TWI464535B - Radiation-sensitive linear resin composition, interlayer insulating film and method of forming same - Google Patents

Description

Radiation-sensitive linear resin composition, interlayer insulating film and method of forming same

The present invention relates to a radiation sensitive resin composition suitable for forming an interlayer insulating film of a flexible display, an interlayer insulating film formed of the composition, and a method of forming the same.

In recent years, conveniences such as light weight and miniaturization have been increasing, and flexible displays such as liquid crystal electronic paper are becoming widespread. As a substrate of such a flexible display, a plastic substrate such as polycarbonate or polyethylene terephthalate was used instead of the glass substrate. However, these plastics have a problem of slightly stretching and shrinking upon heating, which affects the function of the display, and therefore it is urgent to improve heat resistance. On the other hand, in order to reduce the thermal stress applied to the plastic substrate, it has been studied to lower the temperature of the flexible display. In the manufacture of a flexible display, one of the processes requiring the highest temperature is a step of heating and firing the interlayer insulating film, which requires a low temperature.

At present, as a material for forming the interlayer insulating film, a material having a small number of steps for obtaining a necessary pattern shape and having a high surface hardness is preferable, and thus a radiation sensitive resin composition is widely used. As such a radiation-sensitive resin composition, a copolymer comprising an unsaturated carboxylic acid and/or an anhydride thereof, an epoxy group-containing unsaturated compound, or the like is disclosed, for example, in JP-A-2001-354822. The radiation sensitive resin composition is subjected to a ring-opening crack reaction of a carboxyl group and an epoxy group to obtain a surface hardness as an interlayer insulating film. However, in order to increase the surface hardness of the interlayer insulating film to the actual commercial surface hardness, it is necessary to have a heating step at a high temperature of 200 ° C or higher. In consideration of the heat resistance of the plastic substrate, the temperature of the heating step is preferably 180 ° C or less, and the substrate may be deformed when heated at a high temperature of 200 ° C or higher.

In addition, a negative-type radiation-sensitive resin composition for forming a spacer of a liquid crystal display element, which comprises an unsaturated carboxylic acid and/or thereof, is disclosed in Japanese Laid-Open Patent Publication No. 2008-77067 A copolymer formed of an anhydride, an epoxy group-containing unsaturated compound, or the like, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a thiol compound having two or more mercapto groups in one molecule. However, the radiation sensitive resin composition of this document is excellent in radiation sensitivity and adhesion to a substrate, but it is not possible to achieve low-temperature heating and firing suitable for a plastic substrate.

Based on the above-mentioned problem, it is disclosed in JP-A-2009-4394 that solvent resistance, electrical resistivity, semiconductor mobility, and the like can be obtained by firing a polyimide precursor which can be cured at a low temperature at 180 ° C or lower. Excellent gate insulating film for flexible displays. However, the coating liquid containing the polyimine precursor of the above document is a chemical curing system, and there is no pattern forming energy for exposure and development, so that a fine pattern cannot be formed. Further, when an insulating film is formed using a coating liquid containing such a polyimide precursor, it takes a time of heating or baking the cured film for 1 hour or longer. Therefore, there is a strong demand for the development of a radiation-sensitive resin composition suitable for use in the production of an insulating film for use in a flexible display, which can be heated and fired at a low temperature for a short period of time, and is simply formed into a film. And forming a fine pattern.

Further, in the process of the apparatus for a flexible display, it may be necessary to form a laminate by coating the upper layer of the interlayer insulating film. Therefore, in addition to having a high relative dielectric constant, the interlayer insulating film is required to have excellent solvent resistance to a solvent used for coating to form a laminate.

Prior art literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2001-354822

Patent Document 2 Japanese Patent Laid-Open Publication No. 2008-77067

Patent Document 3 Japanese Patent Laid-Open Publication No. 2009-4394

The present invention has been made in view of the above problems, and an object thereof is to provide a radiation sensitive resin composition which can be heated and fired at a low temperature for a short period of time, and which has high radiation sensitivity and is suitable for forming a flexible An interlayer insulating film of a sexual display. Further, another object of the present invention is to provide a radiation sensitive resin composition which can form an interlayer insulating film excellent in solvent resistance and relative dielectric constant.

The present invention has been made in order to solve the above problems, and is a radiation sensitive resin composition for forming an interlayer insulating film, comprising:

[A] a copolymer alkali-soluble resin obtained by copolymerizing a monomer containing (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, and (a2) an epoxy group-containing unsaturated compound,

[B] 1,2-quinonediazide compound, and

[C] A compound having two or more mercapto groups in one molecule.

In addition to the alkali-soluble resin of the [A] component and the 1,2-quinonediazide compound of the component [B], the resin composition further contains a compound having two or more mercapto groups in one molecule of the [C] component. The cross-linking agent has high radiation sensitivity, and can form an interlayer insulating film at a low temperature and for a short period of heating and firing, and can form an interlayer insulating film excellent in solvent resistance and relative dielectric constant, so that it is suitable It is used as a material for forming an interlayer insulating film of a flexible display.

The compound having two or more mercapto groups in one molecule of the component [C] in the radiation-sensitive resin composition is preferably a compound represented by the following formula (1). Further, as the compound represented by the formula (1), an esterified product of a mercaptocarboxylic acid and a polyhydric alcohol can be typically used. By using the compound represented by the following formula (1) as the [C] component, high curability can be obtained in the heating step of the radiation sensitive resin composition.

(In the formula (1), R ¹ is a methylene group, an alkylene group having 2 to 10 carbon atoms or an alkylmethylene group, and Y is a single bond, -CO- or -O-CO-* (wherein The linkage with "*" is linked to R ¹ ), n is an integer from 2 to 10, and X is an n-valent hydrocarbon group having from 2 to 70 carbon atoms which may have one or more ether linkages, or n is At 3 o'clock, it is a group represented by the formula (2). In the formula (2), each of the three R ^{2 is} independently a methylene group or an alkylene group having 2 to 6 carbon atoms, and three "*" are respectively Indicates the connection key.)

The radiation sensitive resin composition preferably further contains [D] a compound represented by the following formula (3). By using the compound represented by the following formula (3) as the component [D], higher curability can be obtained in the heating step of the radiation sensitive resin composition.

(In the formula (3), Z ¹ , Z ² , Z ³ and R ³ each independently represent a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent , Z ² and Z ³ can be connected to each other to form a ring.)

In addition, the method of forming an interlayer insulating film of the present invention comprises:

(1) a step of forming a coating film of the radiation sensitive resin composition on a substrate,

(2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation,

(3) a step of developing the coating film irradiated with radiation in the step (2), and

(4) A step of heating and baking the coating film developed in the step (3).

In addition, "firing" as used herein means heating to a surface hardness required as an interlayer insulating film.

When the interlayer insulating film is formed by the above-described steps using the radiation sensitive resin composition, a pattern is formed by radiation exposure and development by radiation, so that a fine and delicate pattern can be easily formed. Further, by using the radiation sensitive resin composition, an interlayer insulating film having a sufficient surface hardness can be formed by exposure and development at a low temperature by heating for a short period of time.

In the method of forming the interlayer insulating film, the firing temperature in the step (4) is preferably 180 ° C or lower. The method is suitable for forming an interlayer insulating film on a plastic substrate of a flexible display because it is fired at such a low temperature, in addition to the radiation pattern forming ability.

As described above, the radiation sensitive resin composition for forming an interlayer insulating film of the present invention has high radiation sensitivity, and can form an interlayer insulating film having a high surface hardness by heating at a low temperature for a short period of time, so that solvent resistance can be formed. And an interlayer insulating film excellent in relative dielectric constant. Therefore, the radiation sensitive resin composition is suitable as a material for forming an interlayer insulating film of a flexible display.

Form of implementing the invention

The radiation-sensitive resin composition for forming an interlayer insulating film of the present invention contains an alkali-soluble resin of the component [A], a 1,2-quinonediazide compound of the component [B], and a component [C] in one molecule. Two or more thiol-based compounds (crosslinking agents) and other optional components. Hereinafter, each component will be described.

[A] component

The component [A] is a copolymer alkali-soluble resin obtained by copolymerizing a monomer containing (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride and (a2) an epoxy group-containing unsaturated compound (hereinafter, the copolymerization) This is called "copolymer [A]"). The copolymer [A] can be produced by radically polymerizing a monomer containing the compound (a1) and the compound (a2) in the presence of a polymerization initiator in a solvent. Further, in the production of the copolymer [A], it is preferred to radically polymerize the compound (a1) and the compound (a2) together with the unsaturated compound other than the above (a1) and (a2) as the compound (a3). The copolymer [A] preferably contains 5 to 40% by mass, particularly preferably 5 to 25% by mass based on the total amount of the structural units derived from the compounds (a1) and (a2) (and any compound (a3)). % of a structural unit derived from the compound (a1). By making the ratio of the structural unit derived from the compound (a1) in the copolymer [A] 5 to 40% by mass, the solubility of the copolymer in the alkaline aqueous solution can be optimized, and radiation sensitivity and development can be obtained. A radiation sensitive linear resin composition excellent in properties.

