JP5504824B2 - Positive radiation-sensitive resin composition, interlayer insulating film and method for forming the same - Google Patents

Description

  The present invention relates to a positive-type radiation-sensitive resin composition suitable as a material for forming an interlayer insulating film such as a liquid crystal display element (LCD), an interlayer insulating film formed from the composition, and an interlayer insulating film It relates to a forming method.

  In an electronic component such as a thin film transistor (hereinafter referred to as “TFT”) type liquid crystal display element, magnetic head element, integrated circuit element, and solid-state imaging element, interlayer insulation is generally used in order to insulate between wirings arranged in layers. A membrane is provided. As a material for forming the interlayer insulating film, a positive radiation sensitive resin composition is widely used because the number of steps for obtaining a required pattern shape is small and a material having sufficient flatness is preferable. (See Patent Document 1).

  Among the electronic components, for example, a TFT liquid crystal display element is manufactured through a process of forming a transparent electrode film on an interlayer insulating film and forming a liquid crystal alignment film thereon. In the manufacture of such a TFT type liquid crystal display element, the interlayer insulating film is exposed to high temperature conditions in the transparent electrode film forming process, exposed to a resist stripping solution used for electrode pattern formation, Since it is exposed to light of a wavelength, sufficient heat resistance, solvent resistance and light resistance are required. In addition, since the interlayer insulating film may be subjected to a dry etching process, sufficient resistance to dry etching is required (see Patent Document 2 and Patent Document 3).

  In recent years, TFT-type liquid crystal display elements have a tendency to increase screen size, increase brightness, increase definition, increase response speed, reduce thickness, and the like. Therefore, the radiation-sensitive resin composition for forming an interlayer insulating film used in TFT-type liquid crystal display elements is highly sensitive to radiation, and the formed interlayer insulating film has a low dielectric constant and a high light transmittance. In such cases, superior performance is required compared to the prior art. Further, in the development process when forming the interlayer insulating film, if the development time is slightly longer than the optimum time, the developer permeates between the pattern and the substrate, and the pattern is likely to peel off from the substrate. . Therefore, in the development process when forming the interlayer insulating film, it is necessary to strictly control the development time, which is problematic in terms of product yield.

  Thus, in forming an interlayer insulating film from a radiation-sensitive resin composition, the composition is required to have high sensitivity to radiation, and in the development process when forming the interlayer insulating film Even when the development time is longer than a predetermined time, the pattern does not peel off and shows good adhesion, and the formed interlayer insulating film has heat resistance, solvent resistance, low dielectric property, light beam It is required to be excellent in transmittance, light resistance, dry etching resistance and the like. However, a radiation-sensitive resin composition that satisfies all such requirements has not been known.

JP 2001-354822 A JP 2000-241832 A JP 2005-345757 A

  The present invention has been made on the basis of the circumstances as described above, and its purpose is high in radiation sensitivity and resistance to peeling of the pattern from the substrate in the development process, as well as heat resistance, solvent resistance, and low dielectric properties. , Positive-type radiation-sensitive resin composition capable of forming an interlayer insulating film excellent in light transmittance, light resistance and dry etching resistance, an interlayer insulating film obtained from the composition, and the interlayer insulating film It is to provide a forming method.

The invention made to solve the above problems is
[A] A positive-type radiation-sensitive resin composition containing an alkali-soluble resin having a hindered amine structure and / or a hindered phenol structure, and [B] a 1,2-quinonediazide compound.

  The positive radiation sensitive resin composition contains [A] an alkali-soluble resin having a hindered amine structure and / or a hindered phenol structure, and [B] 1,2-quinonediazide compound. Interlayer insulation with high tolerance of development time (development margin) against peeling of pattern from substrate in process, and excellent heat resistance, solvent resistance, low dielectric property, light transmittance, light resistance and dry etching resistance It is possible to form a film. The “alkali-soluble resin having a hindered amine structure” herein means an amine-structure-containing alkali-soluble resin in which at least one carbon atom adjacent to the nitrogen atom of the amino group forms a tertiary group, The “alkali-soluble resin having a hindered phenol structure” means a phenol-structure-containing alkali-soluble resin in which a tertiary group is bonded to at least one benzene ring carbon atom adjacent to the bonding site of the phenolic hydroxyl group.

（式（１）中、Ｒ^１は水素原子又は炭素数１〜４のアルキル基であり、Ｒ^２〜Ｒ^５は各々独立に炭素数１〜６のアルキル基であり、Ｒ^６は水素原子又は炭素数１〜６のアルキル基であり、Ｂ_１は、単結合、−ＣＯＯ−＊又は−ＣＯＮＨ−＊であり、ｍは０〜３の整数である。但し、−ＣＯＯ−＊又は−ＣＯＮＨ−＊における各々の＊の結合手は（ＣＨ_２）_ｍの炭素と結合する。
式（２）中、Ｒ^１は水素原子又は炭素数１〜４のアルキル基であり、Ｒ^７〜Ｒ^１０は各々独立に水素原子又は炭素数１〜６のアルキル基であり、Ｒ^８及びＲ^９の少なくとも一方がｔ−ブチル基又はｔ−ペンチル基であり、Ｂ_１は、単結合、−ＣＯＯ−＊又は−ＣＯＮＨ−＊であり、ｎは０〜３の整数である。但し、−ＣＯＯ−＊又は−ＣＯＮＨ−＊における各々の＊の結合手は（ＣＨ_２）_ｎの炭素と結合する。
式（３）中、Ｒ^１は水素原子又は炭素数１〜４のアルキル基であり、Ｒ^１１は各々独立に水素原子又は炭素数１〜６のアルキル基であり、ｔは１〜４の整数であり、Ｒ^１５〜Ｒ^１８は各々独立に水素原子又は炭素数１〜６のアルキル基であり、Ｒ^１５及びＲ^１６の少なくとも一方がｔ−ブチル基又はｔ−ペンチル基であり、Ｂ_１は、単結合、−ＣＯＯ−＊又は−ＣＯＮＨ−＊であり、Ｂ_２は、単結合、−ＣＯ−、−Ｓ−、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−又は−Ｃ（ＣＨ_３）_２−であり、ｋは０〜３の整数である。但し、−ＣＯＯ−＊又は−ＣＯＮＨ−＊における各々の＊の結合手は（ＣＨ_２）_ｋの炭素と結合する。） In the positive radiation sensitive resin composition, [A] the alkali-soluble resin includes (a1) a monomer containing one or more selected from unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, and (a2) It is preferably a copolymer obtained from a monomer represented by the formula (1), a compound represented by the following formula (2), or a monomer containing one or more selected from the compound represented by the following formula (3). .

(In Formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^{2 to} R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms, and R ⁶ is a hydrogen atom or An alkyl group having 1 to 6 carbon atoms, B ₁ is a single bond, —COO— * or —CONH— *, and m is an integer of 0 to 3. However, —COO— * or —CONH— Each * bond in * is bonded to (CH ₂ ) _m carbon.
In the formula (2), R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^{7 to} R ¹⁰ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁸ and R ^At least one of ⁹ is a t-butyl group or a t-pentyl group, B ₁ is a single bond, —COO— * or —CONH— *, and n is an integer of 0 to 3. However, each * bond in —COO— * or —CONH— * is bonded to carbon of (CH ₂ ) _n .
In Formula (3), R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹¹ is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and t is an integer of 1 to 4. R ^{15 to} R ¹⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, at least one of R ¹⁵ and R ¹⁶ is a t-butyl group or a t-pentyl group, and B ₁ is , Single bond, —COO— * or —CONH— *, and B ₂ is a single bond, —CO—, —S—, —CH ₂ —, —CH (CH ₃ ) — or —C (CH ₃ ). _2- and k is an integer of 0-3. However, each * bond in —COO— * or —CONH— * is bonded to carbon of (CH ₂ ) _k . )

  [A] By using a compound having these hindered structures as a constituent of the copolymer of the alkali-soluble resin, the heat resistance, light resistance and interlayer insulation film formed from the positive radiation-sensitive resin composition The dry etching resistance can be further improved.

