JP5526766B2 - Radiation-sensitive resin composition, interlayer insulating film and method for forming the same - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition suitably used for forming an interlayer insulating film for a display element, an interlayer insulating film formed from the composition, and a method for forming the same.

  In recent years, flexible displays such as liquid crystal electronic paper have become widespread due to improvements in convenience such as weight reduction and size reduction. As a substrate for such a flexible display, a plastic substrate such as polycarbonate or polyethylene terephthalate has been studied instead of a glass substrate. However, these plastics have a problem that they are slightly expanded and contracted when heated, thereby impeding the function as a display, and improvement in heat resistance is an urgent need. 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 manufacturing process. One of the processes requiring the highest temperature in manufacturing a flexible display is a process of baking an interlayer insulating film by heating, and a reduction in the heating process is required.

  At present, as a material for forming an interlayer insulating film, a radiation-sensitive resin composition is widely used because it has a small number of steps for obtaining a required pattern shape and preferably has a high hardness. . As such a radiation sensitive resin composition, for example, JP-A No. 2001-354822 discloses a sensitivity containing a copolymer composed of an unsaturated carboxylic acid and / or an anhydride thereof, an epoxy group-containing unsaturated compound, and the like. A radiation resin composition is disclosed, and is configured to obtain hardness as an interlayer insulating film by a cleavage reaction between a carboxyl group and an epoxy group. However, a heating process at a high temperature of 200 ° C. or higher is required to increase the hardness to a level that is actually required commercially as an interlayer insulating film. Furthermore, since the interlayer insulating film is sufficiently cured by low-temperature firing, there is a concern that mixing of an uncured substance into the liquid crystal layer may cause deterioration of electrical characteristics. Considering the heat resistance of the plastic substrate, the temperature of the heating process is preferably 180 ° C. or lower, and thus the above-mentioned composition is not suitable for the plastic substrate.

In view of the above circumstances, Japanese Unexamined Patent Application Publication No. 2009-4394 discloses a flexible display that is excellent in terms of solvent resistance, specific resistance, semiconductor mobility, etc. by firing a low-temperature curable polyimide precursor at 180 ° C. or lower. It is disclosed that a gate insulating film can be obtained. However, since the coating liquid containing the polyimide precursor of the above document is a chemical curing system and does not have pattern forming ability by exposure and development, fine pattern formation is impossible. Therefore, a resin composition having a radiation sensitivity capable of being heated and fired at a low temperature so as to be suitably used for producing an insulating film for a flexible display, and capable of simple film formation and fine pattern formation. There is a strong demand for product development.

Japanese Patent Application Laid-Open No. 2009-20246 discloses a photosensitive resin composition containing a polyimide, an acrylic resin, a photoacid generator, and a thermally crosslinkable compound that exhibit insulating properties even at low temperature baking at 150 ° C. However, in this case, the compatibility between the polyimide resin and the acrylic resin is poor, and it has been difficult to provide a positive photosensitive resin composition excellent in pattern formation and resolution.

Moreover, in the device manufacturing process of 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 against the solvent used when forming a laminate by coating.

JP 2001-354822 A JP 2009-4394 A JP 2009-20246 A

  The present invention has been made based on the above circumstances, and its purpose is to enable heating and baking at a low temperature in a short time and to have high radiation sensitivity, and to provide an interlayer insulating film for a flexible display. It is providing the radiation sensitive resin composition used suitably for formation of this. At the same time, it is to provide a positive-type radiation-sensitive resin composition excellent in relative dielectric constant, solvent resistance, film hardness, resolution at the time of pattern formation and electrical characteristics.

The present invention made to solve the above problems is selected from the group consisting of [A] a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine compound and a polyimide obtained by dehydrating and ring-closing the polyamic acid. At least one polymer (hereinafter also referred to as [A] component), [B] 1,2-quinonediazide compound (hereinafter also referred to as [B] component) and [C] at least one in the molecule. A positive radiation-sensitive resin composition comprising a compound having an epoxy group (hereinafter also referred to as [C] component).

The radiation-sensitive resin composition includes a [A] component, a [B] component, and a [C] component. The positive-type radiation-sensitive resin composition is characterized by having a high radiation sensitivity and a low temperature. It is possible to form an interlayer insulating film by heating and baking for a short time, and it is possible to form an interlayer insulating film having excellent solvent resistance and pattern resolution and excellent relative dielectric constant. It is suitably used as a material for forming an interlayer insulating film.

The tetracarboxylic dianhydride used for the component [A] is a compound represented by the following formula (1), a compound represented by the following formula (2), pyromellitic dianhydride, 1,2,4- Tricarboxycyclopentylacetic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride and 1,2,4,5-cyclohexanetetracarboxylic Those containing a polymer selected from the group consisting of acid dianhydrides are desirable.

(In the formula (1), ^{R 1} each independently represent a hydrogen atom, a chlorine atom or an alkyl group having 1 to 6 carbon atoms.)

(In the formula (2), ^{R 2} is, independently, an alkyl group having 1 to 6 carbon atoms, n is an integer from 0-4.)

The diamine compound used for the component [A] is preferably a diamine compound having a steroid skeleton.

Moreover, the positive radiation sensitive resin composition of the present invention is preferably used for forming an interlayer insulating film for a display element,
(1) The process of forming the coating film of the said radiation sensitive resin composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) It includes a step of developing the coating film irradiated with radiation in step (2), and a step of (4) baking the coating film developed in step (3) by heating. Here, “firing” means heating until the required hardness for the interlayer insulating film is obtained.