The compound (a1) is an unsaturated carboxylic acid having a radical polymerizable property and/or an unsaturated carboxylic anhydride. Specific examples of the compound (a1) include a monocarboxylic acid, a dicarboxylic acid, an anhydride of a dicarboxylic acid, and a mono[(meth)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid at both ends. A mono(meth)acrylate of a polymer having a carboxyl group and a hydroxyl group, a polycyclic compound having a carboxyl group, an anhydride thereof, and the like.

Specific examples of the compound (a1) include acrylic acid, methacrylate, and crotonic acid, and dicarboxylic acids, which may be exemplified by maleic acid, fumaric acid, citraconic acid, and Zhongkang. Examples of the acid anhydride of the dicarboxylic acid include an anhydride of the compound exemplified as the above dicarboxylic acid; and a mono[(meth)acryloxyalkylalkyl ester as a polyvalent carboxylic acid; Examples of the succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene methoxyethyl] ester, etc.; Examples of the mono(meth)acrylate of the polymer of a carboxyl group and a hydroxyl group include ω-carboxypolycaprolactone mono(meth)acrylate; and examples of the polycyclic compound having a carboxyl group and an anhydride thereof include 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-methylbicyclo[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 Wait.

Among these compounds (a1), an anhydride of a monocarboxylic acid or a dicarboxylic acid is preferably used from the viewpoints of copolymerization reactivity, solubility to an alkaline aqueous solution, and easy availability. In particular, acrylic acid, methacrylic acid, maleic anhydride. These compounds (a1) can be used individually or in combination of 2 or more types.

The copolymer [A] is based on the total amount of the structural units derived from the compounds (a1) and (a2) (and any compound (a3)), preferably 10 to 80% by mass, particularly preferably 30 to 80% by mass. % of structural units derived from compound (a2). When the ratio of the structural unit derived from the compound (a2) in the copolymer [A] is from 10 to 80% by mass, an interlayer insulating film having excellent solvent resistance and alkali resistance can be formed.

The compound (a2) is an epoxy group-containing unsaturated compound having a radical polymerizable property. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) and an propylene oxide group (1,3-epoxy structure).

Specific examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, glycidyl α-n-propyl acrylate, and α. - glycidyl butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-cyclomethacrylate Oxyheptyl ester, α-ethyl acrylate 6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate or the like. Among these epoxy group-containing unsaturated compounds, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinyl benzyl Glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, etc. are preferably used from the viewpoint of improving copolymerization reactivity and curability of the resin composition. .

Specific examples of the unsaturated compound having an oxypropylene group include 3-(acryloxymethyl) propylene oxide and 3-(acryloxymethyl)-2-methyl propylene oxide. 3-(Allyloxymethyl)-3-ethyl propylene oxide, 3-(acryloxymethyl)-2-trifluoromethyl propylene oxide, 3-(acryloxymethyl) -2-pentafluoroethyl propylene oxide, 3-(acryloxymethyl)-2-phenyl propylene oxide, 3-(acryloxymethyl)-2,2-difluoroepoxy Propane, 3-(acryloxymethyl)-2,2,4-trifluoroepoxypropane, 3-(acryloxymethyl)-2,2,4,4-tetrafluoropropylene oxide , 3-(2-propenyloxyethyl) propylene oxide, 3-(2-propenyloxyethyl)-2-ethyl propylene oxide, 3-(2-propenyloxyethyl) 3-ethyl propylene oxide, 3-(2-propenyl methoxyethyl)-2-trifluoromethyl propylene oxide, 3-(2-propenyloxyethyl)-2-pentafluoroethyl Propylene oxide, 3-(2-propenyloxyethyl)-2-phenyl propylene oxide, 3-(2-propenyl methoxyethyl)-2,2-difluoro propylene oxide, 3-(2-propenyloxyethyl)-2,2,4-trifluoroepoxypropane, 3-(2-propenyloxyethyl)-2,2,4,4- Acrylate such as fluoropropylene oxide; 3-(methacryloxymethyl) propylene oxide, 3-(methacryloxymethyl)-2-methyl propylene oxide, 3-(A) Propylene methoxymethyl)-3-ethyl propylene oxide, 3-(methacryloxymethyl)-2-trifluoromethyl propylene oxide, 3-(methacryl oxime 2-pentafluoroethyl propylene oxide, 3-(methacryloxymethyl)-2-phenyl propylene oxide, 3-(methacryloxymethyl)-2,2 -difluoropropylene oxide, 3-(methacryloxymethyl)-2,2,4-trifluoroepoxypropane, 3-(methacryloxymethyl)-2,2, 4,4-tetrafluoropropylene oxide, 3-(2-methylpropenyloxyethyl) propylene oxide, 3-(2-methylpropenyloxyethyl)-2-ethyl epoxy Propane, 3-(2-methylpropenyloxyethyl)-3-ethyl propylene oxide, 3-(2-methylpropenyloxyethyl)-2-trifluoromethyl propylene oxide, 3-(2-Methylacryloxyethyl)-2-pentafluoroethyl propylene oxide, 3-(2-methylpropenyloxyethyl)-2-phenyl propylene oxide, 3- (2-methylpropenyloxyethyl)-2,2-difluoroepoxypropane, 3-(2-methylpropenyloxyethyl)-2,2,4 a methacrylate such as trifluoropropylene oxide or 3-(2-methylpropenyloxyethyl)-2,2,4,4-tetrafluoropropylene oxide. These compounds (a2) can be used individually or in combination of 2 or more types.

The copolymer [A] used in the present invention is based on the total amount of the structural units derived from the compounds (a1) and (a2) and the compound (a3), preferably 1 to 50% by mass, particularly preferably 5 to 50% by mass. % is a structural unit derived from the compound (a3) which is an optional component. By setting the ratio of the structural unit to 1 to 50% by mass, it is possible to obtain a radiation-sensitive resin composition which is excellent in developability of an alkaline aqueous solution and solvent resistance of the formed interlayer insulating film.

The compound (a3) is not particularly limited as long as it is a radical polymerizable unsaturated compound other than the compound (a1) and the compound (a2). Examples of the compound (a3) include a chain alkyl methacrylate, a cyclic alkyl methacrylate, a methacrylate having a hydroxyl group, a cyclic alkyl acrylate, and an aryl methacrylate. , aryl acrylate, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran An unsaturated compound having a skeleton, a pyran skeleton, a skeleton represented by the following formula (4), an unsaturated compound containing a phenolic hydroxyl group represented by the following formula (5), and other unsaturated compound.

(In the formula (4), R ⁴ is a hydrogen atom or a methyl group, and m is an integer of 1 or more)

(In the formula (5), R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ to R ^{10 are the} same or differently a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms; B is a single bond, -COO- or -CONH-, and p is an integer of 0 to 3, wherein at least one of R ⁶ to R ¹⁰ is a hydroxyl group.)

Specific examples of the compound (a3) include, as the chain alkyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and butyl methacrylate. Tert-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-octadecane methacrylate a base ester or the like; as a cyclic alkyl methacrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0 ^2,6 ]癸-8-yl group Methacrylate, tricyclo[5.2.1.0 ^2,6 ]癸-8-yloxyethyl methacrylate, isophorone methacrylate, etc.; as a methacrylate having a hydroxyl group, exemplified Hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, methacrylic acid 2,3 -dihydroxypropyl ester, 2-methylpropenyloxyethyl glucoside, 4-hydroxyphenyl methacrylate, etc.; Acid cyclic alkyl esters include acrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6] deca-8-yl acrylate, tricyclo [5.2.1.0 ^{2 , 6} ] 癸-8-yloxyethyl acrylate, isophorone acrylate, etc.; as the aryl methacrylate, phenyl methacrylate, benzyl methacrylate, etc.; Examples of the aryl acrylate include phenyl acrylate and acrylate benzyl; and examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, and itaconic acid. Ester and the like; as the bicyclic unsaturated compound, bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo[2.2.1] hept-2-ene, 5-ethylbicyclo[ 2.2.1]hept-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-tris-butoxycarbonylbicyclo[2.2 .1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5, 6-di(tertiary 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-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxyl -5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, etc.; as a maleimide compound, Examples thereof include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-(4-hydroxyphenyl)maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimine butyric acid Ester, N-succinimide-6-maleimide caproate, N-succinimide-3-maleimide propionate, N-(9-acridinyl) horse Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and the like; Make Examples of the conjugated diene include 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene; and examples of the unsaturated compound containing a tetrahydrofuran skeleton include Tetrahydrofurfuryl (meth)acrylate, 2-methylpropenyloxy-tetrahydrofurfuryl propionate, 3-(meth)acryloxytetrahydrofuran-2-one, etc.; as a furan skeleton Examples of the unsaturated compound include 2-methyl-5-(3-furyl)-1-penten-3-one, decyl (meth)acrylate, and 1-furan-2-butyl-3- En-2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6-(2-furyl)-2-methyl-1-hexene-3- Ketone, 6-furan-2-yl-hex-1-en-3-one, 2-indol-2-yl-1-methyl-ethyl acrylate, 6-(2-furyl)-6- Methyl-1-heptan-3-one or the like; as the unsaturated compound containing a tetrahydropyran skeleton, exemplified is (tetrahydropyran-2-yl)methyl methacrylate, 2,6-dimethyl -8-(tetrahydropyran-2-yloxy)-oct-1-en-3-one, 2-hydropyran-2-yl methacrylate, 1-(tetrahydropyran- 2-oxy)-but-3-en-2-one; etc.; as an unsaturated compound containing a pyran skeleton, 4-(1, 4-dioxa-5-oxo-6-pentenyl)-6-methyl-2-pyran, 4-(1,5-dioxa-6-oxo-7-octenyl) -6-methyl-2-pyran or the like; as the unsaturated compound containing the skeleton represented by the above formula (4), polyethylene glycol (n=2 to 10) mono(meth)acrylate, Polypropylene glycol (n = 2 ~ 10) mono (meth) acrylate and the like.