  In the positive radiation sensitive resin composition, the [A] alkali-soluble resin is a monomer containing (a3) an epoxy group-containing unsaturated compound in addition to the compounds represented by (a1) and (a2) above. It is preferable that the copolymer is obtained from [A] By using an epoxy group-containing unsaturated compound as a constituent of the copolymer of the alkali-soluble resin, the heat resistance and solvent resistance of the interlayer insulating film formed from the positive radiation sensitive resin composition are improved. Further improvement can be achieved.

In addition, the method of forming the interlayer insulating film of the present invention,
(1) The process of forming the coating film of the said positive type radiation sensitive resin composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) a step of developing the coating film irradiated with radiation in step (2), and (4) a step of heating the coating film developed in step (3).

  In this method, an interlayer insulation having a fine and elaborate pattern is formed by using the positive radiation sensitive composition having excellent radiation sensitivity and forming a pattern by exposure, development and heating utilizing radiation sensitivity. A film can be easily formed. The interlayer insulating film thus formed is excellent in heat resistance, solvent resistance, low dielectric property, light transmittance, light resistance and dry etching resistance. Such an interlayer insulating film can be widely used for electronic components such as a TFT type liquid crystal display element, a magnetic head element, an integrated circuit element, and a solid-state imaging element.

  The positive-type radiation-sensitive resin composition of the present invention has a high radiation sensitivity and a development margin (high adhesion in the development process) that can form a good pattern shape even if the optimum development time is exceeded in the development process. ). In addition, the positive-type radiation-sensitive resin composition can form an interlayer insulating film of an electronic component excellent in heat resistance, solvent resistance, low dielectric property, light transmittance, light resistance, and dry etching resistance. Is possible.

  The positive-type radiation-sensitive resin composition of the present invention includes [A] an alkali-soluble resin having a hindered amine structure and / or a hindered phenol structure, [B] 1,2-quinonediazide compound, and other optional components ([C] A heat-sensitive acid generating compound or a heat-sensitive base generating compound, [D] a polymerizable compound having at least one ethylenically unsaturated double bond, and the like).

[A] Alkali-soluble resin having hindered amine structure and / or hindered phenol structure The alkali-soluble resin of component [A] used in the positive radiation-sensitive resin composition contains a hindered amine structure and / or a hindered phenol structure. In addition, the resin is not particularly limited as long as the resin is soluble in an alkaline developer used in the development processing step of the positive radiation sensitive resin composition containing the component. The alkali-soluble resin as the component [A] is preferably an alkali-soluble resin having a hindered amine structure and / or a hindered phenol structure and having a carboxyl group or a carboxylic anhydride group. The alkali-soluble resin of the component [A] includes one or more selected from (a1) an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “compound (a1)”). Monomer, and (a2) one or more selected from the compound represented by the above formula (1), the compound represented by the above formula (2) or the compound represented by the above formula (3) (hereinafter referred to as “compound”) Copolymers obtained from monomers containing (sometimes referred to as (a2)) are particularly preferred. Such an alkali-soluble resin (hereinafter sometimes referred to as copolymer [A]) is a radical polymerization of a monomer containing compounds (a1) and (a2) in a solvent in the presence of a polymerization initiator. Can be manufactured.

  In addition to the compounds (a1) and (a2), the alkali-soluble resin [A] includes (a3) an epoxy group-containing unsaturated compound (hereinafter sometimes referred to as “compound (a3)”). The copolymer [A] obtained from the monomer containing can also be used. Furthermore, as the alkali-soluble resin [A], a copolymer obtained from a monomer containing an unsaturated compound other than these compounds as the compound (a4) together with the compounds (a1), (a2) and (a3) [A] can also be used.

  The compound (a1) used for obtaining the copolymer [A] is an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride having radical polymerizability. Specific examples of the compound (a1) include monocarboxylic acid, dicarboxylic acid, anhydride of dicarboxylic acid, mono [(meth) acryloyloxyalkyl] ester of polyvalent carboxylic acid, polymer having a carboxyl group and a hydroxyl group at both ends. And mono (meth) acrylates, polycyclic compounds having a carboxyl group, and anhydrides thereof.

Specific examples of these compounds (a1) are:
As monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, etc .;
As dicarboxylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;
As anhydrides of dicarboxylic acids, anhydrides of the compounds exemplified as the above dicarboxylic acids, etc .;
As mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and the like;
As a mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, ω-carboxypolycaprolactone mono (meth) acrylate and the like;
As the polycyclic compound having a carboxyl group and its anhydride, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 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 anhydride and the like can be mentioned.

  Among these compounds (a1), monocarboxylic acid and dicarboxylic acid anhydrides are preferably used. In particular, acrylic acid, methacrylic acid, and maleic anhydride are preferably used from the viewpoint of copolymerization reactivity, solubility in an aqueous alkali solution, and availability. These compounds (a1) are used individually or in combination of 2 or more types.

  The copolymer [A] is preferably 5 to 40% by mass, particularly preferably 5 to 40% by mass of the repeating units derived from the compound (a1) based on the total number of repeating units constituting the copolymer [A]. Contains 25% by mass. In the copolymer [A], the solubility of the copolymer in the aqueous alkali solution during the development step is optimized by setting the repeating unit derived from the compound (a1) within the range of 5 to 40% by mass. Can do.

  The compound (a2) used for obtaining the copolymer [A] is a compound represented by the above formula (1), a compound represented by the above formula (2), or a compound represented by the above formula (3). It is 1 or more types chosen from.

  Preferable specific examples of the compound represented by the above formula (1) include (meth) acrylic acid-2,2,6,6-tetramethyl-4-piperidinyl, (meth) acrylic acid (1,2,2, 6,6-pentamethylpiperidin-4-yl), (meth) acrylic acid (1-ethyl-2,2,6,6-tetramethylpiperidin-4-yl), (meth) acrylic acid (1-n- Propyl-2,2,6,6-tetramethylpiperidin-4-yl), (meth) acrylic acid (1-i-propyl-2,2,6,6-tetramethylpiperidin-4-yl), (meta Acrylic acid (1-n-butyl-2,2,6,6-tetramethylpiperidin-4-yl), (meth) acrylic acid (1-i-butyl-2,2,6,6-tetramethylpiperidine) -4-yl), (meth) acrylic acid (1-t-butyl) -2,2,6,6-tetramethylpiperidin-4-yl), methacrylic acid [1- (2-phenylpropyl) -2,2,6,6-tetramethylpiperidin-4-yl] and the like. Can do. Among these, (meth) acrylic acid-2,2,6,6-tetramethyl-4-piperidinyl and (meth) acrylic acid (1,2,2,6,6-pentamethylpiperidin-4-yl) Particularly preferred.

  Preferred specific examples of the compound represented by the formula (2) include 2-t-butyl-5-methyl-4-vinylphenol, 2-t-pentyl-5-methyl-4-vinylphenol, 2-t -Butyl-5-ethyl-4-vinylphenol, 2,5-di-t-butyl-4-vinylphenol, 2-t-butyl-5-methyl-4-i-propenylphenol, 2-t-butyl- 5-ethyl-4-i-propenylphenol, 2,5-di-t-butyl-4-i-propenylphenol, 2-t-butyl-5-methyl-4- (meth) acryloxyphenol, 2-t -Butyl-5-ethyl-4- (meth) acryloxyphenol, 2,5-di-t-butyl-4- (meth) acryloxyphenol and the like.

  Preferable specific examples of the compound represented by the above formula (3) include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl (meth) acrylate. 2- [1- (2-hydroxy-3,5-di-t-butylphenyl) ethyl] -4,6-di-t-pentylphenyl (meth) acrylate, 2- [1- (2-hydroxy- 3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl (meth) acrylate and the like. The compounds represented by the formulas (1) to (3) specifically exemplified here are preferable from the viewpoint of copolymerization reactivity with other compounds and improvement in light resistance of the resulting cured film.