  When using the positive radiation sensitive resin composition and forming an interlayer insulating film by the above process, a pattern is formed by exposure and development utilizing radiation sensitivity. Can be formed. In addition, an interlayer insulating film having sufficient surface hardness and pattern resolution can be formed by heating at a low temperature for a short time by exposure / development using the radiation-sensitive resin composition.

The firing temperature in step (4) in the method for forming an interlayer insulating film is preferably 230 ° C. or lower, more preferably 200 ° C. or lower, and particularly preferably 180 ° C. or lower. In addition to the ability to form fine patterns utilizing radiation sensitivity, the method can be used for the formation of an interlayer insulating film on a plastic substrate of a flexible display by being capable of firing at such a low temperature. Preferably used.

The radiation-sensitive resin composition for forming an interlayer insulating film according to the present invention contains the above-mentioned [A] component, [B] component, [C] component, and other optional components. Hereinafter, each component will be described.

[A] Component [A] The component contains a polymer selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine compound and a polyimide obtained by dehydrating and ring-closing the polyamic acid. .

[Tetracarboxylic dianhydride]
Examples of the tetracarboxylic dianhydride used for synthesizing the polyamic acid or polyimide contained in the present invention include, for example, a compound represented by the above formula (1), a compound represented by the formula (2), and butanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyl Tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,4-tricarboxycyclopentylacetic acid dianhydride, bicyclo [2.2.1] heptane-2,3,5 , 6-tetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, tetracyclo [4.4.0.1 2,5.17,10] dodeca -3,4,8,9-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl- 3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2.2.2] -oct-4-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2. 2] -Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, the following formulas (II-1) and (II-2)

(In the above formula, R ³ and R ⁵ are each a divalent organic group having an aromatic ring, R ⁴ and R ⁶ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁴ and R ^{6 present} may be the same or different from each other.) An aliphatic or alicyclic tetracarboxylic dianhydride such as a compound represented by each of them; pyromellitic dianhydride, 3, 3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic Acid dianhydride 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) ) Diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3 , 3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, Ethylene glycol-bis (anhydro trimellitate), propylene glycol-bis (anhydro trimellitate), 1,4-butanediol-bis (anhydro trimellitate) Retate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis ( Anhydrotrimellitate) and aromatic tetracarboxylic dianhydrides such as compounds represented by the following formulas (3) to (6).

Specific examples of the compound represented by the above formula (1) include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, for example. Acid dianhydride, 1,2-diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1 , 3-Diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4 -Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride and the like, among which 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl -1,2,3 4-cyclobutanetetracarboxylic dianhydride, 1,2-diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid A dianhydride or 1,3-diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride is preferred.

Specific examples of the compound represented by the above formula (2) include, for example, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4 , 9b-Hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5 , 9b-Hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5 , 9b-Hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5 , 9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione.

These tetracarboxylic dianhydrides can be used alone or in combination of two or more. Among these, the compound represented by the above formula (1), the compound represented by the above formula (2), pyromellitic dianhydride, 1,2,4-tricarboxycyclopentylacetic acid dianhydride, 2,3 , 5-tricarboxycyclopentylacetic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride and 1,2,4,5-cyclohexanetetracarboxylic dianhydride It is preferable to use a tetracarboxylic dianhydride containing at least one (hereinafter also referred to as “specific tetracarboxylic dianhydride”).

When the polymer included in the present invention is a polyamic acid, the tetracarboxylic dianhydride used for synthesizing the polymer is a specific tetracarboxylic dianhydride with respect to the total amount of the tetracarboxylic dianhydride. It is preferable to contain more than mol%, more preferably more than 20 mol%, still more preferably more than 40 mol%. In this case, it is preferable to use an alicyclic tetracarboxylic dianhydride as the tetracarboxylic dianhydride other than the specific tetracarboxylic dianhydride.

On the other hand, when the polymer included in the present invention is a polyimide, the tetracarboxylic dianhydride used for synthesizing the polymer is a specific tetracarboxylic dianhydride with respect to the total amount of the tetracarboxylic dianhydride. It is preferable to contain 50 mol% or more, more preferably 70 mol% or more, and further preferably 80 mol% or more. In this case, it is preferable to use an alicyclic tetracarboxylic dianhydride as the tetracarboxylic dianhydride other than the specific tetracarboxylic dianhydride.

[Diamine compound]
Examples of the diamine compound used for synthesizing the polyamic acid or polyimide contained in the present invention include the following formulas (III-1) and (III-2):

(In the above formula, X ¹ is independently of each other a single bond, —O—, —CO—, —COO—, —OCO—, —NHCO—, —CONH—, —S—, methylene group, carbon number, R ⁷ is an alkyl group having 10 to 20 carbon atoms, a monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms, or a fluorine atom having 6 to 20 carbon atoms. And R ⁸ is a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms.) And other diamine compounds. it can.

In the formula (III-1), examples of the alkyl group having 10 to 20 carbon atoms represented by R ⁷ include an n-decyl group, an n-dodecyl group, an n-pentadecyl group, an n-hexadecyl group, and an n-octadecyl group. Group, n-eicosyl group and the like. Examples of the alicyclic skeleton contained in the monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms include alicyclic skeletons derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane and cyclodecane; norbornene and adamantane And the like, and the like.
Here, the steroid skeleton refers to a structure composed of a cyclopentano-perhydrophenanthrene nucleus or a skeleton in which one or more of its carbon-carbon bonds are double bonds. The monovalent organic group having a steroid skeleton of R ⁷ is preferably those having 17 to 40 carbon atoms, and more preferably those having 17 to 29 carbon atoms. Specific examples of R7 having such a steroid skeleton include, for example, cholestane-3-yl group, cholesta-5-en-3-yl group, cholesta-24-en-3-yl group, cholesta-5,24-diene- A 3-yl group etc. can be mentioned.