In addition, the phenolic hydroxyl group-containing unsaturated compound represented by the above formula (5) is a compound represented by the following formulas (6) to (10), and is defined by the definitions of B and m.

(In the formula (6), q is an integer of 1 to 3, and the definitions of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same as defined in the above formula (5).)

(In the formula (7), the definitions of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same as defined in the above formula (5).)

(In the formula (8), r is an integer of 1 to 3, and the definitions of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same as defined in the above formula (5).)

(In the formula (9), the definitions of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same as defined in the above formula (5).)

(In the formula (10), the definitions of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same as defined in the above formula (5).)

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

In the examples of the compound (a3), a chain alkyl ester of methacrylic acid, a cyclic alkyl methacrylate, a maleimide compound, a tetrahydrofuran skeleton, a furan skeleton, and a tetrahydropyran skeleton are preferably used. The pyran skeleton, the unsaturated compound of the skeleton represented by the above formula (4), the phenolic hydroxyl group-containing unsaturated compound represented by the above formula (5), the unsaturated aromatic compound, and the cyclic alkyl acrylate. Among these, especially styrene, butyl methacrylate, n-lauryl methacrylate, tricyclo [5.2.1.0 ^2,6 ] fluoren-8-yl methacrylate, p-methoxy Styrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (n= 2~10) mono(meth)acrylate, 3-(meth)acryloxytetrahydrofuran-2-one, 4-hydroxybenzyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate The ester, o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene are preferred from the viewpoints of copolymerization reactivity and solubility in an aqueous alkaline solution. These compounds (a3) can be used individually or in combination of 2 or more types.

Preferred specific examples of the respective component components of the copolymer [A] include methacrylic acid/tricyclo[5.2.1.0 ^2,6 ]癸-8-ylmethacrylate/2-methylcyclohexyl acrylate. Ester/glycidyl methacrylate/N-(3,5-dimethyl-4-hydroxybenzyl)methacrylamide, methacrylic acid/tetrahydrofurfuryl methacrylate/glycidyl methacrylate Ester/N-cyclohexylmaleimide/n-lauryl methacrylate/α-methyl-p-hydroxystyrene, styrene/methacrylic acid/glycidyl methacrylate/(3-ethyl Propylene oxide-3-yl)methacrylate/tricyclo[5.2.1.0 ^2,6 ]癸-8-yl methacrylate, methacrylic acid/tricyclo[5.2.1.0 ^2,6 ]癸-8 - methacrylic acid ester / 2-methylcyclohexyl acrylate / glycidyl methacrylate / styrene.

The polystyrene-equivalent weight average molecular weight (hereinafter referred to as Mw) obtained by GPC (gel permeation chromatography) of the copolymer [A] is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ³ ~ 5 × 10 ⁴ . By setting the Mw of the copolymer [A] to 2 × 10 ³ to 1 × 10 ⁵ , the radiation sensitivity and developability of the radiation sensitive resin composition (the property of forming a desired pattern shape correctly) can be improved.

Further, the molecular weight distribution "Mw/Mn" of the copolymer [A] (wherein "Mn" is a polystyrene-equivalent number average molecular weight of the copolymer [A] measured by gel permeation chromatography) is preferably 5.0 or less. More preferably 3.0 or less. By setting the Mw/Mn of the copolymer [A] to 5.0 or less, the developability of the obtained interlayer insulating film can be improved. The radiation-sensitive resin composition containing the copolymer [A] does not generate an afterimage at the time of development, and can easily form a desired pattern shape.

Examples of the solvent used in the polymerization reaction for producing the copolymer [A] include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, and propylene glycol monoalkyl groups. Ether, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, other esters, and the like.

Examples of the solvent include, for example, methanol, ethanol, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, and the like, and examples of the ethers such as tetrahydrofuran; Alcohol ether, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.; as ethylene glycol alkyl ether acetate, for example, methyl stilbene acetate, ethyl 赛苏苏乙Acid ester, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc.; as diethylene glycol alkyl ether, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc.; as propylene glycol monoalkyl ether, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, etc.; as propylene glycol monoalkyl ether acetate, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate , propylene glycol monobutyl 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, etc.; as aromatic hydrocarbons, for example, toluene, xylene, etc.; as ketones, for example, methyl ethyl ketone, ring Hexanone, 4-hydroxy-4-methyl-2-pentanone, etc.; as other esters, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, 2 Methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, lactate Ester, 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 propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxylate, butyl Oxyl Propyl acrylate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate , methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate , ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , 3-methoxypropionic acid propyl ester, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate , 3-ethoxypropionic acid butyl ester, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate An ester such as methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate or butyl 3-butoxypropionate.

Among these solvents, preferred are ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, particularly preferably diethylene glycol dimethyl ether, two Glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate.

As the polymerization initiator used in the polymerization reaction for producing the copolymer [A], those known as radical polymerization initiators can be usually used. Examples of the radical initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), and 2,2'-couple. An azo compound such as nitrogen di-(4-methoxy-2,4-dimethylvaleronitrile); benzamidine peroxide, laurel peroxide, tertiary butyl peroxy valerate, 1,1' - an organic peroxide such as di-(tri-butyl peroxide) cyclohexane; and hydrogen peroxide.

When a peroxide is used as the radical polymerization initiator, a peroxide and a reducing agent may be used together to form a redox type initiator.

In the polymerization for producing the copolymer [A], a molecular weight modifier can be used to adjust the molecular weight. Specific examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, and tertiary dodecyl sulfide. Mercaptans such as alcohols and mercaptoacetic acids; xanthates such as dimethyl xanthate sulfide and diisopropyl xanthate disulfide; terpinolene, α-methylstyrene dimer, etc. .

[B] ingredient

The component [B] used in the radiation sensitive resin composition of the present invention is a 1,2-quinonediazide compound which irradiates radiation to generate a carboxylic acid. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as "mother core") and a 1,2-naphthoquinonediazidesulfonic acid halide can be used.

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

As such a mother nucleus, examples of the trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, and the like; as tetrahydroxydiphenyl The ketone may, for example, be 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetra Hydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone And the pentahydroxybenzophenone may, for example, be 2,3,4,2',6'-pentahydroxybenzophenone or the like; and as the hexahydroxybenzophenone, for example, 2, 4 may be mentioned. 6,3',4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-hexahydroxybenzophenone, etc.; as (polyhydroxyphenyl)alkane, For example, bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane can be cited. , 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]benzene Ethylene]biphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1,1' - spirobiindole-5,6,7,5',6'-hexanol, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan, etc.; as other mother The nucleus may, for example, be 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxychroman, 1-[1-(3-{1 -(4-hydroxyphenyl)-1-methylethyl}-4,6-dihydroxyphenyl)-1-methylethyl]-3-(1-(3-{1-(4-hydroxyl) Phenyl)-1-methylethyl}-4,6-dihydroxyphenyl)-1-methylethyl)benzene, 4,6-di{1-(4-hydroxyphenyl)-1-methyl Base ethyl}-1,3-dihydroxybenzene.

Among these cores, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris(p-hydroxyphenyl)ethane, 4,4'-[1-[4 -[1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]biphenol.

Further, as the 1,2-naphthoquinonediazidesulfonic acid halide, 1,2-naphthoquinonediazidesulfonium chloride is preferred. Specific examples of the 1,2-naphthoquinonediazidesulfonium chloride include 1,2-naphthoquinonediazide-4-sulfonyl chloride and 1,2-naphthoquinonediazide-5-sulfonate. chlorine. Among these, it is particularly preferred to use 1,2-naphthoquinonediazide-5-sulfonyl chloride.

In the condensation reaction of a phenolic compound or an alcoholic compound (nuclear core) with a 1,2-naphthoquinonediazidesulfonic acid halide, the equivalent amount of the OH group in the phenolic compound or the alcoholic compound can be used. 30 to 85 mol%, preferably 50 to 70 mol% of 1,2-naphthoquinonediazidesulfonic acid halide. The condensation reaction can be carried out by a known method.

Further, as the 1,2-quinonediazide compound, 1,2-naphthoquinonediazidesulfonate oxime which converts the ester bond of the above-exemplified nucleus to a guanamine bond, for example, 2, 3, is preferably used. 4-Triaminobenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid decylamine and the like.