  As the compound (a2), the compounds represented by the above formulas (1) to (3) can be used alone or in combination of two or more. The copolymer [A] is preferably 1 to 60% by mass, particularly preferably 5 to 5% of repeating units derived from the compound (a2) based on the total number of repeating units constituting the copolymer [A]. Contains 50% by weight. In the copolymer [A], the light resistance of the obtained interlayer insulating film can be sufficiently ensured by setting the repeating unit derived from the compound (a2) to 1% by mass or more. On the other hand, by setting the repeating unit to 60% by mass or less, it is possible to prevent a decrease in transparency and heat resistance of the obtained interlayer insulating film.

  The compound (a3) used for obtaining the copolymer [A] is an unsaturated compound having an epoxy group having radical polymerizability. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).

  Specific examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid-3. , 4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o -Vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3, 4- epoxy cyclohexyl methacrylate, etc. are mentioned. Among these unsaturated compounds having an oxiranyl group, glycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4 -Epoxy cyclohexyl methacrylate etc. are preferably used from a viewpoint of an improvement of copolymerization reactivity.

  Specific examples of the unsaturated compound having an oxetanyl group include 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3 -Ethyloxetane, 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3 -Ethyloxetane, 3 (Methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyl Examples thereof include oxetane and 3- (2-methacryloyloxyethyl) -2-phenyloxetane.

  These compounds (a3) are used alone or in combination. In the copolymer [A], the repeating unit derived from the compound (a3) is preferably 10 to 80% by mass, particularly preferably 30 to 30%, based on the total number of repeating units constituting the copolymer [A]. You may contain 80 mass%. By making this repeating unit into 10-80 mass% in copolymer [A], the heat resistance and solvent resistance of the interlayer insulation film obtained can be improved further.

  The compound (a4) is not particularly limited as long as it is an unsaturated compound having radical polymerizability other than the compounds (a1), (a2) and (a3). Examples of the compound (a4) include methacrylic acid chain 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 diester. , Bicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, unsaturated compound having a skeleton represented by the following formula (4), the following formula ( Examples thereof include phenolic hydroxyl group-containing unsaturated compounds represented by 5) (excluding the compounds represented by the above formulas (2) and (3)) and other unsaturated compounds.

（式（４）中、Ｒ^１９は水素原子又はメチル基であり、ｐは２〜１０の整数である。）

(In Formula (4), R ¹⁹ is a hydrogen atom or a methyl group, and p is an integer of 2 to 10.)

（式（５）中、Ｒ^２０は水素原子又は炭素数１〜４のアルキル基であり、Ｒ^２１〜Ｒ^２５は同一もしくは異なり、水素原子、ヒドロキシル基又は炭素数１〜４のアルキル基であり、Ｂは単結合、−ＣＯＯ−＊又は−ＣＯＮＨ−＊であり、ｑは０〜３の整数である、但し、Ｒ^２１〜Ｒ^２５の少なくとも１つはヒドロキシル基であり、かつヒドロキシル基に隣接する置換基はｔ−ブチル基ではなく、−ＣＯＯ−＊又は−ＣＯＮＨ−＊における各々の＊の結合手は（ＣＨ_２）_ｑの炭素と結合する。）

(In Formula (5), R ²⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^{21 to} R ²⁵ are the same or different, and are a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. , B is a single bond, —COO— * or —CONH— *, q is an integer of 0 to 3, provided that at least one of R ^{21 to} R ²⁵ is a hydroxyl group and is adjacent to the hydroxyl group The substituent to be bonded is not a t-butyl group, but each * bond in —COO— * or —CONH— * is bonded to the carbon of (CH ₂ ) _q .)

Specific examples of the compound (a4) include
As methacrylic acid chain alkyl ester, 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 etc .;
As cyclic alkyl esters of methacrylic acid, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane. -8-yloxyethyl methacrylate, isobornyl methacrylate, etc .;
As a methacrylic acid ester having a hydroxyl group, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethylglycoside, 4-hydroxyphenyl methacrylate and the like;
As cyclic alkyl ester of acrylic acid, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane -8-yloxyethyl acrylate, isobornyl acrylate and the like;
Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate;

As acrylic acid aryl ester, phenyl acrylate, benzyl acrylate, etc .;
As unsaturated dicarboxylic acid diesters, diethyl maleate, diethyl fumarate, diethyl itaconate, etc .;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- as bicyclo unsaturated compounds 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-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyl Oxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2.2 .1] Hept-2-ene 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6 -Dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydroxyethyl) ) Bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] ] Hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene and the like;

As maleimide compounds, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate, N- Succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like;
Examples of unsaturated aromatic compounds include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and the like;
As conjugated dienes, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like;
Examples of unsaturated compounds containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like;
As unsaturated compounds containing a furan skeleton, 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-en-2- ON, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2-yl- Hex-1-en-3-one, acrylic acid-2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-hepten-3-one, and the like;

Unsaturated compounds containing a tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one, 2 -Methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, etc .;
As an unsaturated compound containing a pyran skeleton, 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran, 4- (1,5-dioxa-6-oxo-7) -Octenyl) -6-methyl-2-pyran and the like;
Examples of the unsaturated compound containing a skeleton represented by the above formula (4) include polyethylene glycol (n = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) mono (meth) acrylate, and the like. It is done.

  Further, examples of the unsaturated compound containing a phenol skeleton include compounds represented by the following formulas (6) to (10) according to the definitions of B and q from the compound represented by the above formula (5).

（式（６）中、ｒは１から３の整数であり、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４及びＲ^２５の定義は上記式（５）における定義と同じである。）

(In formula (6), r is an integer of 1 to 3, and the definition of R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ is the same as the definition in the above formula (5).)

（式（７）中、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４及びＲ^２５の定義は上記式（５）における定義と同じである。）

(In formula (7), the definitions of R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are the same as those in formula (5) above.)

（式（８）中、ｓは１から３の整数であり、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４及びＲ^２５の定義は上記式（５）における定義と同じである。）

(In the formula (8), s is an integer of 1 to 3, and the definitions of R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are the same as the definitions in the above formula (5).)

（式（９）中、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４及びＲ^２５の定義は上記式（５）における定義と同じである。）

(In formula (9), the definitions of R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are the same as those in formula (5) above.)

（式（１０）中、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４及びＲ^２５の定義は上記式（５）における定義と同じである。）

(In formula (10), the definitions of R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are the same as those in formula (5) above.)

  Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Among examples of these compounds (a4), methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, maleimide compound, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, skeleton represented by the above formula (4) An unsaturated compound having a phenol, a phenolic hydroxyl group-containing unsaturated compound represented by the above formula (5), an unsaturated aromatic compound, and a cyclic alkyl ester of acrylic acid are preferably used. Among these, styrene, t-butyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N- Cyclohexylmaleimide, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydrofuran-2-one, 4-hydroxybenzyl (meth) acrylate, 4- Hydroxyphenyl (meth) acrylate, o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.

Preferable specific examples of each component of the copolymer [A] include methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / 2-methylcyclohexyl acrylate / glycidyl methacrylate / (Meth) acrylic acid-2,2,6,6-tetramethyl-4-piperidinyl, methacrylic acid / glycidyl methacrylate / N-cyclohexylmaleimide / 3- (2-methacryloyloxyethyl) oxetane / 2,5-di- t-butyl-4-i-propenylphenol, styrene / methacrylic acid / glycidyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / 2-t-butyl-6- (3 -T-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl (meth) acrylate, Methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / tetrahydrofurfuryl methacrylate / glycidyl methacrylate / (meth) acrylic acid-2,2,6,6-tetramethyl-4 Piperidinyl, methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / tetrahydrofurfuryl methacrylate / glycidyl methacrylate / 2,5-di-t-butyl-4-i-propenyl Phenol, methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / tetrahydrofurfuryl methacrylate / glycidyl methacrylate / 2-tert-butyl-6- (3-tert-pentyl-2 -Hydroxy-5-methylbenzyl) -4-methylphenyl (meth) acrylate , Methacrylic acid / tricyclo [5.2.1.0 ^2,6] decan-8-yl methacrylate / tetrahydrofurfuryl methacrylate / glycidyl methacrylate / 2-t-butyl-6-(3-t-butyl-2 And hydroxy-5-methylbenzyl) -4-methylphenyl (meth) acrylate.

