of (alpha) -methylstyrene dimers were put, and nitrogen substitution was performed, and stirring was started slowly. The polymer solution containing a copolymer (A-2) was obtained by raising the temperature of a solution to 70 degreeC and holding this temperature for 5 hours.

The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A-2) was 8,000, and molecular weight distribution (Mw / Mn) was 2.3. In addition, solid content concentration of the polymer solution obtained here was 31.9 mass%.

<Synthesis of Copolymer (C)>

Synthesis Example 3

28.4 parts by mass of the compound represented by the formula (c1-1) as the compound (c1), and NK-ester M-90G as the compound (c2) in a glass flask equipped with a stirring device, a condenser, and a thermometer (brand name, Shinnakamuraka 20.7 parts by mass of Kaku Co., Ltd., 18.1 parts by mass of the compound represented by the following formula (c3-1-1-1) as the compound (c3), and 5.9 parts by mass of methyl methacrylate as the compound (c4) and 2-ethyl 23.5 mass parts of hexyl acrylate, 3.4 mass parts of compounds which methacrylated both ends of tetramethylene glycol as a (c5) compound, and 414 mass parts of isopropyl alcohol as a solvent are put, and it is a polymerization initiator in reflux in nitrogen gas stream. After adding 0.7 mass part of 2,2'- azobisisobutyronitrile as a 4 mass part of lauryl mercaptans as a chain transfer agent, and copolymerizing by refluxing at 75 degreeC for 8 hours, copolymer (C-1) was made into The solution containing was obtained. Then, the copolymer (C-1) was isolated by removing a solvent on 70 degreeC or less heating conditions using the evaporator.

The number average molecular weight (Mn) of the obtained copolymer (C-1) was 2,800, the weight average molecular weight (Mw) was 5,300, and molecular weight distribution (Mw / Mn) was 1.9.

(In the formula, Me is a methyl group.)

Synthesis Example 4

In the said synthesis example 3, the copolymer (C-2) was obtained similarly to the synthesis example 3 except having made the addition amount of the lauryl mercaptan as a chain transfer agent into 1 mass part.

The number average molecular weight (Mn) of the obtained copolymer (C-2) was 4,700, the weight average molecular weight (Mw) was 11,000, and molecular weight distribution (Mw / Mn) was 2.3.

Synthesis Example 5

In the said Synthesis example 3, copolymer (C-3) was carried out similarly to the synthesis example 3 except having used lauryl mercaptan as a chain transfer agent, and making copolymerization temperature and time into 73 degreeC and 10 hours, respectively. Got.

The number average molecular weight (Mn) of the obtained copolymer (C-3) was 5,600, the weight average molecular weight (Mw) was 21,000, and molecular weight distribution (Mw / Mn) was 3.8.

Synthesis Example 6

In a glass flask equipped with a stirring device, a condenser, and a thermometer, 39.4 parts by mass of the compound represented by the formula (c1-1) as the compound (c1), and NK-ester M-90G (Shinnakamura Kagaku) as the compound (c2) 21.6 mass parts of compounds represented by said formula (c3-1-1-1) as 31.6 mass parts and (c3) compounds, and 414 mass parts of isopropyl alcohol as a solvent, and reflux in nitrogen gas stream After adding 0.7 mass part of 2,2'- azobisisobutyronitrile as a polymerization initiator, and 4 mass parts of lauryl mercaptans as a chain transfer agent, copolymerization is carried out by refluxing at 75 degreeC for 8 hours, and a copolymer (C) The solution containing -4) was obtained. Then, the solvent was removed on 70 degreeC or less heating conditions using the evaporator, and the copolymer (C-4) was isolated.

The number average molecular weight (Mn) was 3,000, and the weight average molecular weight (Mw) of the molecular weight of the obtained copolymer (C-4) was 6,000. In addition, the molecular weight distribution (Mw / Mn) was 2.0.