These [B] components can be used individually or in combination of 2 or more types. The use ratio of the component [B] in the radiation sensitive resin composition is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the alkali-soluble resin of the component [A]. When the ratio of use of the component [B] is 5 to 100 parts by mass, the difference in solubility between the portion irradiated with radiation and the portion not irradiated with respect to the alkaline aqueous solution as the developer becomes large, the patterning performance is good, and the obtained interlayer insulating film The solvent resistance is also good.

[C] component

The [C] component used in the radiation sensitive resin composition of the present invention is a compound having two or more mercapto groups in one molecule. The compound of the component [C] is not particularly limited as long as it has two or more mercapto groups in one molecule, and is preferably a compound represented by the following formula (1).

(wherein R ¹ is a methylene group, an alkylene group having 2 to 10 carbon atoms or an alkylmethylene group, and Y is a single bond, -CO- or -O-CO-* (wherein *" is a linkage bond and R ^{1 is} transported), n is an integer of 2 to 10, and X is an n-valent hydrocarbon group having 2 to 70 carbon atoms which may have one or more ether linkages, or when n is 3. It is a group represented by the following formula (2).)

(wherein, three R ² are each independently a methylene group or an alkylene group having 2 to 6 carbon atoms, and three "*" respectively represent a linking bond.)

As the compound represented by the above formula (1), an esterified product of a mercaptocarboxylic acid and a polyhydric alcohol or the like can be typically used. By using such an esterified product, a radiation sensitive resin composition having high curability can be obtained. As the mercaptocarboxylic acid constituting the ester compound, for example, mercaptoacetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, 3-mercaptovaleric acid or the like can be used. Further, examples of the polyhydric alcohol constituting the ester compound include ethylene glycol, propylene glycol, trimethylolpropane, neopentyl alcohol, tetraethylene glycol, dipentaerythritol, 1,4-butanediol, and new Pentaerythritol and the like.

Preferable specific examples of the compound represented by the above formula (1) include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and four. Glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), pentaerythritol tetrakis(mercaptoacetate), 1,4-bis(3-mercaptobutyl) Oxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptovalerate), 1,3,5-tris(3-mercaptobutyloxyethyl) Base)-1,3,5-three -2,4,6(1H,3H,5H)-trione and the like.

As the compound having two or more mercapto groups in one molecule of the component [C], a compound represented by the following formula (11) or (12) can also be used.

(In the formula (11), R ¹¹ is a methylene group or an alkylene group having 2 to 20 carbon atoms, and R ¹² is a methylene group or a linear or branched alkyl group having 2 to 6 carbon atoms; s represents an integer of 1 to 20. In the formula (12), R is the same or different, and is a group represented by -H, -OH or the formula (13). In the formula (13), R ¹³ is a methylene group or a carbon atom. The linear or branched alkyl group having a number of 2 to 6 wherein at least one of the four R groups in the formula (12) is a group represented by the formula (13).

The compound having two or more mercapto groups in one molecule of the component [C] may be used alone or in combination of two or more. The compound of the [C] component having 2 or more fluorenyl groups in one molecule is preferably used in an amount of 0.1 to 60 parts by mass, more preferably 1 to 50 parts by mass, per 100 parts by mass of the alkali-soluble resin of the component [A]. . By using the radiation sensitive linear resin composition in an amount of 0.1 to 60 parts by mass of the component [C], an interlayer insulating film having a sufficient surface hardness can be obtained with a short heating time of 1 hour or shorter.

Other optional ingredients

The radiation sensitive resin composition of the present invention may contain, as an essential component, the [D] imidazole ring-containing compound as a crosslinking assistant, if necessary, in addition to the above-mentioned [A], [B], and [C] components. E] a polymerizable compound having at least one ethylenically unsaturated double bond, an epoxy resin other than [F] copolymer [A], [G] surfactant, [H] adhesion aid, [I] sensible heat Acid generator.

The crosslinking assistant of the component [D] is a compound containing an imidazole ring represented by the following formula (3).

(In the formula (3), Z ¹ , Z ² , Z ³ and R ³ each independently represent a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent , Z ² and Z ³ can be connected to each other to form a ring.)

Specific examples of the hydrocarbon group in the formula (3) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group, tertiary butyl group, and n-pentyl group. Base, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl An alkyl group having 1 to 20 carbon atoms such as n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl or n-icosyl; cyclobutyl, cyclopentyl, a cycloalkyl group having 3 to 20 carbon atoms such as a cyclohexyl group; the number of carbon atoms such as a phenyl group, a tolylhydryl group, a benzyl group, a methylbenzyl group, a xylyl group, a trimethylphenyl group, a naphthyl group, and a fluorenyl group is 6~ 20 aryl; Bridged alicyclic ring having 6 to 20 carbon atoms such as alkyl, tricyclodecyl, tetracyclododecyl, adamantyl, methyladamantyl, ethyladamantyl, butanyl Hydrocarbyl group and the like.

Further, the above hydrocarbon group may be substituted, and specific examples of the substituent include a hydroxyl group; a carboxyl group; a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, and a 2-hydroxypropyl group. Carboxylic acid, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc., having 1 to 4 hydroxyalkyl groups; methoxy group, ethoxy group An alkoxy group having 1 to 4 carbon atoms such as n-propoxy, isopropoxy, n-butoxy, 2-methylpropoxy, 1-methylpropoxy or tert-butoxy; Cyano; cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, etc., having 2 to 5 cyanoalkyl groups; methoxycarbonyl, ethoxycarbonyl Alkoxycarbonyl group having 2 to 5 carbon atoms such as a tertiary butoxycarbonyl group; a carbon atom such as a methoxycarbonylmethoxy group, an ethoxycarbonylmethoxy group or a tertiary butoxycarbonylmethoxy group; It is a 3 to 6 alkoxycarbonylalkoxy group; a halogen atom such as fluorine or chlorine; a fluoroalkyl group such as a fluoromethyl group, a trifluoromethyl group or a pentafluoroethyl group; and the like.

In the above formula (3), Z ² and Z ³ may be bonded to each other to form a cyclic structure, and it is preferred to form an aromatic ring or a saturated or unsaturated nitrogen-containing hetero ring having 2 to 20 carbon atoms. As the nitrogen-containing hetero ring, for example, a benzimidazole ring of the following formula (14) can be formed.

(In the formula (14), W each independently represents a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The dotted line in the formula represents the formula (3) The bond between the carbon atoms formed by the bonding of Z ² and Z ³ in the imidazolyl ring, that is, the carbon-carbon double bond surrounding Z ² , Z ³ and 2 N.)

In addition, examples of the hydrocarbon group of W in the formula (14) include the same groups as those in the above formula (3). By using such a compound in which Z ² and Z ³ are bonded to each other to form an imidazole ring, a radiation-sensitive resin composition having high curability can be obtained.

Examples of the compound of the [D] component which are particularly preferable include 2-phenylbenzimidazole, 2-methylimidazole, and 2-methylbenzimidazole. The imidazole ring-containing compound of the component [D] may be used alone or in combination of two or more. When the imidazole ring-containing compound of the [D] component as the optional component is used, the amount of the alkali-soluble resin of the component (A) is typically 0.01 to 10 parts by mass based on 100 parts by mass of the component. By using the amount of the [D] component in the radiation sensitive resin composition in an amount of 0.01 to 10 parts by mass, an interlayer insulating film having a higher surface hardness can be obtained.

As the polymerizable compound having at least one ethylenically unsaturated double bond as the component [E], for example, a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, or a trifunctional or higher (meth) group is preferably used. Acrylate.

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth)acrylate, carbitol (meth) acrylate, isophorone (meth) acrylate, and (methyl). 3-methoxybutyl acrylate, 2-(methyl) propylene methoxyethyl 2-hydroxypropyl phthalate, and the like. Examples of commercially available products of these monofunctional (meth) acrylates include Aronix M-101, Aronix M-111, Aronix M-114 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, KAYARAD TC-120S (above, manufactured by Nippon Kayaku Co., Ltd.), Viscoat 158, and Viscoat 2311 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Examples of the bifunctional (meth) acrylate include ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9 _- nonanediol di(a). Acrylate, polypropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, diphenoxyethanol oxime diacrylate, diphenoxyethanol oxime diacrylate, and the like. Examples of such a bifunctional (meth) acrylate include Aronix M-210, Aronix M-240, Aronix M-6200 (above, manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, KAYARAD HX-220, and the like. KAYARAD R-604 (above, manufactured by Nippon Kayaku Co., Ltd.), Viscoat 260, Viscoat 312, Viscoat 335HP (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Examples of the trifunctional or higher (meth) acrylate include trimethylolpropane tri(meth)acrylate, neopentyltriol tri(meth)acrylate, and tris((meth)acrylofluorene oxide. Ethyl ethyl) phosphate, neopentyltetrakis (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. As a commercial product of these trifunctional or higher (meth)acrylate, for example, Aronix M-309, Aronix M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M can be cited. -8060 (above, manufactured by East Asia Synthetic Co., Ltd.), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 (above, manufactured by Nippon Chemical Co., Ltd.), Viscoat 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 3PA, Viscoat 400 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like.