  These compounds (a4) may be used alone or in combination of two or more. Copolymer [A] is preferably 0 to 60% by mass, particularly preferably 5 to 60% by mass of repeating units derived from compound (a4) based on the total number of repeating units constituting copolymer [A]. You may contain 50 mass%. In copolymer [A], the fall of developability of positive type radiation sensitive resin composition can be suppressed by making the quantity of this repeating unit 60 mass% or less.

The polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) by GPC (gel permeation chromatography) of the copolymer [A] is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10. ^{3 to} 5 × 10 ⁴ . By setting the Mw of the copolymer [A] to 2 × 10 ³ or more, the development margin of the positive radiation-sensitive resin composition can be increased, and the decrease in heat resistance of the resulting interlayer insulating film can be suppressed. On the other hand, when the Mw of the copolymer [A] is 1 × 10 ⁵ or less, excellent radiation sensitivity and developability can be obtained. The molecular weight distribution (hereinafter referred to as “Mw / Mn”) of the copolymer [A] is preferably 5.0 or less, more preferably 3.0 or less. By making Mw / Mn of the copolymer [A] 5.0 or less, high developability of the obtained interlayer insulating film can be secured.

  Examples of the solvent used in the polymerization reaction for producing the copolymer [A] include diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propylene glycol monoalkyl ether. Examples include propionate, ketones, and other esters.

These solvents include
As diethylene glycol dialkyl ether, for example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like;
Examples of dipropylene glycol dialkyl ethers include dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether and the like;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like;
As propylene glycol monoalkyl ether acetate, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc .;
As propylene glycol monoalkyl ether propionate, for example, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and the like;
Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and the like;

  Examples of other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, hydroxyacetic acid Methyl, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, Methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, Methyl poxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate Propyl acid, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxypropionic acid Ethyl, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-metho Butyl cypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxy Examples thereof include propyl propionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like.

  Of these solvents, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and other esters are preferred, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene It is particularly preferable to use glycol monoethyl ether, propylene glycol monomethyl ether acetate, or methyl 3-methoxypropionate.

  As the polymerization initiator used in the production of the copolymer [A], those generally known as radical polymerization initiators can be used. Specific examples of the polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy- Azo compounds such as 2,4-dimethylvaleronitrile).

  In the production of the copolymer [A], a molecular weight modifier can be used to adjust the molecular weight. Specific examples of molecular weight regulators include mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid; xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide; -A methyl styrene dimer etc. can be mentioned.

[B] 1,2-quinonediazide compound [B] component used for the said positive radiation sensitive resin composition is a 1,2-quinonediazide compound which generate | occur | produces carboxylic acid by irradiation of a radiation. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

  Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei.

As these mother cores,
Examples of trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone;
Examples of tetrahydroxybenzophenone include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3, 4,2′-tetrahydroxy-4′-methylbenzophenone, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone, etc .;
Examples of pentahydroxybenzophenone include 2,3,4,2 ′, 6′-pentahydroxybenzophenone and the like;
Examples of hexahydroxybenzophenone include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone and the like;

  Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, and 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- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl- 4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene 5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl -7,2 ', 4'-trihydroxy flavan like;

  As other mother nucleus, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 2- [bis {(5-isopropyl-4-hydroxy- 2-methyl) phenyl} methyl], 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- ( 1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene.

  Among these mother nuclei, 2,3,4,4′-tetrahydroxybenzophenone, 1,1,1-tri (p-hydroxyphenyl) ethane, 4,4 ′-[1- [4- [1- [ 4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferred.

  The 1,2-naphthoquinone diazide sulfonic acid halide is preferably 1,2-naphthoquinone diazide sulfonic acid chloride. Specific examples of 1,2-naphthoquinone diazide sulfonic acid chloride include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-naphthoquinone diazide-5-sulfonic acid chloride. Among these, it is particularly preferable to use 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazidesulfonic acid halide, preferably 30 to 85 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. %, More preferably 1,2-naphthoquinonediazidesulfonic acid halide corresponding to 50 to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Further, as the 1,2-quinonediazide compound, 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, for example, 2,3,4-trihydroxybenzophenone-1,2 -Naphthoquinonediazide-4-sulfonic acid amide etc. are also used suitably.

  These [B] components can be used alone or in combination of two or more. The proportion of the [B] component used in the positive radiation-sensitive resin composition is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the copolymer [A]. It is. When the proportion of the component [B] is 5 to 100 parts by mass, the difference in solubility between the irradiated portion and the unirradiated portion with respect to the alkaline aqueous solution serving as the developer is large, and the developability is improved and obtained. The heat resistance and solvent resistance of the interlayer insulating film are also improved.

Other optional components In addition to the above-mentioned [A] and [B] components, the positive-type radiation-sensitive resin composition includes [C] a heat-sensitive acid-generating compound as necessary within a range not impairing the intended effect. Or a heat-sensitive base generating compound, [D] a polymerizable compound having at least one ethylenically unsaturated double bond, [E] a surfactant, [F] an adhesion assistant, and [G] a radical scavenger. be able to.

  The heat-sensitive acid generating compound or heat-sensitive base generating compound of component [C] is defined as a compound that can release an acidic active substance or a basic active substance by applying heat. Such a heat-sensitive acid generating compound or a heat-sensitive base generating compound can be added to the positive radiation-sensitive resin composition in order to improve the heat resistance and solvent resistance of the resulting interlayer insulating film.

  Examples of the heat-sensitive acid-generating compound [C] include diphenyliodonium salts, triphenylsulfonium salts, and onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts, phosphonium salts, and tetrahydrothiophenium salts. It is done.

  Examples of diphenyliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyl Iodonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarce Bis (4-tert-butylphenyl) iodonium trifluorometa Examples include sulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium camphorsulfonic acid, and the like. .

  Examples of triphenylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenyl Examples include sulfonium butyl tris (2,6-difluorophenyl) borate.

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

As these sulfonium salts,
Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- ( Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate, etc .;

  Examples of benzylsulfonium salts include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, and benzyl-4-methoxyphenylmethyl. Sulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethyl Sulfonium hexafluorophosphate, etc .;

  Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexa Fluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4 -Hydroxyphenylsulfonium hexafluorophosphate and the like;

  Examples of substituted benzylsulfonium salts include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenylmethyl. Sulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3- And chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

  Examples of benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxy Benzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like.

  Examples of tetrahydrothiophenium salts include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium Nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1- (4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2, 2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydro Ofenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4,7-dibutoxy-1 -Naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate and the like.

  Examples of commercially available products of these heat-sensitive acid generating compounds include Sun-Aid SI-L85, SI-L110, SI-L145, SI-L150, SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like. be able to.

  Among these heat-sensitive acid generating compounds, triphenylsulfonium salts, sulfonium salts, benzothiazonium salts, and tetrahydrothiophenium salts are preferably used from the viewpoint of improving the heat resistance of the obtained interlayer insulating film. Among these, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium Hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexa Fluorophosphate, 1- (4,7-dibutoxy-1 Naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate are preferred.