Synthesis Example 7

28.4 parts by mass of the compound represented by the formula (c1-1) as the compound (c1) and (c2) as NK-ester M-90G (Shin Nakamura Kagaku) in a glass flask equipped with a stirring device, a condenser and a thermometer. 20.7 parts by mass of the company) and 21.5 parts by mass of the compound represented by the formula (c3-1-1-1) as the compound (c3), 5.9 parts by mass of methyl methacrylate and 2-ethylhexyl as the compound (c4). 23.5 parts by mass of acrylate and 414 parts by mass of isopropyl alcohol are added as a solvent, and lauryl mercaptan 4 as 0.7 parts by mass of 2,2'-azobisisobutyronitrile and a chain transfer agent under reflux in a nitrogen gas stream. After adding a mass part, it copolymerized by refluxing at 75 degreeC for 8 hours, and obtained the solution containing copolymer (C-5). Then, the solvent was removed on 70 degreeC or less heating conditions using the evaporator, and the copolymer (C-5) was isolated.

The number average molecular weight (Mn) of the obtained copolymer (C-5) was 2,600, the weight average molecular weight (Mw) was 5,000, and molecular weight distribution (Mw / Mn) was 1.9.

Example 1

[Preparation of radiation sensitive resin composition]

The solution containing the copolymer (A-1) synthesized in Synthesis Example 1 as the copolymer (A) was an amount equivalent to 100 parts by mass (solid content) of the copolymer (A-1), and (B) as a compound. , 4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid 30 parts by mass of a condensate (B-1) with chloride (2.0 mol) and 0.5 parts by mass of the copolymer (C-1) obtained in Synthesis Example 3 as the (C) copolymer were further mixed with diethylene glycol methyl as a solvent. After adding ethyl ether, the radiation sensitive resin composition (S-1) was prepared by filtering by the membrane filter of 0.2 micrometer of diameters.

[Performance Evaluation as an Interlayer Insulation Film]

(1) Appearance Evaluation of Coating Film

On the 550 x 650 mm chromium film-forming glass, the radiation-sensitive resin composition (S-1) prepared above was applied using a slit die coater (manufactured by Tokyo Okako Co., Ltd., model "TR632105-CL"). After setting to 100 Pa and removing a solvent under vacuum, it prebaked further at 90 degreeC for 2 minutes, and formed the coating film of 1.0 micrometer in film thickness.

In this coating film, the external appearance was observed visually under the sodium lamp. At this time, the appearance of the fog was observed as a phenomenon of "fogging" the unevenness generated in the entire coating film, and the nonuniformity derived from the proximity pin of the prebaking furnace as the "pin trace". The case where all of these nonuniformities were hardly seen was evaluated as "good" and the case where either one of these nonuniformities was seen a little "slightly poor" and clearly seen as "bad." The evaluation results are shown in Table 1.

(2) evaluation of sensitivity

Hexamethyldisilazane (HMDS) was apply | coated on 550x650 mm chromium film-forming glass, and it heated at 60 degreeC for 1 minute, and HMDS process was performed.

After apply | coating the radiation sensitive resin composition (S-1) prepared above on the chromium film-forming glass after this HMDS process using the slit die coater "TR632105-CL", setting the arrival pressure to 100 Pa, and removing a solvent under vacuum, Furthermore, the prebaking was carried out at 90 degreeC for 2 minutes, and the coating film of 3.0 micrometers in film thicknesses was formed.

After irradiating radiation with a variable amount of exposure using Canon MPA-600FA exposure machine manufactured by Canon Inc. via the mask which has a pattern of a line and space (10 to 1) of 3.0 micrometers in the obtained coating film, it is shown in Table 1 It developed by the puddle method at 25 degreeC in the tetramethylammonium hydroxide aqueous solution of the density | concentration described. Here, developing time was made into 80 second when the developing solution whose tetramethylammonium hydroxide concentration is 0.4 mass% is used for 80 second, and when using the developing solution which is 2.38 mass%. Subsequently, flowing water wash | cleaned with ultrapure water for 1 minute, and after that, it dried and the pattern was formed on the chromium film-forming glass substrate after HMDS process.

At this time, the exposure amount required in order for the space pattern of the line-and-space (10: 1) of 3.0 micrometers to melt | dissolve completely was investigated. Table 1 shows this value as the sensitivity. When this value is 2,000 J / m <2> or less, it can be said that a sensitivity is favorable, and when it is 1,700 J / m <2> or less, it can be said that a sensitivity is very excellent.