In the monovalent organic group having an alicyclic skeleton of R ⁷ , part or all of the hydrogen atoms may be substituted with a halogen atom, preferably a fluorine atom. Examples of the monovalent organic group having a fluorine atom having 6 to 20 carbon atoms include a linear alkyl group having 6 to 20 carbon atoms such as an n-hexyl group, an n-octyl group, and an n-decyl group; A part or all of hydrogen atoms in an organic group such as an alicyclic hydrocarbon group having 6 to 20 carbon atoms such as a cyclooctyl group; an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group and a biphenyl group is fluorine. Examples thereof include a group substituted with an atom or a fluoroalkyl group (however, the carbon number of R ⁷ is 20 or less including the carbon of the fluoroalkyl group).

X ¹ in the above formula (III-1) is preferably —O—, —CO—, —COO— or —OCO—.
Specific examples of the diamine compound represented by the above formula (III-1) include, for example, dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2. , 4-diaminobenzene, compounds represented by the following formulas (7) to (22), and the like.

In the above formula (III-2), examples of the alicyclic skeleton contained in the divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms represented by R ⁸ include cyclobutane, cyclopentane, cyclohexane, Examples thereof include alicyclic skeletons derived from cycloalkanes such as cyclodecane; bridged alicyclic skeletons such as norbornene and adamantane; steroid skeletons and the like.

Here, the steroid skeleton are the same as the steroid skeleton in the R ^7. The divalent organic group having an R ⁸ steroid skeleton preferably has 17 to 40 carbon atoms, and more preferably has 17 to 29 carbon atoms. Specific examples of R ⁸ having a steroid skeleton include, for example, cholestane-3,3-diyl group, cholestane-3,6-diyl group, cholesta-5-ene-3,6-diyl group, cholesta-24-ene- Examples include 3,6-diyl group and cholesta-5,24-diene-3,6-diyl group.

In the divalent organic group having an alicyclic skeleton of R ⁸ , part or all of the hydrogen atoms may be substituted with a halogen atom, preferably a fluorine atom.
Specific examples of the diamine compound represented by the above formula (III-2) include compounds represented by the following formulas (23) to (27).

Examples of the other diamine compounds include p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2-ethyl-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, , 5-diethyl-1,4-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl Ethane, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4 '-Diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl 3,3′-di (trifluoromethyl) -4,4′-diaminobiphenyl, 3,3′-diethyl-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 4,4′- Diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 6- Amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 3,4′-diaminodiphenyl ether, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′- Diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoro Propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1, 4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10 -Hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetra Chloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphe 1,4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoro) Methylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy]- Aromatic diamines such as octafluorobiphenyl, 4- (4-n-heptylcyclohexyl) phenoxy-2,4-diaminobenzene; 1,3-bis (aminomethyl) benzene, 1,3-propanediamine, tetramethylenediamine, Pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nona Aliphatic diamines such as tylenediamine; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5 , 6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino- 6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2 , 4-Diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamidine No-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxy Two primary amino acids in the molecule, such as acridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine And a diamine having a nitrogen atom other than the primary amino group;
The following formulas (28) to (30)

(In the above formula, each R ⁹ is independently a hydrocarbon group having 1 to 12 carbon atoms, p is each independently an integer of 1 to 3, q is an integer of 1 to 20, y is an integer of 2 to 12, and z is an integer of 1 to 5).

Examples of the other diamine compounds include p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2-ethyl-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,5 -Diethyl-1,4-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminobiphenyl 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl 3,3′-diethyl-4,4′-diaminobiphenyl, 3,3′-di (trifluoromethyl) -4,4′-diaminobiphenyl, 4,4′- Aminodiphenyl ether, 4,4′-diaminobenzophenone, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,6-diaminopyridine or 3,4- Diaminopyridine is preferred.

The said diamine compound can be used individually by 1 type, or can mix and use 2 or more types.

[Synthesis of polyamic acid]
The polyamic acid that can be contained in the alkali-soluble resin of the present invention can be obtained by reacting the tetracarboxylic dianhydride as described above with a diamine compound.
The ratio of tetracarboxylic dianhydride and diamine used in the polyamic acid synthesis reaction is such that the acid anhydride group of tetracarboxylic dianhydride is 0.2 to 2.0 with respect to 1 equivalent of amino group of diamine. The ratio which becomes an equivalent is preferable, More preferably, it is the ratio which becomes 0.8-1.2 equivalent. The polyamic acid synthesis reaction is preferably carried out in an organic solvent, preferably at −20 ° C. to 150 ° C., more preferably at 0 to 100 ° C., preferably 0.5 to 24 hours, more preferably 2 For 10 hours.

The organic solvent that can be used here is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, 1-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl is used. Examples include aprotic polar solvents such as formamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. The amount of organic solvent used (α) is such that the total amount (β) of tetracarboxylic dianhydride and diamine compound is 0.1 to 30% by mass with respect to the total amount (α + β) of the reaction solution. It is preferable.
The above-mentioned organic solvent is used by replacing a part of the amount used with a poor solvent for polyamic acid, such as alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon, etc., so long as the generated polyamic acid does not precipitate. be able to.

Specific examples of the poor solvent include, for example, methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol. Monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, Diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether Ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1, Examples include 2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, and xylene.
When a part of the organic solvent is replaced with a poor solvent, the amount of the poor solvent used is preferably 50% by mass or less based on the total amount of the organic solvent.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This polyamic acid solution may be used for the dehydration ring-closing reaction in the next step as it is, may be subjected to the dehydration ring-closing reaction after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid May be subjected to a dehydration ring closure reaction after purification. The polyamic acid is isolated by pouring the above polyamic acid solution into a large amount of poor solvent to obtain a precipitate, and drying this precipitate under reduced pressure, or by distilling the polyamic acid solution under reduced pressure with an evaporator. It can be carried out. Also, the polyamic acid is purified by a method in which the polyamic acid thus obtained is dissolved again in an organic solvent and then precipitated in a poor solvent, or a method in which the step of distilling off with an evaporator under reduced pressure is performed once or several times. be able to.