  Examples of the heat-sensitive base-generating compound of the component [C] include 2-nitrobenzylcyclohexyl carbamate, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, N- (2-nitrobenzyloxycarbonyl) pyrrolidine. Bis [[(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine, triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyloxime, 4- (methylthiobenzoyl) -1-methyl-1- Morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, hexaamminecobalt (III) tris (triphenyl) Methyl borate) It is below. Among these heat-sensitive base-generating compounds of the [C] component, 2-nitrobenzylcyclohexyl carbamate and O-carbamoylhydroxyamide are particularly preferable from the viewpoint of improving the heat resistance of the obtained interlayer insulating film.

  The heat-sensitive acid generating compound or the heat-sensitive base generating compound of the component [C] may be used alone or in combination of two or more. In the positive radiation-sensitive resin composition, the amount of the [C] component used is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 100 parts by mass of the copolymer [A]. 5 to 5 parts by mass. By setting the usage ratio of the component [C] to 0.1 to 10 parts by mass, an interlayer insulating film having good heat resistance and solvent resistance can be formed.

  As the polymerizable compound having at least one ethylenically unsaturated double bond as the component [D], for example, monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional or higher (meth) acrylate, and the like are preferable. Can be used.

  Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl- Examples thereof include 2-hydroxypropyl phthalate. As a commercial item of these monofunctional (meth) acrylates, for example, Aronix M-101, M-111, M-114 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, TC-120S ( As mentioned above, Nippon Kayaku Co., Ltd.), Biscoat 158, 2311 (above, Osaka Organic Chemical Industry Co., Ltd.) and the like can be mentioned.

  Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples thereof include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, and bisphenoxyethanol full orange (meth) acrylate. As a commercial item of these bifunctional (meth) acrylates, for example, Aronix M-210, M-240, M-6200 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R -604 (manufactured by Nippon Kayaku Co., Ltd.), Biscoat 260, 312, and 335HP (manufactured by Osaka Organic Chemical Industries, Ltd.).

  Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, Examples include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Examples of commercially available products of these (meth) acrylates having three or more functional groups include Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, and M-8060. (Above, manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-60, DPCA-120 (above, Nippon Kayaku Co., Ltd.), Biscote 295 , 300, 360, GPT, 3PA, 400 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

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

  These monofunctional, bifunctional, or trifunctional or higher (meth) acrylates are used alone or in combination. The amount of the component [D] used in the positive radiation sensitive resin composition is preferably 1 to 50 parts by mass, more preferably 3 to 100 parts by mass of the copolymer [A]. 30 parts by mass. By making the usage-amount of a [D] component into 1-50 mass parts, the heat resistance and solvent resistance of the obtained interlayer insulation film can be improved more.

  In the positive radiation-sensitive resin composition, a surfactant can be used as the [E] component in order to further improve the coating property at the time of coating film formation. Examples of the surfactant that can be suitably used include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.

  Examples of fluorosurfactants include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,1) 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether and other fluoroethers; sodium perfluorododecylsulfonate; 1,1,2 , 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexaph Fluoroalkanes such as orodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides; fluoroalkylpolyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxylates And fluorine-based alkyl esters.

  Commercially available products of these fluorosurfactants include BM-1000, BM-1100 (manufactured by BM Chemie), MegaFack F142D, F172, F173, F183, F178, F191, F191, and F471. (Above, Dainippon Ink & Chemicals, Inc.), Florard FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Limited), Surflon S-112, S-113 S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (Manufactured by Asahi Glass Co., Ltd.), Ftop EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.) and the like.

  Specific examples of the silicone-based surfactant include commercially available product names such as DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ. -6032 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above, manufactured by GE Toshiba Silicone Co., Ltd.) And the like.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Polyoxyethylene aryl ethers; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (meth) acrylic acid copolymers and the like. As a typical commercially available nonionic surfactant, Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

  [E] Surfactant of a component can be used individually or in combination of 2 or more types. The amount of the component [E] used in the positive radiation sensitive resin composition is preferably 0.01 to 3 parts by mass, more preferably 0.001 parts by mass with respect to 100 parts by mass of the copolymer [A]. It is 05-2 mass parts. By setting the use ratio of the component [E] to 0.01 to 3 parts by mass, it is possible to suppress the occurrence of coating unevenness when a coating film is formed on the substrate.

  In the positive radiation sensitive resin composition, an adhesion assistant as the [F] component can be used in order to improve the adhesion between the obtained interlayer insulating film and the substrate. As such an adhesion assistant, a functional silane coupling agent is preferably used. Examples of functional silane coupling agents include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, and epoxy groups. Specific examples of functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxy Examples thereof include propyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

  [F] Component adhesion assistants can be used alone or in combination of two or more. In the positive radiation-sensitive resin composition, the amount of the component [F] used is preferably 0.01 to 20 parts by weight, more preferably 0.00 with respect to 100 parts by weight of the copolymer [A]. It is 05-15 mass parts. By setting the blending amount of the [F] component adhesion assistant to 0.01 to 20 parts by mass, the adhesion between the obtained interlayer insulating film and the substrate becomes the best.

[G] Radical scavenger [G] A radical scavenger can be further added to the positive radiation sensitive resin composition. [G] As the radical scavenger, at least one selected from the group consisting of a hindered phenol compound, a hindered amine compound, an alkyl phosphate compound, and a compound containing a sulfur atom can be used.

  Examples of the hindered phenol compound include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [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-α, α ′, α ″-(mesitylene-2,4,6-to Yl) 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, hexamethylenebis [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-xylin) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl- -(4,6-bis (octylthio) -1,3,5-triazin-2-ylamine) phenol, 1,3,5-tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) ) Isocyanuric acid and the like.

Examples of these commercially available products include 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 (and above). Manufactured by ADEKA Corporation);
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, IRGANOGAX 3114 ;
Yoshinox BHT, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox 250, Yoshinox 930, Yoshinox SS, Yoshinox TT, Yoshinox 917, Yoshinox 314 (above, manufactured by API Corporation), and the like.

Examples of the hindered amine compound include tetrakis (2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 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 etc. can be mentioned, and these commercial products include, for example, ADK STAB LA-52, ADK STAB LA57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63P, ADK STAB LA-68LD, ADK STAB LA-77, ADK STAB LA-82, ADK STAB LA-87 (above, ADEK Co., Ltd.) A);
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 Ciba Specialty Chemicals).

Examples of the alkyl phosphate compound include butylidenebis {2-tert-butyl-5-methyl-p-phenylene} -P, P, P, P-tetratridecylbis (phosphine), distearyl pentaerythritol diphosphite, 2 , 2′-methylenebis (4,6-di-tert-butyl-1-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.

As these commercial products, for example, 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 Corporation);
IRGAFOS 168 (manufactured by Ciba Specialty Chemicals) and the like can be mentioned.

Examples of the compound containing a sulfur atom include pentaerythritol tetrakis (3-laurylthiopropionate), di (propionic acid-n-tridecanyl) sulfide, thiodiethylene bis [3- (3,5-di-tert-butyl). -4-hydroxyphenyl) propionate] and the like, and commercially available products of value ether include, for example, ADK STAB AO-412S, ADK STAB AO-503 (above, manufactured by ADEKA Corporation);
sumilizer TPL-R, sumilizer TPM, sumilizer TPS, sumilizer TP-D, sumilizer MB (manufactured by Sumitomo Chemical Co., Ltd.);
IRGANOX PS800FD, IRGANOX PS802FD, IRGANOX 1035 (above, manufactured by Ciba Specialty Chemicals);
DLTP, DSTP, DMTP, DTTP (above, manufactured by API Corporation) and the like can be mentioned.

  The radical scavenger of the component [G] can be used alone or in combination of two or more. The amount in the case of using the [G] component in the positive radiation sensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass of the [A] alkali-soluble resin. 1 to 30 parts by mass. When the amount used is 0.1 to 30 parts by mass, the pattern dimension of the interlayer insulating film to be formed is unstable, the transparency is lowered, and the resolution of the interlayer insulating film is reduced. A decrease in storage stability of the radiation resin composition can be prevented.