(3) Evaluation of developing margin

The HMDS process of the chromium film-forming glass was performed like the thing in said "(2) evaluation of sensitivity". On the chromium film-forming glass after this HMDS process, the radiation sensitive resin composition (S-1) prepared above was apply | coated using the slit die coater "TR632105-CL", the arrival pressure was set to 100 Pa, and the solvent was removed by vacuum drying. Thereafter, the film was further baked at 90 ° C. for 2 minutes to form a coating film having a film thickness of 3.0 μm.

Of the sensitivity irradiated by said "(2) evaluation of sensitivity" using the MPA-600FA exposure machine manufactured by Canon Inc. via the mask which has a pattern of a line and space (10 to 1) of 3.0 micrometers in the obtained coating film. Exposure was performed at the exposure amount corresponding to a value, and it developed by the puddle method at 25 degreeC using the tetramethylammonium hydroxide aqueous solution of the density | concentration shown in Table 1 as a variable, and developing time. Subsequently, flowing water wash | cleaned with ultrapure water for 1 minute, and after that, the pattern was formed on the chromium film-forming glass substrate after HMDS process.

At this time, the developing time required for the line line width to be 3 µm is shown in Table 1 as the optimum developing time. In addition, when developing was further continued from this optimum developing time, the time until the line pattern of 3.0 micrometers was peeled off was measured, and this time was shown in Table 1 as a developing margin. When this value is 30 seconds or more, the development margin can be said to be good.

(4) Evaluation of solvent resistance

On the 550x650 mm chromium film-forming glass, the radiation-sensitive resin composition (S-1) prepared above was applied using a slit die coater (manufactured by Tokyo Okako Corp., model "TR632105-CL") to obtain the arrival pressure. After setting to 100 Pa and removing a solvent under vacuum, it prebaked further at 90 degreeC for 2 minutes, and formed the coating film. This coating film was exposed to a cumulative irradiation amount of 9,000 J / m 2 using a Canon Co., Ltd., MPA-600FA exposure machine, and then heated in a clean oven at 220 ° C. for 1 hour to form a chromium film. A cured film with a film thickness of 3.0 µm was formed.

The film thickness (T1) of the cured film obtained here was measured. And after immersing the chromium film-forming glass substrate in which this cured film was formed for 20 minutes in the dimethyl sulfoxide temperature-controlled at 70 degreeC, the film thickness t1 of a cured film was measured again, and the film thickness change rate by immersion ｛| t1-T1 / T1'x100 [%] was calculated. This result is shown in Table 1. When this value is 5% or less, it can be said that solvent resistance is favorable.

(5) Evaluation of heat resistance

A cured film with a film thickness of 3.0 µm was formed on the chromium film-forming glass in the same manner as in the above "(4) Evaluation of solvent resistance".

The film thickness (T2) of the cured film obtained here was measured. Subsequently, after further heating the chromium film-formed glass substrate on which the cured film was formed at 240 ° C. for 1 hour in a clean oven, the film thickness t2 of the cured film was measured again, and the film thickness change rate due to additional heating ｛| t2-T2 | / T2xx100 [%] was calculated. This result is shown in Table 1. When this value is 5% or less, it can be said that heat resistance is favorable.

(6) evaluation of transparency

In the above "(4) Evaluation of solvent resistance", it hardened on the glass substrate similarly except having used 550x650 mm glass substrate "NA35 (made by NH Techno Glass Co., Ltd.") instead of the chromium film-forming glass substrate. Formed a film. The light transmittance of the glass substrate having this cured film was measured using a spectrophotometer "150-20 type double beam (manufactured by Hitachi Seisakusho Co., Ltd.)" with a wavelength of 400 to 800 nm in terms of a glass substrate having no protective film as a reference side. Measured. Table 1 shows the values of the minimum light transmittance at that time. When this value is 90% or more, it can be said that transparency is favorable.

(7) Evaluation of film thickness uniformity

The cured film was formed on the glass substrate similarly to said "(6) transparency evaluation". About this cured film, the film thickness was measured in 20 measuring points, and the film thickness uniformity was computed by the following formula.