[Synthesis of polyimide]
The polyimide that can be contained in the alkali-soluble resin of the present invention can be synthesized by dehydrating and ring-closing the polyamic acid. The polyimide used in the alkali-soluble resin of the present invention may be a completely imidized product in which all of the amic acid structure of the polyamic acid is imidized, or only a part of the amic acid structure is imidized to form an amic acid structure. And a partially imidized product in which an imide structure coexists. When the polymer contained in the alkali-soluble resin of the present invention is polyimide, the imidation ratio is preferably 40% or more. Here, the “imidation ratio” refers to a value representing the percentage of the number of imide structures in the total number of amic acid structures and imide structures in the polymer. The imidation ratio was calculated from ¹ H-NMR obtained by dissolving sufficiently dried polyimide in a suitable deuterated solvent such as deuterated dimethyl sulfoxide and measuring at room temperature using tetramethylsilane as a reference substance. i)

(In Formula (i), A1 is a peak area derived from protons of NH groups (around 10 ppm), A2 is a peak area derived from protons of aromatic rings (7 to 8 ppm), and α is a precursor of a polymer ( It is the ratio of the number of protons in the aromatic ring to one proton in the NH group in the polyamic acid).

The polyamic acid is dehydrated and closed by (1) a method in which the polyamic acid is heated, or (2) a method in which the polyamic acid is dissolved in an organic solvent and a dehydrating agent and a dehydrated ring-closing catalyst are added to the solution and heated as necessary. Can be performed.
The reaction temperature in the method of heating the polyamic acid (1) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the resulting polyimide may decrease. The reaction time is preferably 0.5 to 72 hours, more preferably 1 to 10 hours.

On the other hand, in the method of adding a dehydrating agent and a dehydrating ring closure catalyst to the polyamic acid solution of (2) above, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used. Can do. Although the usage-amount of a dehydrating agent is based on the desired imidation rate, it is preferable to set it as 0.01-20 mol with respect to 1 mol of the amic acid structure which polyamic acid has. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. The imidation rate can be increased as the amount of the above dehydrating agent and dehydrating ring-closing agent increases. Examples of the organic solvent used in the dehydration ring closure reaction include the same organic solvents as exemplified for use in the synthesis of polyamic acid.
The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1 to 12 hours, more preferably 1 to 6 hours.

The imidized polymer obtained in the above method (1) may be subjected to preparation as it is, or may be subjected to preparation after purifying the obtained imidized polymer. On the other hand, in the above method (2), a reaction solution containing an imidized polymer is obtained. This reaction solution may be used for preparation as it is, may be used for preparation after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and may be used for preparation after isolating the imidized polymer. Alternatively, the isolated imidized polymer may be purified and subjected to preparation. In order to remove the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, for example, a method such as solvent replacement can be applied. Isolation and purification of the imidized polymer can be performed by performing the same operations as described above as the method for isolating and purifying the polyamic acid.

[End-modified polymer]
The polyamic acid or polyimide used in the alkali-soluble resin of the present invention may be of a terminal modified type whose molecular weight is adjusted. By using a terminal-modified polymer, the coating properties and the like can be further improved without impairing the effects of the present invention.
Such a terminal-modified polymer can be synthesized by adding an appropriate molecular weight regulator such as acid monoanhydride, monoamine compound, monoisocyanate compound to the reaction system when synthesizing polyamic acid. . Here, as the acid monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride , N-hexadecyl succinic anhydride and the like. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n -Dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine . Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The use ratio of the molecular weight regulator is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass in total of the tetracarboxylic dianhydride and diamine used when the polyamic acid is synthesized. It is.
The polyamic acid or imidized polymer obtained as described above preferably has a solution viscosity of 20 to 800 mPa · s, when it is made into a solution having a concentration of 10% by weight, and preferably has a solution viscosity of 30 to 500 mPa · s. More preferably, it has a solution viscosity.
The solution viscosity (mPa · s) of the above polymer is E for a polymer solution having a concentration of 10% by mass prepared using a good solvent for the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25 ° C. using a mold rotational viscometer.

  [A] component of the present invention is a polymer selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine compound and a polyimide obtained by dehydrating and ring-closing this, preferably It is desirable to use polyimide and polyamic acid in combination. When polyimide is used alone, developability is poor, and polyamic acid alone causes a decrease in voltage holding ratio. When the total amount of polyimide and polyamic acid used is 100 parts by mass, the preferred range of the amount used is preferably a mass ratio of polyimide: polyamic acid = 1: 99 to 50:50, more preferably polyimide. : Polyamic acid = range of mass ratio of 10:90 to 30:70. When the mass ratio of the polyimide and the polyamic acid is in the range of 1:99 to 50:50, a radiation sensitive resin composition in which developability and voltage holding ratio are highly balanced can be obtained. .

[B] 1,2-quinonediazide compound
The 1,2-quinonediazide compound (hereinafter also referred to as [B] component) used in the radiation-sensitive resin composition of the present invention is a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with radiation. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

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

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

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

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

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

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

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

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

  These [B] components can be used individually or in combination of 2 or more types. The use ratio of the [B] component in the radiation-sensitive resin composition is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin of the [A] component. is there. When the proportion of the component [B] used is 5 to 100 parts by mass, the difference in solubility between the irradiated portion and the unirradiated portion with respect to the alkaline aqueous solution serving as the developer is large, the patterning performance is improved, and the obtained interlayer insulation The solvent resistance of the film is also good.