Positive-type radiation-sensitive resin composition The positive-type radiation-sensitive resin composition of the present invention uniformly mixes the above-mentioned [A] and [B] components and optional components ([C] to [G] components). It is prepared by. Usually, the positive radiation-sensitive resin composition is preferably used after being dissolved in an appropriate solvent and stored in a solution state. For example, a positive radiation sensitive resin composition in a solution state can be prepared by mixing [A] and [B] components and optional components in a solvent at a predetermined ratio.

  As a solvent used for the preparation of the positive radiation sensitive resin composition, the above [A] and [B] components and optional components ([C] to [G] components) are uniformly dissolved, And as long as it does not react with each component, it is not specifically limited. As such a solvent, the thing similar to the solvent illustrated as a solvent which can be used in order to manufacture copolymer [A] can be mentioned.

  Of these solvents, alcohols, glycol ethers, ethylene glycol monoalkyl ether acetates, esters, diethylene glycol monomonomers, etc. from the standpoints of solubility of each component, non-reactivity with each component, and ease of coating formation. Alkyl ether acetate, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, and propylene glycol monoalkyl ether acetate are preferably used. Among these solvents, 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, diethylene glycol dimethyl ether, dipropylene glycol Dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl 2- or 3-methoxypropionate, or ethyl 2- or 3-ethoxypropionate can be particularly preferably used.

  Furthermore, in order to improve the in-plane uniformity of the coating film to be formed, a high boiling point solvent can be used in combination with the solvent. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl Examples include cellosolve acetate. Of these high boiling solvents, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferred.

  When a high boiling point solvent is used in combination as the solvent for the positive radiation sensitive resin composition, the amount used is 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, based on the total amount of the solvent. can do. By setting the use ratio of the high boiling point solvent to 50% by mass or less, it is possible to improve the film thickness uniformity of the coating film and to suppress a decrease in radiation sensitivity.

  When preparing the positive radiation-sensitive resin composition in a solution state, the proportion of components other than the solvent in the solution (that is, the total amount of the above-mentioned [A] and [B] components and other optional components) Can be arbitrarily set according to the purpose of use, desired film thickness and the like, but is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 35% by mass. The solution of the positive radiation sensitive resin composition thus prepared can be used after being filtered using a Millipore filter having a pore diameter of about 0.2 μm.

Formation of Interlayer Insulating Film Next, a method for forming an interlayer insulating film of the present invention using the positive radiation sensitive resin composition will be described. The method includes the following steps in the order described below.
(1) forming a coating film of the positive radiation sensitive resin composition of the present invention on a substrate;
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) a step of developing the coating film irradiated with radiation in step (2), and (4) a step of heating the coating film developed in step (3).

(1) Step of forming a coating film of a positive radiation sensitive resin composition on a substrate In the step (1), a solution of the positive radiation sensitive resin composition of the present invention is applied to the substrate surface, preferably Removes the solvent by pre-baking to form a coating film of the positive radiation-sensitive resin composition. Examples of the types of substrates that can be used include glass substrates, silicon wafers, and substrates on which various metals are formed.

  The method for applying the composition solution is not particularly limited. For example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet method is adopted. can do. Among these coating methods, the spin coating method and the slit die coating method are particularly preferable. The pre-baking conditions vary depending on the type of each component, the use ratio, and the like, but can be, for example, 60 to 110 ° C. for 30 seconds to 15 minutes. As a film thickness of the coating film formed, 2-5 micrometers is preferable as a value after a prebaking, for example.

(2) Step of irradiating at least a part of the coating film In the step (2), the formed coating film is irradiated with radiation through a mask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.

Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet light include a KrF excimer laser. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam. Among these radiations, ultraviolet rays are preferable, and among the ultraviolet rays, radiation containing g-line and / or i-line is particularly preferable. The exposure amount is preferably 50 to 1,500 J / m ² .

(3) Development step (3) In the development step, the coating film irradiated with radiation in the step (2) is developed to remove the irradiated portion and form a desired pattern. it can. Examples of the developer used for the development processing include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propyl. An aqueous solution of an alkali (basic compound) such as amine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, and tetraethylammonium hydroxide can be used. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent or surfactant such as methanol or ethanol to the aqueous alkali solution described above, or an alkaline aqueous solution containing a small amount of various organic solvents for dissolving the radiation-sensitive resin composition, Can be used as Furthermore, as a developing method, for example, an appropriate method such as a liquid filling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. Although development time changes with compositions of a radiation sensitive resin composition, it can be made into 30 to 120 second, for example.

  In addition, in the conventionally known radiation-sensitive resin composition, if the development time exceeds about 20 to 25 seconds from the optimum value, the formed pattern is peeled off, so the development time needs to be strictly controlled. On the other hand, the positive radiation sensitive resin composition of the present invention has a high development margin, so that a good pattern can be formed even if the excess time from the optimum development time is 30 seconds or more, which increases the product yield. The benefits are great.

(4) Heating step (4) In the heating step, after the developing step (3) above, the patterned thin film is preferably rinsed with running water, and then preferably irradiated with radiation from a high-pressure mercury lamp or the like. By irradiating the entire surface (post-exposure), the 1,2-quinonediazide compound remaining in the thin film is decomposed. Next, the thin film is subjected to a heat treatment (post-bake treatment) by using a heating device such as a hot plate or an oven, whereby the thin film is cured. The exposure amount in the post-exposure is preferably about 2,000 to 5,000 J / m ² . Moreover, the baking temperature in this hardening process is 120-250 degreeC, for example. Although heating time changes with kinds of heating apparatus, for example, when performing heat processing on a hotplate, it can be set to 30 to 90 minutes when performing heat processing in oven, for 30 to 90 minutes. At this time, a step baking method or the like in which a heating process is performed twice or more can be used. In this way, a patterned thin film corresponding to the target interlayer insulating film can be formed on the surface of the substrate.

  The interlayer insulating film thus formed is excellent in heat resistance, solvent resistance, low dielectric property, light transmittance, light resistance, and dry etching resistance, as will be clarified from examples described later. It is.

When an electronic component such as a liquid crystal display element is manufactured using such an interlayer insulating film, dry etching is performed as necessary. Examples of the etching gas used in such a dry etching process include O ₂ , N ₂ , CF ₄ , SiF _{6 and the} like. As an etching method, reactive ion etching that causes ions to collide with the substrate by applying a voltage between the substrate on which the interlayer insulating film is patterned and the electrode, and plasma that causes radicals to collide with the substrate are performed. There are two types of etching. These gas types and etching methods are appropriately selected depending on the base metal type of the interlayer insulating film. As described above, the interlayer insulating film formed from the positive radiation-sensitive resin composition of the present invention has excellent resistance to dry etching.

  Hereinafter, the present invention will be described more specifically with reference to synthesis examples and examples, but the present invention is not limited to the following examples.

Hereinafter, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the copolymer were measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 (manufactured by Showa Denko KK) Mobile phase: Tetrahydrofuran Detector: Differential refractometer Standard substance: Monodisperse polystyrene

Copolymer synthesis examples and comparative synthesis examples [Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 18 parts by mass of methacrylic acid, 20 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 12 parts by mass of tetrahydrofurfuryl methacrylate, 45 parts by mass of glycidyl methacrylate, methacrylic acid-2, 2,5,6-Tetramethyl-4-piperidinyl (5 parts by mass) and α-methylstyrene dimer (3 parts by mass) were charged and purged with nitrogen, and then gently stirred. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-1]. The copolymer [A-1] had a polystyrene equivalent weight average molecular weight (Mw) of 10,000 and a molecular weight distribution (Mw / Mn) of 2.3. Further, the solid content concentration of the obtained polymer solution (the ratio of the copolymer contained in the polymer solution to the total mass of the polymer solution; the same applies hereinafter) was 33.3% by mass. It was.