Uniformity (%) of film thickness = (maximum value-minimum value of coating film thickness) * 100 / ((average of 20 coating film thicknesses) * 2)

If uniformity of the coating film thickness computed in this way is 1% or less, it can be said that uniformity is favorable.

In addition, the said 20 measurement point was determined as follows. That is, the inner region (450x550mm) excluding the 50mm range from each of the long side and short sides of the substrate (550x650mm) is used as the measurement area, and each 40 mm interval in a straight line in the long side direction and the short side direction in the region. Each 10 points (20 points in total) were determined, and these were made into measurement points.

(8) Evaluation of dielectric constant

The radiation sensitive resin composition (S-1) prepared above was apply | coated by the spin coating method on the SUS304 board | substrate which grind | polished by the sisal buff and smoothed the surface, and the arrival pressure is 100 Pa. After setting to remove the solvent under vacuum, it prebaked further at 90 degreeC for 2 minutes, and formed the coating film of 3.0 micrometers in film thicknesses. The cured film was formed on the SUS board | substrate by exposing so that the accumulated irradiation amount might be 9,000 J / m <2> by the Canon Co., Ltd. product and the MPA-600FA exposure machine, and heating this board | substrate at 220 degreeC in clean oven for 1 hour. The Pt / Pd electrode pattern was formed on this cured film by the vapor deposition method, and the sample for dielectric constant measurement was produced.

About the board | substrate which has this electrode pattern, the dielectric constant was measured by the CV method using the HP16451B electrode manufactured by Yokogawa Hewlett-Packard Co., Ltd., and the HP4284A fresh LCR meter at the frequency of 10 kHz. The measurement results are shown in Table 1. When this value is 3.9 or less, it can be said that the permittivity is good.

Examples 2-7, Comparative Examples 1-3

[Preparation of radiation sensitive resin composition]

In Example 1, it carried out similarly to Example 1 except having performed the kind and usage-amount of each component of a radiation sensitive resin composition as Table 1, respectively, and a radiation sensitive resin composition (S-2)-( S-7) and (s-1)-(s-3) were prepared.

It evaluated using these compositions.

B-1 as the compound (B) used in these Examples and the comparative example is 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene ] A condensate of bisphenol (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol).

In Comparative Examples 1 and 2, the following surfactants were used instead of the copolymer (C).

c-1 (comparative example 1): Silicone type surfactant (Toray Dow Corning Silicone Co., Ltd. make, brand name: SH-193)

c-2 (comparative example 2): Fluorine type surfactant (Neosu Co., Ltd. make, brand name)

FTERGENT 222F)

In Comparative Example 3, neither a copolymer (C) nor a surfactant was used.

[Performance Evaluation as an Interlayer Insulation Film]

In Example 1, instead of the radiation sensitive resin composition (S-1), the radiation sensitive resin compositions (S-2) to (S-7) and (s-1) to (s-3) Various evaluation was performed similarly to Example 1 except having used each. The evaluation results are shown in Table 1.

Examples 8-10

In Example 1, after mixing the (A) copolymer, the (B) compound, and the (C) copolymer, and before the addition of the solvent, in Example 8, 1,3,5-tris (3 ', 5) '-Di-tert-butyl-4'-hydroxybenzyl) isocyanuric acid (brand name "ADK STAB AO-20", manufactured by ADEKA Corporation) in Example 9, 1,3,5-trimethyl -2,4,6-tris (3,5-di-tert-butyl- 4-hydroxybenzyl) benzene (brand name "ADK STAB AO-330", the product made by ADEKA Corporation) is a disc in Example 10 Tearyl pentaerythritol diphosphite (trade name "ADK STAB PEP-8", manufactured by ADEKA Corporation) was added in the same manner as in Example 1 except that 2 parts by mass of 100 parts by mass of the copolymer (A) were further added. Radioactive resin composition (S-8)-(S-10) was prepared and evaluated.

As a result, in all of Examples 8-10, the external appearance of the coating film was "good", and the sensitivity, image development margin, solvent resistance, heat resistance, transparency, and dielectric constant showed the same value as Example 1, respectively. In addition, the film thickness uniformity was 0.45% in Example 8, 0.48% in Example 9, and 0.43% in Example 10. In FIG.