[C] Compound having at least one epoxy group in the molecule Compound having at least one epoxy group in the molecule used for the radiation-sensitive resin composition of the present invention (hereinafter also referred to as [C] component) .) Is effective in improving the surface hardness, solvent resistance and heat resistance of the resulting cured film.
Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane. Diol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N′— Tetraglycidyl-p-phenylenediamine, N, N, N ′, N′-tetraglycidyl-m-phenylenediamine, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodi Phenylmethane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenyl ether, N, N, N ′, N′-tetraglycidyl-2,2′-dimethyl-4,4′-diamino Biphenyl, N, N, N ′, N′-tetraglycidyl-1,2-diaminocyclohexane, N, N, N ′, N′-tetraglycidyl-1,3-diaminocyclohexane, N, N, N ′, N '-Tetraglycidyl-1,4-diaminocyclohexane, bis (N, N-diglycidyl-4-aminocyclohexyl) methane, bis (N, N-diglycidyl-2-methyl-4-aminocyclohexyl) methane, bis (N, N-diglycidyl-3-methyl-4-aminocyclohexyl) methane, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1,4-bis (N, N-diglycidylaminomethyl) cyclohexane, 1,3-bis (N, N-diglycidylaminomethyl) benzene, 1,4-bis (N, N-diglycidylaminomethyl) benzene, 1,3,5-tris Examples include (N, N-diglycidylaminomethyl) cyclohexane, 1,3,5-tris (N, N-diglycidylaminomethyl) benzene, and compounds represented by the following formulas (31) to (35). be able to. The blending ratio of these epoxy compounds is preferably 0.1 with respect to 100 parts by mass of the total amount of the component [A] (referred to as the total amount of contained polyamic acid and its imidized polymer). It is -40 mass parts, More preferably, it is 0.5-30 mass parts. When the addition amount of the component [C] is 0.1 to 40 parts by mass, the storage stability of the radiation-sensitive resin composition is good and the surface hardness, solvent resistance, and heat resistance of the resulting cured film are obtained. It is effective in improving the sex.

[Optional additives]
The radiation-sensitive resin composition of the present invention contains the above-mentioned [A] component, [B] component, and [C] component as essential components, but [D] at least one ethylenically non-reactive component as necessary. A polymerizable compound having a saturated double bond (hereinafter also referred to as [D] component), [E] surfactant (hereinafter also referred to as [E] component), [F] adhesion assistant (hereinafter referred to as [F] ] Component)). The [D] component, [E] component, and [F] component will be described in detail below.

First, regarding the component [D], as the polymerizable compound having at least one ethylenically unsaturated double bond, for example, monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional or higher (meth) acrylate, and the like. It can be used suitably.

  Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl- Examples include 2-hydroxypropyl phthalate. Examples of commercial products of these monofunctional (meth) acrylates include Aronix M-101, M-111, M-114 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, TC-120S. (Nippon Kayaku Co., Ltd.), Biscote 158, 2311 (Osaka Organic Chemical Co., Ltd.) and the like.

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

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

  Of these meth (acrylates), trifunctional or higher functional (meth) acrylates are preferably used from the viewpoint of improving the curability of the radiation-sensitive resin composition. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are particularly preferable. These monofunctional, bifunctional, or trifunctional or higher (meth) acrylates are used alone or in combination.

The ratio of the [D] component used in the radiation-sensitive resin composition is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the [A] component. Inclusion of the [D] component in the range of 1 to 50 parts by mass can improve the curability of the radiation-sensitive resin composition and cause film roughness in the coating film forming process on the substrate. Can be suppressed.

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

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

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

  Specific examples of the silicone-based surfactant include commercially available product names such as DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ. -6032, SH 8400 FLUID (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above, GE Toshiba Silicone) For example).

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

  In the radiation sensitive resin composition, the surfactant of the [E] component is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the [A] component. Used. [E] When the range of the addition amount of the component is 0.01 to 5 parts by mass, it is possible to suppress film roughness when forming a coating film.

  In the radiation sensitive resin composition of this invention, in order to improve adhesiveness with a board | substrate, the adhesion assistant which is a [F] component can be used. As such an adhesion assistant, a functional silane coupling agent is preferably used. Examples of functional silane coupling agents include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, and epoxy groups (preferably oxiranyl groups). Specific examples of functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxy Propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxy Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropi Triethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3 , 6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3- Aminopropyltrie Toxisilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3 -(N, N-diglycidyl) aminopropyltrimethoxysilane and the like can be mentioned. Such an adhesion assistant is preferably used in an amount of 1 to 20 parts by mass, more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the component [A]. When the range of the addition amount of the adhesion assistant is 1 to 20 parts by mass, the adhesion between the formed interlayer insulating film and the substrate is improved.

Examples of the organic solvent used in the present invention include the same solvents as those exemplified as those used in the polyamic acid synthesis reaction. However, in the synthesis reaction, it is sufficient to select a solvent considering only the solubility of raw materials and reactants, but for interlayer insulation film applications, further consideration is given to storage stability, printability and coatability in the next process, etc. Since it is necessary, a solvent different from the organic solvent used for the synthesis reaction such as polyamic acid may be used. Among these, a solvent having a boiling point of 160 ° C. or higher is preferable from the viewpoint of printability. Examples of such solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol, phenol, cyclohexanol, and ethylene. Glycol, propylene glycol, 1,4-butanediol, triethylene glycol, diacetone alcohol, butyl lactate, butyl acetate, ethyl ethoxypropionate, propylene carbonate, diethyl oxalate, diethyl malonate, ethylene glycol monobutyl ether (butyl cellosolve) ), Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Examples include ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, 1,4-dichlorobutane, o-dichlorobenzene, N-methyl-2-pyrrolidone, γ-butyrolactone, diacetone alcohol, ethylene glycol Monobutyl ether (butyl cellosolve), propylene carbonate, and diethylene glycol diethyl ether are preferred.