[Synthesis Example 2]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 18 parts by mass of methacrylic acid, 20 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 12 parts by mass of tetrahydrofurfuryl methacrylate, 45 parts by mass of glycidyl methacrylate, 2,5-di -T-butyl-4-i-propenylphenol 5 parts by mass and α-methylstyrene dimer 3 parts by mass were charged with nitrogen, and then gently stirred. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-2]. The copolymer [A-2] had a polystyrene equivalent weight average molecular weight (Mw) of 10,200 and a molecular weight distribution (Mw / Mn) of 2.2. Moreover, the solid content concentration of the obtained polymer solution was 33.5 mass%.

[Synthesis Example 3]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 18 parts by mass of methacrylic acid, 20 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 12 parts by mass of tetrahydrofurfuryl methacrylate, 45 parts by mass of glycidyl methacrylate, 2-t-butyl -6- (3-t-pentyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate 5 parts by mass and α-methylstyrene dimer 3 parts by mass were charged with nitrogen, and then gently stirred. I started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-3]. The copolymer [A-3] had a polystyrene equivalent weight average molecular weight (Mw) of 9,900 and a molecular weight distribution (Mw / Mn) of 2.2. Moreover, the solid content concentration of the obtained polymer solution was 33.1% by mass.

[Synthesis Example 4]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of dipropylene glycol dimethyl ether. Subsequently, 18 parts by mass of methacrylic acid, 20 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 12 parts by mass of tetrahydrofurfuryl methacrylate, 45 parts by mass of glycidyl methacrylate, 2-t-butyl -6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate 2 parts by weight, methacrylic acid-2,2,6,6-tetramethyl-4-piperidinyl 3 parts by weight, And 3 parts by mass of α-methylstyrene dimer were charged and purged with nitrogen, and then gently stirred. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-4]. The copolymer [A-4] had a weight average molecular weight (Mw) in terms of polystyrene of 9,900 and a molecular weight distribution (Mw / Mn) of 2.2. Moreover, solid content concentration of the obtained polymer solution was 32.8 mass%.

[Comparative Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 18 parts by mass of methacrylic acid, 20 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 12 parts by mass of tetrahydrofurfuryl methacrylate, 45 parts by mass of glycidyl methacrylate, 5 parts by mass of methyl methacrylate. And 3 parts by mass of α-methylstyrene dimer were charged and purged with nitrogen, and then gently stirred. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [a-1]. The copolymer [a-1] had a polystyrene equivalent weight average molecular weight (Mw) of 9,900 and a molecular weight distribution (Mw / Mn) of 2.2. Moreover, the solid content concentration of the obtained polymer solution was 33.1% by mass.

Preparation of positive radiation sensitive resin composition [Example 1]
100 parts by mass (solid content) of the copolymer [A-1] obtained in Synthesis Example 1 as the [A] component and 4,4 ′-[1- [4- [1- [4-] as the [B] component Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) condensate (B-1) 25 mass Part, [E] component, 0.1 part by weight of “SH-28PA” manufactured by Toray Dow Corning Silicone Co., which is a silicone surfactant, and γ-glycidoxypropyltrimethoxy as [F] component 0.1 parts by mass of silane is mixed, dissolved in diethylene glycol ethyl methyl ether so that the solid content concentration is 30% by mass, and then filtered through a membrane filter having a diameter of 0.2 μm, and positive radiation sensitive The solution of the resin composition (S-1) was prepared.

[Examples 2 to 4 and Comparative Example 1]
As in Example 1, a solution of positive radiation-sensitive resin composition (A), [B] component, and other components were used in the same manner as in Example 1 except that the types and amounts shown in Table 1 were used. S-2) to (S-4) and (s-1) were prepared.

[Example 5]
It was dissolved in diethylene glycol ethyl methyl ether / propylene glycol monomethyl ether acetate (mass ratio 6/4) so that the solid content concentration was 20% by mass, and 1,1,1-tri (p-hydroxy) as the [B] component Example 1 except that 20 parts by mass of a condensate (B-2) of (phenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) was used. Similarly, a solution (S-5) of a positive radiation sensitive resin composition was prepared.

[Examples 6 to 12 and Comparative Example 2]
As in Example 5, except that the [A] component, [B] component, and other components were used in the types and amounts shown in Table 1, a solution of a positive radiation sensitive resin composition ( S-6) to (S-12) and (s-2) were prepared.

In Table 1, the abbreviations of the components indicate the following compounds.
B-1: 4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensation product with sulfonic acid chloride (2.0 mol) B-2: 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid Condensate with chloride (2.0 mol) C-1: benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate D-1: trimethylolpropane triacrylate D-2: dipentaerythritol hexaacrylate E-1: silicone system Surfactant ("SH-28PA" manufactured by Toray Dow Corning Silicone Co., Ltd.)
F-1: γ-Glycidoxypropyltrimethoxysilane G-1: 1,3,5-tris (3 ′, 5′-di-tert-butyl-4′-hydroxybenzyl) isocyanuric acid (Adeka Co., Ltd.) "ADK STAB AO-20")
G-2: distearyl pentaerythritol diphosphite (“ADEKA STAB PEP-8” manufactured by ADEKA Corporation)

Characteristic Evaluation as Interlayer Insulating Film Using the positive radiation sensitive resin composition prepared as described above, various characteristics as an interlayer insulating film were evaluated as follows.

[Evaluation of radiation sensitivity of positive radiation-sensitive resin composition]
About Examples 1-4 and the comparative example 1 on a silicon substrate, after apply | coating the said composition (S-1)-(S-4), (s-1) using a spinner, it was 90 degreeC. And prebaked on a hot plate for 2 minutes to form a coating film having a thickness of 3.0 μm. For Examples 5 to 12 and Comparative Example 2, the compositions (S-5) to (S-12) and (s-2) were applied using a slit die coater, and vacuum was applied at 0.5 Torr. After drying, it was prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was subjected to a pattern mask having a 3.0 μm line and space (10 to 1) pattern using a PLA-501F exposure machine (extra high pressure mercury lamp) manufactured by Canon Inc. After performing exposure by changing the exposure time, development was performed with a liquid mass method at 25 ° C. for 80 seconds in a 0.4 mass% tetramethylammonium hydroxide aqueous solution. Subsequently, the substrate was washed with ultrapure water for 1 minute and dried to form a pattern on the wafer. At this time, the exposure amount necessary for completely dissolving the 3.0 μm line-and-space (10 to 1) space pattern was measured. This value is shown in Table 1 as radiation sensitivity. It can be said that the radiation sensitivity is good when this value is 1,000 J / m ² or less.

[Evaluation of development margin of positive radiation-sensitive resin composition]
In the same manner as in [Evaluation of radiation sensitivity of positive radiation-sensitive resin composition], a coating film was formed on a silicon substrate. Using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc., a mask having a 3.0 μm line and space (10 to 1) pattern was applied to the obtained coating film. Exposure is performed at an exposure amount corresponding to the value of the radiation sensitivity measured in the above [Evaluation of Radiation Sensitivity], and the development time is changed at 25 ° C. with a 0.4 mass% tetramethylammonium hydroxide aqueous solution. Developed by the liquid method. Next, running water was washed with ultrapure water for 1 minute and dried to form a pattern on the wafer. At this time, the development time necessary for the line width to be 3.0 μm is shown in Table 1 as the optimum development time. Further, when the development is further continued from the optimum development time, the time until the 3.0 μm line pattern is peeled off is measured and shown in Table 1 as a development margin (allowable development time range). When this value is 30 seconds or more, it can be said that the development margin is good.