Among these methyl (acrylate)s, from the viewpoint of improving the curability of the radiation sensitive resin composition, it is preferred to use a trifunctional or higher (meth)acrylate. Among these, trimethylolpropane tri(meth)acrylate, neopentyltetrakis(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are particularly preferable. These monofunctional, bifunctional or trifunctional or higher (meth) acrylates may be used singly or in combination.

The use ratio of the component [E] in the radiation sensitive resin composition is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less, based on 100 parts by mass of the copolymer [A]. By containing the component [E] in such a ratio, the curability of the radiation sensitive resin composition can be improved, and the film splitting occurring in the step of forming a coating film on the substrate can be suppressed.

The epoxy resin other than the copolymer [A] as the component [F] is not particularly limited as long as it does not adversely affect the compatibility of each component contained in the radiation sensitive resin composition. As an example of such an epoxy resin, a bisphenol A type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a cyclic aliphatic epoxy resin, and a glycidyl ester type ring are preferable. An oxygen resin, a glycidylamine type epoxy resin, a heterocyclic epoxy resin, a resin obtained by (co)polymerizing glycidyl methacrylate, and the like. Among these, a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, a glycidyl ester type epoxy resin, etc. are especially preferable.

The use ratio of the [F] component in the radiation sensitive resin composition is preferably 30 parts by mass or less based on 100 parts by mass of the copolymer [A]. By using the [F] component in such a ratio, the curability of the radiation sensitive resin composition can be further improved. Further, although the copolymer [A] may also be referred to as "epoxy resin", it differs from the [F] component in that it has alkali solubility. The [F] component is insoluble in alkali.

In order to further improve the coatability at the time of forming a coating film, the [G] component can be used as a surfactant in the radiation sensitive resin composition. As a surfactant suitable for use, a fluorosurfactant, a polyoxynitride surfactant, and a nonionic surfactant are mentioned.

Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether and 1,1,2,2-tetrafluoro. Octyl hexyl ether, octaethylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether a fluoroether such as octapropylene glycol bis(1,1,2,2-tetrafluorobutyl)ether or hexapropylene glycol bis(1,1,2,2,3,3-hexafluoropentyl)ether; Sodium perfluorododecyl sulfate; 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexa Fluoroalkanes such as fluorodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyl oxyalkylene ethers; fluoroalkylammonium iodides; fluoroalkyl polyoxyethylene ethers; perfluoro Alkyl polyoxyethylenes; perfluoroalkyl alkoxylates; fluoroalkyl esters.

As a commercial product of these fluorinated surfactants, BM-1000, BM-1100 (above, BM Chemie), Megafac F142D, Megafac F172, Megafac F173, Megafac F183, Megafac F178, Megafac F191, Megafac F471 ( Above, manufactured by Dainippon Ink Chemical Industry Co., Ltd., Fluorad FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M (share) manufacturing), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 ( Asahi Glass Co., Ltd., EFTOP EF301, EFTOP 303, EFTOP 352 (manufactured by New Akita Chemicals Co., Ltd.).

Specific examples of the organic quinone surfactant include commercially available products, and examples thereof include DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, and SH. -193, SZ-6032 (above, Toray ‧ Dow Corning ‧ Polyoxane (manufactured)), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, GE Toshiba polyoxyl (manufacturing) and so on.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; and polyoxyethylene octylbenzene; Polyoxyethylene aryl ethers such as alkyl ethers and polyoxyethylene nonylphenyl ethers; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (methyl) Acrylic copolymers and the like. Typical products of the nonionic surfactant include Polyflow No. 57 and 95 (manufactured by Kyoeisha Chemical Co., Ltd.). These surfactants can be used individually or in combination of 2 or more types.

In the radiation sensitive resin composition, the surfactant of the component [G] is preferably used in an amount of 5 parts by mass or less, more preferably 2 parts by mass or less, per 100 parts by mass of the copolymer [A]. By using the [G] surfactant in an amount of 5 parts by mass or less, it is possible to suppress the splitting of the film when the coating film is formed on the substrate.

In the radiation sensitive resin composition of the present invention, an adhesion aid can be used as the [H] component to improve the adhesion to the substrate. As such an adhesion aid, a functional decane coupling agent is preferably used. Examples of the functional decane coupling agent include a decane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group or an epoxy group (preferably an oxiran group). Specific examples of the functional decane coupling agent include trimethoxymethyl decyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethylene decyl decane, and vinyl trimethyl. Oxaloxane, γ-isocyanatepropyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. In the radiation sensitive resin composition, the adhesion aid is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 3 parts by mass or more, based on 100 parts by mass of the copolymer [A]. The amount below the mass part is used. By setting the amount of the adhesion aid to 1 part by mass or more and 20 parts by mass or less, the adhesion between the formed interlayer insulating film and the substrate can be improved.

The thermosensitive acid generator of the component [I] is defined as a compound which can be used as an acidic active material which acts as a catalyst when the component [A] is cured by heat release. By using the compound of the component [I], the curing reaction of the component [A] can be further promoted in the heating step after development of the radiation sensitive composition, and an interlayer insulating film excellent in surface hardness and heat resistance can be formed.

An ionic compound and a nonionic compound may be contained in the thermosensitive acid generator of the component [I]. The ionic compound is preferably a compound containing no heavy metal or halogen ion. Examples of the ionic thermosensitive acid generator include triphenylsulfonium, 1-dimethylthionaphthalene, 1-dimethylthio-4-hydroxynaphthalene, and 1-dimethylthio-4,7. -dihydroxynaphthalene, 4-hydroxyphenyldimethylhydrazine, benzyl-4-hydroxyphenylmethylhydrazine, 2-methylbenzyl-4-hydroxyphenylmethylhydrazine, 2-methylbenzyl- 4-Ethylphenylmethylhydrazine, 2-methylbenzyl-4-benzylideneoxyphenylmethylhydrazine, their mesylate, trifluoromethanesulfonate, camphorsulfonate, P-toluenesulfonate, hexafluorophosphonate, and the like. Further, examples of the product of the benzyl sulfonium salt include SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, and SI-110L. , SI-145L, SI-150L, SI-160L, SI-180L (made by Sanxin Chemical Industry Co., Ltd.).

Examples of the nonionic heat-sensitive acid generator include a halogen-containing compound, a diazomethane compound, an anthraquinone compound, a sulfonate compound, a carboxylate compound, a phosphate compound, and a sulfonimide compound. A benzotriazole compound or the like.

Examples of the halogen-containing compound include a halogenated alkyl group-containing hydrocarbon compound and a halogenated alkyl group-containing heterocyclic compound. As an example of a preferable halogen-containing compound, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, 2-phenyl-4,6-di(III) can be cited. Chloromethyl)-s-three 2-naphthyl-4,6-di(trichloromethyl)-s-three Wait.

Examples of the diazomethane compound include bis(trifluoromethanesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and bis(phenylsulfonyl)diazomethane. , bis(p-toluenesulfonyl)diazomethane, bis(2,4-xylsulfonyl)diazomethane, bis(p-chlorophenylsulfonyl)diazomethane, methylsulfonyl - p-Toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl) Diazomethane, benzenesulfonyl (benzhydryl) diazomethane, and the like.

Examples of the ruthenium compound include a β-carbonyl ruthenium compound, a β-sulfonyl fluorene compound, and a diaryl ruthenium compound. As an example of a preferable hydrazine compound, 4-triphenylhydrazine methyl hydrazine, trimethylphenyl hydrazine methyl hydrazine, bis(phenylsulfonyl)methane, and 4-chlorophenyl-4-methyl group are exemplified. A phenyl dihydrazine compound or the like.

Examples of the sulfonate compound include an alkylsulfonate, a halogenated alkylsulfonate, an arylsulfonate, and an iminosulfonate. Examples of preferred sulfonate compounds include benzoin tosylate, pyrogallol trisulphonate, and nitrobenzyl-9,10-diethoxyindole-2-sulfonate. 2,6-dinitrobenzylbenzenesulfonate and the like. Examples of the mercaptosulfide ester product include PAI-101 (manufactured by Midori Chemical Co., Ltd.), PAI-106 (manufactured by Midori Chemical Co., Ltd.), and CGI-1311 (manufactured by Ciba Specialty Chemicals Co., Ltd.). .

Examples of the carboxylic acid ester compound include o-nitrobenzyl carboxylic acid ester.