  Examples of solvents other than the above include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, Aromatic hydrocarbons, ketones, other esters and the like can also be used.

Examples of alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol;
Ethers such as tetrahydrofuran;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of the diethylene glycol alkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;

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 and the like;
As propylene glycol monoalkyl ether propionate, for example, propylene monoglycol methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, etc .;
Examples of aromatic hydrocarbons include toluene and xylene;
Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc .;

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

Radiation-sensitive resin composition The radiation-sensitive resin composition of the present invention comprises the above-mentioned [A] component, [B] component, [C] component, and optional components ([D] component, [E] component, [F] ] Component) is uniformly mixed and filtered using a Millipore filter or the like having a pore diameter of about 0.2 μm, and then used. Usually, the radiation-sensitive resin composition is preferably used after being dissolved in an appropriate solvent and stored in a solution state.

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

(1) The process of forming the coating film of a radiation sensitive resin composition on a board | substrate In the process of said (1), the solution of the radiation sensitive resin composition of this invention is apply | coated to a substrate surface, Preferably it prebakes. Thus, the solvent is removed to form a coating film of the radiation sensitive resin composition. Examples of the types of substrates that can be used include glass substrates, silicon wafers, and substrates on which various metals are formed.

  The method for applying the composition solution is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die method, a bar coating method, or an ink jet method is adopted. be able to. Among these coating methods, the spin coating method is preferable. The prebaking conditions vary depending on the type of each component, the use ratio, and the like, but can be, for example, 60 to 90 ° C. for 30 seconds to 15 minutes. The film thickness of the coating film to be formed is preferably 0.1 to 8 μm, more preferably 0.1 to 6 μm, and further preferably 0.1 to 4 μm as a value after pre-baking.

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

  Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet light include a KrF excimer laser. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam. Among these radiations, ultraviolet rays are preferable, and among the ultraviolet rays, radiation containing g-line and / or i-line is particularly preferable. The exposure amount is preferably 30 to 1,500 J / m2.

(3) Development step (3) In the development step, the coating film irradiated with radiation in the step (2) is developed to remove the irradiated portion and form a desired pattern. it can. Examples of the developer used for the development processing include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine. , Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5- An aqueous solution of an alkali (basic compound) such as diazabicyclo [4,3,0] -5-nonane can be used. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent or surfactant such as methanol or ethanol to the aqueous alkali solution described above, or an alkaline aqueous solution containing a small amount of various organic solvents for dissolving the radiation-sensitive resin composition, Can be used as Furthermore, as a developing method, for example, an appropriate method such as a liquid filling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. Although development time changes with compositions of a radiation sensitive resin composition, it can be made into 30 to 120 second, for example.
After this development step, the patterned thin film is rinsed by running water washing, and subsequently irradiated with a high-pressure mercury lamp or the like on the entire surface (post-exposure), thereby remaining in the thin film 1,2- It is preferable to perform a decomposition treatment of the quinonediazide compound.

(4) Heating step Next, in the (4) heating step, the thin film is cured by heating and baking treatment (post-baking treatment) using a heating device such as a hot plate or an oven. The exposure amount in the post-exposure is preferably about 2,000 to 5,000 J / m ² . The firing temperature in this heating step is preferably 230 ° C. or lower, more preferably 200 ° C. or lower, and particularly preferably 180 ° C. or lower. The heating time can be 30 to 80 minutes when the heat treatment is performed in an oven, and particularly preferably within 60 minutes when the heat treatment is performed in the oven. In this way, a patterned thin 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 formed by heating at a low temperature for a short time has sufficient surface hardness as well as solvent resistance and relative dielectric constant, as will be apparent from examples described later. The rate is excellent. Therefore, this interlayer insulating film is suitably used as an interlayer insulating film for flexible displays.

EXAMPLES Hereinafter, although a synthesis example and an Example demonstrate this invention further in detail, this invention is not limited to these Examples.

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 1
2,3,5-tricarboxycyclopentylacetic acid dianhydride 112.09 g (0.5 mol) and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 as tetracarboxylic dianhydride (Tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione 157.15 g (0.5 mol), and diamine compound 93.54 g (0 .865 mol), 3,3 ′-(tetramethyldisiloxane-1,3-diyl) bis (propylamine) 24.85 g (0.1 mol) and 12.86 g of the diamine represented by the above formula (7) ( 0.02 mol) as well as 8.09 g (0.03 mol) of n-octadecylamine as a monoamine were dissolved in 950 g of N-methyl-2-pyrrolidone. Reacted for hours. A small amount of the obtained polyamic acid solution was taken, NMP was added, and the viscosity was measured with a solution having a solid content concentration of 10% by mass. As a result, it was 60 mPa · s. To the obtained polyamic acid, 2,700 g of N-methyl-2-pyrrolidone was added and dissolved, 400 g of pyridine and 410 g of acetic anhydride were added, and dehydration ring closure was performed at 110 ° C. for 4 hours. After the imidization reaction, the solvent in the system was replaced with new γ-butyrolactone (the pyridine and acetic anhydride used for the imidization reaction were removed from the system in this operation), and the solid content concentration was 10% by mass. 4,000 g of an imidized polymer having a solution viscosity of 55 mPa · s at a partial concentration of 10% by mass (γ-butyrolactone solution) was obtained (hereinafter referred to as “polymer (A-1)”).