[Evaluation of solvent resistance of interlayer insulation film]
A coating film was formed on a silicon substrate in the same manner except that the exposure was not performed in the above [Evaluation of radiation sensitivity of positive-type radiation-sensitive resin composition]. The obtained coating film was exposed using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. so that the integrated irradiation amount was 3,000 J / m ^2. A cured film was obtained by heating at 220 ° C. for 1 hour in a clean oven. The film thickness (T1) of the obtained cured film was measured. And after immersing the silicon substrate in which this cured film was formed in dimethyl sulfoxide temperature-controlled at 70 degreeC for 20 minutes, the film thickness (t1) of the said cured film was measured, and the film thickness change rate by immersion { | T1-T1 | / T1} × 100 [%] was calculated. Table 1 shows the evaluation results of the solvent resistance. When this value is 5% or less, it can be said that the solvent resistance is good. In the evaluation of solvent resistance, since the patterning of the film to be formed is unnecessary, the development process is omitted, and only the coating film forming process, the radiation irradiation process, and the heating process are performed for evaluation.

[Evaluation of heat resistance of interlayer insulation film]
A cured film was formed in the same manner as in the above [Evaluation of solvent resistance of interlayer insulating film], and the thickness (T2) of the obtained cured film was measured. Next, the silicon substrate on which the cured film is formed is additionally baked in a clean oven at 240 ° C. for 1 hour, and then the thickness (t2) of the cured film is measured, and the rate of change in film thickness due to the additional baking {| t2−T2 | / T2} × 100 [%] was calculated. Table 1 shows the evaluation results of heat resistance. When this value is 1% or less, it can be said that the heat resistance is good.

[Evaluation of light resistance of interlayer insulation film]
A cured film was formed in the same manner as in [Evaluation of Solvent Resistance of Interlayer Insulating Film], and was exposed to light of 310 nm at 200 J / m ² without using a photomask. About the cured film thus exposed, head space gas chromatography / mass spectrometry (head space sampler: manufactured by Nippon Analytical Industries, Ltd., model name “JHS-100A”; gas chromatography / mass spectrometer: Nippon Analytical Industry) Analysis was performed by “JEOL JMS-AX505W type mass spectrometer” manufactured by Co., Ltd. The purge area was set to 100 ° C./10 min, and the peak area A related to generation of volatile components derived from the photopolymerization initiator was determined. Using n-octane (specific gravity: 0.701; injection amount: 0.02 μl) as a standard substance, the amount of volatile components derived from the photopolymerization initiator in terms of n-octane is calculated from the following formula based on the peak area. did. When the amount of the volatile component is 2 μg or less, it can be said that there are few sublimates from the cured film and light resistance is good. The evaluation results of light resistance are shown in Table 1.
Formula for calculating the amount of volatile components in terms of n-octane Volatile component amount (μg) = A × (n-octane amount (μg)) / (n-octane peak area)

[Evaluation of dry etching resistance of interlayer insulation film]
A cured film is formed in the same manner as in the above [Evaluation of solvent resistance of interlayer insulating film], and the resulting cured film is etched using a dry etching apparatus “CDE-80N” (manufactured by Shibaura Mechatronics). Dry etching was performed under the conditions of CF ₄ 50 ml / min, O ₂ 10 ml / min, output 400 mW, and etching time 90 seconds as gases, and the film thickness was measured before and after the treatment. The evaluation results of dry etching resistance are shown in Table 1. When the thickness reduction is less than 0.70 μm, it can be said that the dry etching resistance is good.

[Evaluation of transparency of interlayer insulation film]
In the above [Evaluation of solvent resistance of interlayer insulating film], a cured film was formed on the glass substrate in the same manner except that a glass substrate “Corning 7059” (manufactured by Corning) was used instead of the silicon substrate. The light transmittance of the glass substrate on which this cured film was formed was measured at a wavelength in the range of 400 to 800 nm using a spectrophotometer “150-20 type double beam” (manufactured by Hitachi, Ltd.). 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 the transparency is good.

[Evaluation of relative dielectric constant of interlayer insulating film]
About Examples 1-4 and the comparative example 1 on the grind | polished SUS304 board | substrate, after apply | coating each composition using a spinner, after prebaking on a hotplate for 2 minutes at 90 degreeC, film thickness 3. A 0 μm coating film was formed. For Examples 5 to 12 and Comparative Example 2, each composition was applied using a slit die coater, vacuum dried at 0.5 Torr, and then pre-baked on a hot plate at 90 ° C. for 2 minutes. Thus, a coating film having a thickness of 3.0 μm was formed. The resulting coating film was exposed to a cumulative irradiation amount of 3,000 J / m ² using a Canon-made PLA-501F exposure machine (extra-high pressure mercury lamp), and then in a clean oven. The cured film was obtained by baking at 220 ° C. for 1 hour. On this cured film, a Pt / Pd electrode pattern was formed by vapor deposition to prepare a sample for measuring relative permittivity. About the obtained sample, the relative dielectric constant in the frequency of 10 kHz was measured by CV method using the HP16451B electrode and HP4284A precision LCR meter by Yokogawa and Hewlett-Packard Co., Ltd. Table 1 shows the measurement results of the relative dielectric constant. When this value is 3.9 or less, it can be said that the relative dielectric constant is good. In the evaluation of the relative dielectric constant, since the patterning of the film to be formed is unnecessary, the development process was omitted, and only the coating film forming process, the radiation irradiation process, and the heating process were performed for evaluation.

  From the results shown in Table 1, the positive radiation sensitive compositions of Examples 1 to 12 have high radiation sensitivity and development margin, and the interlayer insulating film formed from the composition has good heat resistance. It has been found that the film has excellent properties in terms of light resistance and dry etching resistance as compared with the compositions of Comparative Examples 1 and 2.

  Since the interlayer insulating film formed from the positive radiation sensitive resin composition of the present invention is excellent in various properties as described above, it includes not only TFT liquid crystal display elements but also magnetic head elements, integrated circuit elements, solids. It is suitably used as an electronic component such as an image sensor.

Claims (4)

[A] an alkali-soluble resin having a hindered amine structure and / or a hindered phenol structure, and [B] a 1,2-quinonediazide compound ,
[A] a monomer in which the alkali-soluble resin contains at least one selected from (a1) an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, (a2) a compound represented by the following formula (1), the following formula ( A copolymer obtained from a compound represented by 2) and a monomer containing one or more compounds selected from the compounds represented by the following formula (3), and (a3) a monomer containing an epoxy group-containing unsaturated compound. A positive radiation sensitive resin composition.

(In Formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^{2 to} R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms, and R ⁶ is a hydrogen atom or An alkyl group having 1 to 6 carbon atoms, B ₁ is a single bond, —COO— * or —CONH— *, and m is an integer of 0 to 3. However, —COO— * or —CONH— Each * bond in * is bonded to (CH ₂ ) _m carbon.
In the formula (2), R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^{7 to} R ¹⁰ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁸ and R ^At least one of ⁹ is a t-butyl group or a t-pentyl group, B ₁ is a single bond, —COO— * or —CONH— *, and n is an integer of 0 to 3. However, each * bond in —COO— * or —CONH— * is bonded to carbon of (CH ₂ ) _n .
In Formula (3), R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹¹ is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and t is an integer of 1 to 4. R ^{15 to} R ¹⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms , at least one of R ¹⁵ and R ¹⁶ is a t-butyl group or a t-pentyl group, and B ₁ is , Single bond, —COO— * or —CONH— *, and B ₂ is a single bond, —CO—, —S—, —CH ₂ —, —CH (CH ₃ ) — or —C (CH ₃ ). _2- and k is an integer of 0-3. However, each * bond in —COO— * or —CONH— * is bonded to carbon of (CH ₂ ) _k . ) The positive radiation sensitive resin composition according to claim 1 , which is used for forming an interlayer insulating film. The interlayer insulation film formed from the positive radiation sensitive resin composition of Claim 2 . (1) The process of forming the coating film of the positive radiation sensitive resin composition of Claim 2 on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A step of developing the coating film irradiated with radiation in step (2), and (4) A method of forming an interlayer insulating film, including a step of heating the coating film developed in step (3).