Claims (9)

(A) alkali-soluble resin,
(B) 1,2-quinonediazide compound, and
(C) (c1) a compound represented by the following formula (1 ⁰ ),
(c2) a compound represented by the following General Formula (2 ⁰ ), and
(c3) Polymerizable unsaturated compound which has group represented by following General formula (3)
Copolymer of polymerizable unsaturated compounds
A radiation sensitive resin composition characterized by containing.
CH ₂ = CR ¹ COO-C _α H _{2 α} -C _β F _{2β + 1} (1 ⁰ )
(In formula (1 ⁰ ), R ¹ is a hydrogen atom or a methyl group, α is an integer of 0 to 6, and β is an integer of 1 to 20.)
CH ₂ = CR ² COO- (C _γ H _{2 γ} -O) _a -R ³ (2 ⁰ )
(In formula (2 ⁰ ), R ² is a hydrogen atom or a methyl group, R ³ is an alkyl group having 1 to 12 carbon atoms, γ is 2 or 3, a is the number of repeating units, and the number average thereof is 1 to 30). .)
<Formula 1>

(In formula (3), R <^4> , R <^5> , R <^6> , R <^7> and R <^8> are respectively independently group represented by a C1-C20 alkyl group, a phenyl group, or the following general formula (4), b is an integer of 0 to 3)
<Formula 2>

(In formula (4), R <^9> , R <^10> and R <^11> is respectively independently a C1-C20 alkyl group or a phenyl group, and c is an integer of 0-3.) The method of claim 1,
Polymeric unsaturation in which the said (C) copolymer contains the polymerizable unsaturated compound which has a (c4) C1-C8 alkyl group other than the said compound (c1), a compound (c2), and a compound (c3) further A radiation sensitive resin composition which is a copolymer of a compound. The method of claim 2,
In addition to the compound (c1), the compound (c2), the compound (c3) and the compound (c4), the copolymer (C) may further include a polymerizable unsaturated compound having two or more unsaturated bonds in (c5) 1 molecule. A radiation sensitive resin composition which is a copolymer of the polymerizable unsaturated compound containing. The method of claim 3,
The compound (c1) is a compound represented by the following formula (1),
The compound (c2) is a compound represented by the following general formula (2), further
(C) the copolymer,
25-35 mass% of compound (c1),
20-30 mass% of compound (c2),
15-20 mass% of compound (c3),
25-35 mass% of compound (c4), and
1-5 mass% of compound (c5)
A radiation sensitive resin composition which is a copolymer of the polymerizable unsaturated compound which consists of.
CH ₂ = CR ¹ COOCH ₂ CH ₂ C ₈ F ₁₇ (1)
(In formula (1), R ¹ is as defined in the formula (1 ⁰ ).)
CH ₂ = CR ² COO (C ₂ H ₄ O) _a R ³ (2)
(Formula (2) of, R ² and R ³ are, respectively, as defined in the formula ^(20), the number average value of a number of repeating units is 4 to 12). The method according to any one of claims 1 to 4,
(A) alkali-soluble resin,
(a1) at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and
(a2) Polymerizable unsaturated compound having an epoxy group
A radiation sensitive resin composition, which is a copolymer of a monomer comprising a. It formed with the radiation sensitive resin composition in any one of Claims 1-4, The interlayer insulation film characterized by the above-mentioned. The following process is included in the procedure described below, The formation method of the interlayer insulation film.
(1) Process of apply | coating the radiation sensitive resin composition of any one of Claims 1-4 on a board | substrate, and forming a coating film,
(2) irradiating at least a part of the coating film with radiation;
(3) the developing step;
(4) heating step. It formed by the formation method of the interlayer insulation film of Claim 7, The interlayer insulation film characterized by the above-mentioned. The method according to any one of claims 1 to 4,
(A) alkali-soluble resin,
(a1) at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and
(a2) In addition to the polymerizable unsaturated compound having an epoxy group, further
(a3) A radiation sensitive resin composition which is a copolymer of the monomer containing the unsaturated compound which has radical polymerizability.