Synthesis example 2
As tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 19.2 g (0.1 mol), p-phenylenediamine 3.2 g (0.034 mol) as diamine compound, 4, 8.5 g (0.05 mol) of 4′-diaminodiphenylmethane and 6.7 g (0.015 mol) of the diamine represented by the above formula (14) and 0.16 g (0.002 mol) of N-octadecylamine as a monoamine Was dissolved in 150 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours. A small amount of the resulting polyamic acid solution was taken, NMP was added, and the viscosity was measured with a solution having a solid content concentration of 10% by mass. As a result, it was 85 mPa · s. The resulting polyamic acid was dissolved by adding 351 g of N-methyl-2-pyrrolidone, added with 18.6 g of pyridine and 17.6 g of acetic anhydride, and dehydrated and closed at 110 ° C. for 4 hours. After the imidization reaction, the solvent in the system was replaced with new γ-butyrolactone (the pyridine and acetic anhydride used for the imidization reaction were removed from the system in this operation), and the solid content concentration was 10% by mass. 480 g of an imidized polymer having a solution viscosity of 80 mPa · s at a partial concentration of 10% by mass (γ-butyrolactone solution) was obtained (hereinafter referred to as “polymer (A-2)”).

Synthesis example 3
As tetracarboxylic dianhydride, 2,09,5-tricarboxycyclopentyl acetic acid dianhydride 20.09 g (0.1 mol), as a diamine compound 7.86 g (0.08 mol) p-phenylenediamine and the above formula 10.6 g (0.02 mol) of the diamine represented by (14) was dissolved in 150 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours. A small amount of the resulting polyamic acid solution was taken, NMP was added, and the viscosity was measured with a solution having a solid content concentration of 10% by mass. As a result, it was 120 mPa · s. The obtained polyamic acid was dissolved by adding 320 g of N-methyl-2-pyrrolidone, 6.7 g of pyridine and 8.6 g of acetic anhydride were added, and dehydration ring closure was performed at 110 ° C. for 4 hours. After the imidization reaction, the solvent in the system was replaced with new γ-butyrolactone (the pyridine and acetic anhydride used for the imidization reaction were removed from the system in this operation), and the solid content concentration was 10% by mass. 360 g of an imidized polymer having a solution viscosity of 110 mPa · s at a partial concentration of 10% by mass (γ-butyrolactone solution) was obtained (hereinafter referred to as “polymer (A-3)”).

Synthesis example 4
As tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 19.06 (0.1 mol), p-phenylenediamine 6.66 g (0.07 mol) as a diamine compound, the above formula Dissolve 2.22 g (0.01 mol) of the diamine represented by (II-2) and 9.20 g (0.02 mol) of the diamine represented by the above formula (14) in 150 g of N-methyl-2-pyrrolidone. And reacted at 60 ° C. for 4 hours. A small amount of the obtained polyamic acid solution was taken, NMP was added, and the viscosity was measured with a solution having a solid content concentration of 10% by mass. As a result, it was 70 mPa · s. The resulting polyamic acid was dissolved by adding 350 g of N-methyl-2-pyrrolidone, 6.7 g of pyridine and 8.6 g of acetic anhydride were added, and dehydration ring closure was performed at 110 ° C. for 4 hours. After the imidization reaction, the solvent in the system was replaced with new γ-butyrolactone (the pyridine and acetic anhydride used for the imidization reaction were removed from the system in this operation), and the solid content concentration was 10% by mass. 340 g of an imidized polymer having a solution viscosity of 66 mPa · s at a partial concentration of 10% by mass (γ-butyrolactone solution) was obtained (hereinafter referred to as “polymer (A-4)”).

Synthesis example 5
124.36 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and 140.38 g (1. of diamine represented by the above formula (II-2) as a diamine compound. 0 mol) was dissolved in 1,500 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours. Then, 1,150 g of γ-butyllactone was added, the solid content concentration was 10% by mass, and the solution viscosity was 60 mPa.s. -About 2600 g of a polyamic acid solution (referred to as "polyamic acid (A-5)") in s was obtained.

Synthesis Example 6
As tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride 64.07 g (0.5 mol), 1,2,3,4-cyclobutanetetracarboxylic dianhydride 56.05 g (0 0.5 mol), 144.63 g (1.0 mol) of the diamine represented by the above formula (II-2) as a diamine compound was dissolved in 1,500 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours. After adding 1,150 g of γ-butyllactone, a polyamic acid solution having a solid content of 10% by mass and a solution viscosity of 85 mPa · s (referred to as “polyamic acid (A-6)”), about 2,600 g Got.

Synthesis example 7
115.34 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 149.41 g of diamine represented by the above formula (II-2) as diamine compound ( 1.0 mol) is dissolved in 1,500 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours. Then, 1,150 g of γ-butyllactone is added, and the solid content concentration is 10% by mass. About 2,600 g of a polyamic acid (referred to as “polyamic acid (A-7)”) solution having a viscosity of 65 mPa · s was obtained.

Synthesis example 8
196.11 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 2,2′-dimethyl-4,4′-diaminobiphenyl 212 as diamine compound .30 g (1.0 mol) is dissolved in 370 g of N-methyl-2-pyrrolidone and 3,300 g of γ-butyllactone and reacted at 40 ° C. for 3 hours to obtain a solid content concentration of 10% by mass and a solution viscosity of 160 mPa · s. About 4,000 g of a polyamic acid solution (referred to as “polyamic acid (A-8)”) was obtained.