As an example of the sulfonimide compound, N-(trifluoromethylsulfonyloxy) succinimide (trade name "SI-105" (Midori Chemical Co., Ltd.)), N-(camphorsulfonate) Amber succinimide (trade name "SI-106" (Midori Chemical Co., Ltd.)), N-(4-methylphenylsulfonyloxy) amber ylide (trade name "SI-101" (Midori Chemical Co., Ltd.), N-(2-trifluoromethylphenylsulfonyloxy) succinimide, N-(4-fluorophenylsulfonyloxy) succinimide, N-(trifluoromethylsulfonyloxy) phthalimide, N-(camphorsulfonyloxy) phthalimide, N-(2-trifluoromethylphenylsulfonate) Oxyl) phthalimide, N-(2-fluorophenylsulfonyloxy) phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmalay醯imine (trade name "PI-105" (Midori Chemical Co., Ltd.)), N-(camphorsulfonyloxy)diphenylmaleimide, 4-methylphenylsulfonyloxy) Diphenylmaleimide, N-(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenyl Kamalyimide, N-(4-fluorophenylsulfonyloxy)diphenyl horse Yttrium, N-(phenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine (trade name "NDI-100" (Midori Chemical Co., Ltd.) Manufactured)), N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine (trade name "NDI-101" (Midori) Chemical (manufacturing))), N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine (trade name "NDI-105" ( Manufactured by Midori Chemical Co., Ltd.), N-(nonafluorobutoxysulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine (trade name "NDI-109" (Midori Chemical Co., Ltd.), N-(camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine (trade name "NDI-106" (Midori Chemical Co., Ltd.)), N-(camphorsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-( Trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4-methylphenylsulfonyloxy) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(4-methylphenylsulfonyloxy)-7-oxabicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2. 2.1] H--5-ene-2,3-dicarboxy quinone imine, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N -(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(trifluoromethylsulfonate) Oxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxyindenine, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5 ,6-oxy-2,3-dicarboxy quinone imine, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3 -Dicarboxy quinone imine, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxy quinone imine, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxyindenine, N-(trifluoromethylsulfonate) Oxy) naphthoquinone imine (trade name "NAI-105" (manufactured by Midori Chemical Co., Ltd.)), N-(camphorsulfonyloxy)naphthoquinone imine (trade name "NAI-106" (Midori Chemical Co., Ltd.), N-(4-methylphenylsulfonyloxy)naphthoquinone imine (trade name "NAI-101" (Midori Chemistry ( )))), N-(phenylsulfonyloxy)naphthoquinone imine (trade name "NAI-100" (Midori Chemical Co., Ltd.)), N-(2-trifluoromethylphenyl) Sulfomethoxy)naphthoquinone imine, N-(4-fluorophenylsulfonyloxy)naphthoquinone imine, N-(pentafluoroethylsulfonyloxy)naphthoquinone Amine, N-(heptafluoropropylsulfonyloxy)naphthoquinone imine, N-(nonafluorobutoxysulfonyloxy)naphthoquinone imine (trade name "NAI-109" ( Midori Chemical Co., Ltd.)), N-(ethylsulfonyloxy)naphthoquinone imine, N-(propylsulfonyloxy)naphthoquinone imine, N-(butylsulfonate) Oxy) naphthoquinone imine (trade name "NAI-1004" (Midori Chemical Co., Ltd.)), N-(pentylsulfonyloxy)naphthoquinone imine, N-(hexylsulfonium) Oxy)naphthylimine, N-(heptylsulfonyloxy)naphthylimine, N-(octylsulfonyloxy)naphthylimine, N-(decylsulfonate)醯oxy)naphthylquinoneimine and the like.

As another example of the thermosensitive acid generator, 1-(4-n-butoxynaphthalen-1-yl)tetrathiothiobenzoate trifluoromethanesulfonate, 1-(4,7) a tetrahydrothiobenzoquinone salt such as dibutoxy-1-naphthyl)tetrahydrothiobenzoquinone trifluoromethanesulfonate.

Among the heat-sensitive acid generators exemplified so far, benzyl-4-hydroxyphenylmethyl hexafluorophosphate, 1 is particularly preferable from the viewpoint of the catalyst action of the curing reaction of the component [A]. -(4,7-dibutoxy-1-naphthyl)tetrahydrothiobenzoquinone trifluoromethanesulfonate, N-(trifluoromethylsulfonyloxy)naphthoquinone imine.

The heat-sensitive acid generator of the component [I] may be used singly or in combination of two or more. The amount of the component [I] is preferably 0.1 parts by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass, per 100 parts by mass of the component [A]. When the amount of the component [I] is from 0.1 part by mass to 10 parts by mass, the radiation sensitivity of the positive-type radiation sensitive composition can be optimized, and an interlayer insulating film having a high surface hardness can be formed while maintaining transparency.

Radiation-sensitive resin composition

The radiation sensitive resin composition of the present invention can be prepared by uniformly mixing the above [A], [B] and [C] components and optional components ([D] to [I] components). Usually, the radiation sensitive resin composition is preferably dissolved in a suitable solvent and stored and used in a solution state. For example, a radiation-sensitive resin composition in a solution state can be prepared by mixing [A], [B], and [C] components and optional components in a predetermined ratio in a solvent.

As the solvent to be used in the preparation of the radiation sensitive resin composition, the components of the above [A], [B], and [C] components and the optional components ([D] to [I] components) can be uniformly dissolved, and The solvent to be reacted with each component is not particularly limited. As such a solvent, those which are the same as those exemplified as the solvent used in the production of the copolymer [A] can be mentioned.

Among these solvents, alcohols, glycol ethers, and ethylene glycol alkyl ether acetates are preferably used from the viewpoints of solubility of each component, non-reactivity of each component, easiness of formation of a coating film, and the like. , esters and diethylene glycol alkyl ethers. Among these solvents, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol are particularly preferred. Diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2- or 3-methoxypropionate methyl ester, Ethyl 2- or 3-ethoxypropionate.

Further, the aforementioned solvent and the high boiling point solvent may be used together to improve the in-plane uniformity of the film thickness of the formed coating film. Examples of the high boiling point solvent which can be used together include N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, and N. N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl racelus acetate Wait. Among these high boiling solvents, N-methylpyrrolidone, γ-butyrolactone, and N,N-dimethylacetamide are preferred.

When a high boiling point solvent is used as a solvent for the radiation sensitive resin composition, the amount thereof is 50% by mass or less, preferably 40% by mass or less, and more preferably 30% by mass or less based on the total of the solvent. When the use ratio of the high boiling point solvent is 50% by mass or less, the film thickness uniformity of the coating film can be improved, and the radiation sensitivity can be suppressed from being lowered.

When the radiation sensitive resin composition is prepared in a solution state, the ratio of the components other than the solvent in the solution (that is, the total amount of the copolymer [A], [B], and [C] components, and other optional components) may be The purpose of use and the desired film thickness are arbitrarily set, and it is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 15 to 35% by mass. The solution of the radiation sensitive resin composition thus prepared may be filtered using a micropore filter having a pore size of about 0.2 μm or the like, and then used.

Formation of interlayer insulating film

Next, a method of forming the interlayer insulating film of the present invention using the above-described radiation sensitive resin composition will be described. The method includes the following steps in the order described below.

(1) a step of forming a coating film of the 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 the step (1) with radiation,

(3) a step of developing the coating film irradiated with radiation in the step (2), and

(4) A step of heating and baking the coating film developed in the step (3).

(1) Step of forming a coating film of a radiation sensitive resin composition on a substrate

In the step (1), a solution of the radiation sensitive resin composition of the present invention is applied onto the surface of the substrate, and it is preferred to remove the solvent by prebaking to form a coating film of the radiation sensitive resin composition. Examples of the type of substrate that can be used include a glass substrate, a tantalum wafer, a plastic substrate, and a substrate on which various metals are formed on the surface. Examples of the plastic substrate include a resin substrate formed of a plastic such as polyethylene terephthalate (PET), polybutylene terephthalate, polyether oxime, polycarbonate, or polyimide.

The coating method of the composition solution is not particularly limited, and for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or a spray method can be employed. Appropriate methods such as ink method. Among these coating methods, a spin coating method, a bar coating method, and a slit extrusion coating method are preferred. The conditions for the prebaking may vary depending on the type of the various components, the ratio of use, and the like, and may be, for example, 30 to 10 minutes at 60 to 90 °C. The film thickness of the formed coating film is preferably from 0.1 to 8 μm, more preferably from 0.1 to 6 μm, still more preferably from 0.1 to 4 μm, as a value after baking.

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

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

Examples of the ultraviolet rays include a g line (wavelength: 436 nm), an i line (wavelength: 365 nm), and the like. Examples of the far ultraviolet rays include KrF excimer lasers and the like. Examples of the X-rays include radiation of a synchrotron and the like. Examples of the charged particle beam include an electron beam and the like. Among these radiations, ultraviolet rays, particularly ultraviolet rays, containing radiation of g-line and/or i-line are preferable. The exposure amount is preferably from 30 to 1,500 J/m ² .

(3) Development step

In the (3) development step, the coating film irradiated with radiation in the step (2) is developed to remove a portion irradiated with radiation, whereby a desired pattern can be formed. As the developer used in the development treatment, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, or the like can be used. Di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, acridine, 1,8-diaza An aqueous solution of a base (basic compound) such as heterobicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonane. In addition, an aqueous solution of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be appropriately added to the alkaline aqueous solution, or a small amount of an aqueous alkaline solution containing various organic solvents in which the radiation sensitive resin composition is dissolved may be used as a developing solution. . Further, as the developing method, an appropriate method such as a liquid-filling method, a dipping method, a shaking dipping method, or a shower method can be used. The development time varies depending on the composition of the radiation sensitive resin composition, and may be, for example, 30 to 120 seconds.

After the development step, it is preferred that the patterned film is subjected to a rinsing treatment by running water washing, and then the entire surface is irradiated with radiation (post-exposure) by a high-pressure mercury lamp or the like to deposit a 1,2-醌 stack remaining in the film. The nitrogen compound is subjected to decomposition treatment.

(4) Heating step

Next, in the heating step (4), the film is heated and fired (post-baking treatment) using a heating device such as a hot plate or an oven to cure the film. The exposure amount of the above post exposure is preferably about 2,000 to 5,000 J/m ² . Further, the firing temperature in the heating step is preferably from 120 to 180 ° C, particularly preferably from 120 to 150 ° C. The heating time varies depending on the type of the heating device, for example, 5 to 40 minutes when heat treatment is performed on a hot plate, and 30 to 80 minutes when heat treatment is performed in an oven, and particularly, on a hot plate. In the case of heat treatment, it is carried out within 30 minutes, and in the case of heat treatment in an oven, it is within 60 minutes. Thus, a pattern-like film corresponding to the target interlayer insulating film can be formed on the surface of the substrate.

As described above, the interlayer insulating film of the present invention which is formed by heating at a low temperature for a short period of time has sufficient surface hardness and is excellent in solvent resistance and relative dielectric constant as is apparent from the examples described later. Therefore, the interlayer insulating film is suitable for use as an interlayer insulating film of a flexible display.

Example

Hereinafter, the present invention will be described in more detail by way of Synthesis Examples and Examples, but the present invention is not limited by these 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.

Measuring device: "HLC8220 System" (manufactured by Tosoh)

Separation column: 4 TSKgel GMH _HR -N (manufactured by Tosoh) series connection

Column temperature: 40 ° C

Eluent solvent: tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.)

Flow rate: 1.0 mL / min

Sample concentration: 1.0% by mass

Sample injection amount: 100μm

Detector: Differential Refractometer

Reference material: monodisperse polystyrene

Further, the solution viscosity of the radiation sensitive resin composition was measured at 30 ° C using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.).

Synthesis example of copolymer [Synthesis Example 1]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were added. Then, 16 parts by mass of methacrylic acid, 16 parts by mass of tricyclo [5.2.1.0 ^2,6 ] fluoren-8-yl methacrylate, 20 parts by mass of 2-methylcyclohexyl acrylate, and 40 parts by mass of methacrylic acid were added. Glycidyl ester, 10 parts by mass of styrene, after nitrogen replacement, began to stir slowly. The temperature of the solution was raised to 70 ° C and maintained at this temperature 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 8,000 and a molecular weight distribution (Mw/Mn) of 2.3. Further, the solid content concentration of the polymer solution obtained here (the ratio of the mass of the copolymer contained in the polymer solution to the total weight of the polymer solution. The same applies hereinafter) was 34.4% by mass.

[Synthesis Example 2]

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethyl methyl ether were added. Then, 11 parts by mass of methacrylic acid, 12 parts by mass of tetrahydrofurfuryl methacrylate, 40 parts by mass of glycidyl methacrylate, 15 parts by mass of N-cyclohexylmaleimide, and 10 parts by mass of methacrylic acid were added. After the lauryl ester and 10 parts by mass of α-methyl-p-hydroxystyrene were replaced with nitrogen, stirring was started slowly. The temperature of the solution was raised to 70 ° C and maintained at this temperature for 5 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 8,000 and a molecular weight distribution (Mw/Mn) of 2.3. Further, the solid content concentration of the polymer solution obtained here was 31.9% by mass.

[Comparative Synthesis Example 1]

In a flask equipped with a cooling tube and a stirrer, 18 parts by mass of 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane was added under a nitrogen stream, and dissolved to 75 parts by mass of N-A. After the pyridine-2-pyrrolidone was added, 9.5 parts by mass of 1,2,3,4-cyclobutyric anhydride was added, and the mixture was stirred at room temperature for 8 hours to carry out a polymerization reaction. The obtained polyaminic acid solution was diluted to 10% by mass with N-methyl-2-pyrrolidone. To the solution, 26 parts by mass of acetic anhydride and 16 parts by mass of pyridine as a ruthenium imidization catalyst were added, and the mixture was reacted at room temperature for 30 minutes, and then reacted at 40 ° C for 90 minutes to obtain a polyimine solution. This solution was poured into a large amount of a mixed solution of methanol and water, and the obtained white precipitate was filtered and dried to give a white powder of the polyimine [P-1]. The polyimine powder was dissolved in propylene glycol monomethyl ether to obtain a solution containing polyimine [P-1].

<Preparation of Resin Composition> [Example 1]

The copolymer [A-1] solution containing Synthesis Example 1 as the component [A] was added in an amount corresponding to 100 parts by mass of the copolymer (solid content), and 30 parts by mass of 4, 4' as the component [B] was added. -[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]biphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 a condensate (B-1) of sulfonium chloride (2.0 mol) and 30 parts by mass of pentaerythritol tetrakis(3-mercaptopropionate) (C-1) as a component [C] (crosslinking agent), Then, diethylene glycol ethyl methyl ether was added as a solvent to have a solid content concentration of 30% by mass, and then filtered through a membrane filter having a diameter of 0.2 μm to prepare a radiation sensitive resin composition (S-1).

[Embodiment 2]

The copolymer [A-1] solution containing Synthesis Example 1 as the component [A] was added in an amount corresponding to 100 parts by mass of the copolymer (solid content), and 30 parts by mass of 4, 4' as the component [B] was added. -[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]biphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 a condensate (B-1) of sulfonium chloride (2.0 mol), 30 parts by mass of pentaerythritol tetrakis(3-mercaptopropionate) (C-1) as a component [C] (crosslinking agent), and 0.5 parts by mass of 2-phenylbenzimidazole (D-1) as a component [D] (crosslinking aid), followed by addition of diethylene glycol ethyl methyl ether as a solvent to have a solid content concentration of 30% by mass The radiation sensitive resin composition (S-2) was prepared by filtration through a membrane filter having a diameter of 0.2 μm.

[Example 3]

The radiation sensitive resin composition (S-3) was prepared by mixing the components in the same manner as in Example 2 except that the copolymer [A-2] was used instead of the copolymer [A-1].

[Example 4]

A radiation sensitive resin was prepared by mixing the components in the same manner as in Example 2 except that trimethylolpropane tris(3-mercaptopropionate) (C-2) was used instead of the compound (C-1) as the component [C]. Composition (S-4).

[Example 5]

A radiation sensitive resin was prepared by mixing the components in the same manner as in Example 2 except that dipentaerythritol hexakis(3-mercaptopropionate) (C-3) was used as the component (C-1). Composition (S-5).

[Embodiment 6]

A radiation sensitive resin composition (S-6) was prepared by mixing the components in the same manner as in Example 2 except that 2-methylimidazole (D-2) was used instead of the compound (D-1) as the component [D].

[Embodiment 7]

A radiation sensitive resin composition (S-7) was prepared by mixing the components in the same manner as in Example 2 except that 2-methylbenzimidazole (D-3) was used instead of the compound (D-1) as the component [D]. ).

[Embodiment 8]

In addition to using 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione (C-4) In place of the compound (C-1), as the component [C], the components were mixed in the same manner as in Example 2 to prepare a radiation-sensitive linearity. Resin composition (S-8).

[Embodiment 9]

A radiation sensitive resin combination was prepared by mixing the components in the same manner as in Example 2 except that neopentyl alcohol tetrakis(3-mercaptobutyrate) (C-5) was used instead of the compound (C-1) as the component [C]. (S-9).

[Embodiment 10]

A radiation sensitive resin combination was prepared by mixing the components in the same manner as in Example 2 except that neopentyl alcohol tetrakis(3-mercaptovalerate) (C-6) was used instead of the compound (C-1) as the component [C]. (S-10).

[Example 11]

A radiation sensitive resin composition was prepared by mixing the components in the same manner as in Example 2 except that tetraethylene glycol bis(3-mercaptopropionate) (C-7) was used instead of the compound (C-1) as the component [C]. (S-11).

[Embodiment 12]

A radiation sensitive resin composition was prepared by mixing the components in the same manner as in Example 2, except that neopentyltetrakis(mercaptoacetate) (C-8) was used instead of the compound (C-1) as the component [C]. S-12).

[Example 13]

The components were mixed in the same manner as in Example 2 except that 1,4-bis(3-mercaptobutoxy)butane (C-9) was used instead of the compound (C-1) as the component [C], and radiation was prepared. Resin composition (S-13).

[Embodiment 14]

A radiation sensitive resin composition (S-) was prepared by mixing the components in the same manner as in Example 9 except that benzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate (I-1) was used as the component [I]. 14).

[Example 15]

In addition to using 1-(4,7-dibutoxy-1-naphthyl)tetrahydrothiobenzene In the same manner as in Example 9, except that the trifluoromethanesulfonate (I-2) was used as the component [I], a radiation sensitive resin composition (S-15) was prepared.

[Example 16]

A radiation sensitive resin composition was prepared by mixing the components in the same manner as in Example 9 except that N-(trifluoromethylsulfonyloxy)naphthylimine (I-3) was used as the component [I]. S-16).

[Comparative Example 1]

The radiation-sensitive resin composition (s-1) was prepared by mixing the components in the same manner as in Example 1 except that the component [C] was not used.

[Comparative Examples 2 and 3]

A solution containing the polyimine [P-1] obtained in Comparative Synthesis Example 1 was prepared as a composition (s-2) of these comparative examples.

[Reference Example 1]

The same radiation sensitive resin composition (S-2) as in Example 2 was prepared and used as this reference example.

In Table 1, the abbreviation of the component means the following compound.

C-1: pentaerythritol tetrakis(3-mercaptopropionate)

C-2: Trimethylolpropane tris(3-mercaptopropionate)

C-3: dipentaerythritol hexa(3-mercaptopropionate)

C-4: 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione

C-5: pentaerythritol tetrakis(3-mercaptobutyrate)

C-6: pentaerythritol tetrakis(3-mercaptovalerate)

C-7: tetraethylene glycol bis(3-mercaptopropionate)

C-8: pentaerythritol tetrakis(mercaptoacetate)

C-9: 1,4-bis(3-mercaptobutyloxy)butane

D-1: 2-phenylbenzimidazole

D-2: 2-methylimidazole

D-3: 2-methylbenzimidazole

I-1: benzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate

I-2: 1-(4,7-dibutoxy-1-naphthalenyl)tetrahydrothiobenzoquinone trifluoromethanesulfonate

I-3: N-(trifluoromethylsulfonyloxy)naphthoquinone imine ("NAI-105" manufactured by Midori Chemical Co., Ltd.)

<Evaluation of properties as interlayer insulating film>

Using the resin composition prepared as above, various properties as an interlayer insulating film were evaluated as follows.

[Evaluation of Radiation Sensitivity]

In addition to Example 16, a spin coater was used to apply any one of the above compositions (S-1) to (S-15) and (s-1) to (s-2) on a tantalum substrate at 90 ° C. Next, it was prebaked on a hot plate for 2 minutes to form a coating film having a film thickness of 3.0 μm. The obtained coating film was irradiated with a predetermined amount of ultraviolet rays by a mercury lamp through a pattern mask having a pattern of lines and spaces having a width of 10 μm. Next, using a developing solution formed of a 2.38 mass% aqueous solution of tetramethylammonium hydroxide, the developing treatment was carried out at 25 ° C for 60 seconds, and then washed with ultrapure water for 1 minute. At this time, the minimum ultraviolet irradiation amount of the pattern which can form the line and space of the width of 10 micrometer was measured. When the value is less than 800 J/m ² , the sensitivity is referred to as good. This value is shown in Table 1 as the radiation sensitivity.

In Example 16, a PET film (Teijin Tetron Film O3, thickness: 188 μm) was used instead of the ruthenium substrate, and the above composition (S-16) was used to form a coating film by a bar coater. The film was prebaked in a clean oven at 90 ° C for 2 minutes to form a coating film having a film thickness of 3.0 μm. The subsequent evaluation was carried out in the same manner as in Examples 1 to 15 except for the evaluation of the voltage holding ratio.

[Evaluation of solvent resistance]

Applying any one of the above compositions (S-1) to (S-16) and (s-1) to (s-2) on a crucible substrate using a spin coater, at 90 ° C in a hot plate The film was prebaked for 2 minutes to form a coating film having a film thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the cumulative irradiation amount was 3,000 J/m ² . Next, the composition of Examples 1 to 16 and Comparative Examples 1 and 2 was heated on the hot plate at 150 ° C for 30 minutes, and the composition of Comparative Example 3 was heated at 150 ° C for 60 minutes. The composition of Reference Example 1 was heated at 220 ° C for 30 minutes, and the coating film was heat-treated, and the film thickness (T1) of the obtained cured film was measured. Then, the ruthenium substrate on which the cured film was formed was immersed in dimethyl sulfoxide having a temperature of 70 ° C for 20 minutes, and then the film thickness (t1) of the cured film was measured, and the film thickness change rate by immersion was calculated. {(t1-T1)/T1}×100[%]. When the absolute value of this value is less than 5%, it is called solvent resistance. The results are shown in Table 1.

[Evaluation of relative dielectric constant]

Applying any one of the above compositions (S-1) to (S-16) and (s-1) to (s-2) on a crucible substrate using a spin coater, at 90 ° C in a hot plate The film was prebaked for 2 minutes to form a coating film having a film thickness of 3.0 μm. Using the MPA-600FA exposure machine manufactured by Canon, the obtained coating film was exposed and the cumulative exposure amount was 9,000 J/m ² , and the substrate was heated in a clean oven at 150 ° C for 30 minutes on the SUS substrate. A cured film is formed thereon. A Pt/Pd electrode pattern was formed on the cured film by a vapor deposition method, and a sample for measuring conductivity was produced. For the substrate having the electrode pattern, the relative dielectric constant was measured by a CV method at a frequency of 10 kHz using an HP16451B electrode manufactured by Yokogawa ‧ Hewlett Packard Co., Ltd. and an HP 4284A precision LCR meter. When the value is 3.9 or less, the dielectric constant can be considered to be good. The measurement results are shown in Table 1.

[Evaluation of pencil hardness (surface hardness)]

The pencil hardness (surface hardness) of the cured film was measured by a 8.4.1 pencil scratching test of JIS K-5400-1990 on the substrate having the cured film formed in the above [evaluation of solvent resistance]. When the value is 3H or more, the surface hardness of the interlayer insulating film is good, and it is considered that the resin composition for forming the cured film has sufficient curability.

From the results shown in Table 1, it is understood that the radiation sensitive resin composition prepared in Examples 1 to 16 has high radiation sensitivity, and heating at a low temperature for a short time can obtain a cured film having a high surface hardness, and the cured film Both excellent solvent resistance and relative dielectric constant. On the other hand, in Comparative Example 1 in which the [C] component was not used, sufficient curing property was not exhibited at a low temperature and for a short period of time, and the solvent resistance and the relative dielectric constant of the cured film were inferior. In Comparative Examples 2 and 3 in which the polyimide reaction solution was used, a pattern based on exposure development could not be formed, and sufficient curability could not be exhibited at a low temperature and a short time of heating, and the solvent resistance of the cured film was poor. Further, as a result of evaluation of various properties in Example 2, the same radiation sensitive resin composition as in Example 2 was used, but the evaluation results of Reference Example 1 in which the heating temperature and time were increased were equal. That is, it is known that by using the radiation sensitive resin composition of the present invention, an interlayer insulating film which satisfies various properties such as required surface hardness can be formed at a lower temperature than the present time and in a shorter time.

Industrial use possibility

The radiation sensitive resin composition of the present invention can form an interlayer insulating film by heating at a low temperature and for a short period of time, and can form an interlayer insulating film excellent in solvent resistance and relative dielectric constant, and is therefore suitable for use as an interlayer insulating film of a flexible display. Form the material.

Claims (6)

A radiation sensitive resin composition for forming an interlayer insulating film comprising: [A] a single article containing an unsaturated polymer of (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride, and (a2) an epoxy group-containing unsaturated compound a copolymer-formed alkali-soluble resin, [B] 1,2-quinonediazide compound, and [C] a compound having two or more mercapto groups in one molecule as shown in the following formula (1), but Tetraol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), neopentyltetrakis(2-mercaptoacetate), pentaerythritol tris(2-mercaptoacetate) Acid ester), trimethylolpropane tris(3-mercaptopropionate), trimethylolethane tris(3-mercaptopropionate), trimethylolpropane tris(2-mercaptoacetate) and Except for trimethylolethane tris(2-mercaptoacetate), the content of the [B] component is 5 to 100 parts by mass with respect to 100 parts by mass of the component [A], and the component [C] The content is 0.1 to 60 parts by mass, (In the formula (1), R ¹ is a methylene group, an alkylene group having 2 to 10 carbon atoms or an alkylmethylene group, and Y is a single bond, -CO- or -O-CO-* (wherein The linkage with "*" is linked to R ¹ ), n is an integer from 2 to 10, and X is an n-valent hydrocarbon group having from 2 to 70 carbon atoms which may have one or more ether linkages, or n is 3 is a group represented by formula (2); in formula (2), 3 R ² are each independently a methylene group or an alkyl group having 2 to 6 carbon atoms, and 3 "*" respectively Indicates the connection key). The radiation sensitive linear resin composition according to claim 1, wherein the compound represented by the formula (1) of the [C] component is an esterified product of a mercaptocarboxylic acid and a polyhydric alcohol. The radiation sensitive resin composition according to claim 1 or 2, further comprising [D] a compound represented by the following formula (3), (In the formula (3), Z ¹ , Z ² , Z ³ and R ³ each independently represent a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Z ² and Z ³ may be connected to each other to form a ring). A method of forming an interlayer insulating film, comprising: (1) a step of forming a coating film of a radiation sensitive resin composition according to any one of claims 1 to 3 on a substrate, and (2) a step of 1) A step of irradiating at least a part of the formed coating film with radiation. (3) a step of developing the coating film irradiated with radiation in the step (2), and (4) a step of heating and baking the coating film developed in the step (3). The method of claim 4, wherein the firing temperature of the step (4) is 180 ° C or less. An interlayer insulating film formed of the radiation sensitive resin composition according to any one of claims 1 to 3.