Comparative Synthesis Example 1
Under a nitrogen stream, 18.45 g (0.051 mol) of 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane was placed in a 200 mL four-necked flask, and N-methyl-2-pyrrolidone ( (Hereinafter abbreviated as NMP) After dissolving in 75.92 g, 9.48 g (0.048 mol) of 1,2,3,4-cyclobutanetetracarboxylic acid anhydride was added, and this was stirred at room temperature for 8 hours to polymerize. Reaction was performed. The obtained polyamic acid solution was diluted to 10% by mass with NMP. To this solution, 26 g of acetic anhydride and 16.1 g of pyridine were added as imidation catalysts, reacted at room temperature for 30 minutes, and then reacted at 40 ° C. for 90 minutes to obtain a polyimide solution. This solution was put into a large amount of a mixed solution of methanol and water, and the resulting white precipitate was filtered and dried to obtain a white polyimide powder. This was dissolved in 46 g of propylene glycol monomethyl ether to obtain an 8% by mass solution of polyimide. (This is referred to as “polymer (a-1)”).
Comparative Synthesis Example 2
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 16 parts by mass of methacrylic acid, 16 parts by mass of tricyclo [5.2.1.02,6] decan-8-yl methacrylate, 20 parts by mass of 2-methylcyclohexyl acrylate, 40 parts by mass of glycidyl methacrylate, and 10 parts by mass of styrene. After charging and replacing with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer having a solid content concentration of 34.4% by mass (hereinafter referred to as “polymer (a-2)”). .

<Preparation of resin composition>
[Example 1]
As the component [A], the imidized polymer (A-1) obtained in Synthesis Example 1 and the polyamic acid (A-5) obtained in Synthesis Example 5 were converted into polyimide (A-1): polyamic acid (A- 5) = an amount corresponding to 20:80 (mass ratio), and 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene as the [B] component ] 30 parts by mass of a condensate (B-1) of bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) is added, and the above formula is used as [C] component. 10 parts by mass of the compound represented by (31) is added, 0.2 part by mass of (E-1) is added as an [E] component, and diisopentyl ether: N-methyl-2-pyrrolidone: butyl cellosolve = 5 as a solvent. : Add 50:45 (mass ratio) After the addition, a radiation sensitive resin composition was prepared by filtering through a membrane filter having a diameter of 0.2 μm.

[Examples 2 to 8 and Comparative Examples 1 to 3]
A positive radiation-sensitive composition was prepared in the same manner as in Example 1 except that the types and amounts of each component were as described in Table 1.

<Characteristic evaluation as interlayer insulation film>
Using the resin composition prepared as described above, various characteristics as an interlayer insulating film were evaluated as follows.

[Evaluation of sensitivity]
About Examples 1-7 and Comparative Examples 1-3 on a silicon substrate, after apply | coating each composition using a spinner, after prebaking on a hotplate for 2 minutes at 90 degreeC, film thickness of 4.0 micrometers The coating film was formed. For Example 8, after applying the composition using a slit die coater, the pressure was reduced to 0.5 Torr over 15 seconds at room temperature, the solvent was removed, and then prebaked on a hot plate at 100 ° C. for 2 minutes. As a result, a coating film having a thickness of 3.0 μm was formed. For the obtained coating film, the exposure time was adjusted through a mask having a 10 μm line-and-space (one-to-one) pattern using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. After changing the exposure, the resist film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds by a puddle method. Next, the substrate was washed with running ultrapure water for 1 minute and then dried to form a pattern on the silicon substrate. At this time, the minimum exposure amount necessary for the space line width (bottom) to be 10 μm was measured. This minimum exposure amount is shown in Table 1 as radiation sensitivity. It can be said that the sensitivity is good when the minimum exposure amount is 800 (J / m ² ) or less.

[Evaluation of resolution]
A pattern was formed in the same manner as in the sensitivity evaluation, except that exposure was performed using a mask having a contact hole pattern with a diameter of 8 μm, 12 μm, and 15 μm at the exposure amount obtained in the sensitivity evaluation. At this time, if the 8 μm contact hole pattern is resolved, the resolution is good, and if only the 15 μm contact hole pattern is resolved, the resolution is poor. Table 1 shows the hole pattern sizes that could be resolved.

[Evaluation of relative permittivity]
The above composition was applied onto a silicon substrate using a spinner and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Using an MPA-600FA exposure machine manufactured by Canon Inc., the coating film obtained was exposed so that the integrated dose was 9,000 J / m ^2, and this substrate was subjected to two temperature conditions in a clean oven. And heated. The two types of post-baking temperature conditions are 150 ° C. for 30 minutes and 230 ° C. for 30 minutes. A dielectric film measurement sample was prepared by forming a Pt / Pd electrode pattern on the cured film by vapor deposition on the cured film subjected to the heat treatment under each post-bake temperature condition. With respect to the substrate having this electrode pattern, the relative dielectric constant was measured by the CV method at a frequency of 10 kHz using an HP16451B electrode and HP4284A Precision LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd. The measurement results are shown in Table 1. When there is no difference of 0.3 or more in the relative dielectric constant between the two kinds of post-bake temperature conditions, it can be determined that a cured film having an excellent relative dielectric constant is obtained even at a temperature of 150 ° C.

[Evaluation of solvent resistance]
The above composition was applied onto a silicon substrate using a spinner and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays with a mercury lamp so that the cumulative irradiation amount was 3,000 J / m ² . Next, this silicon substrate was heated in a clean oven under two temperature conditions. The two types of post-baking temperature conditions are 150 ° C. for 30 minutes and 230 ° C. for 30 minutes. After performing the heat treatment under each temperature condition, the thickness (T1) of the cured film obtained under each condition was measured. Then, after immersing the silicon substrate on which these cured films were formed in dimethyl sulfoxide whose temperature was controlled at 70 ° C. for 20 minutes, the film thickness (t1) of the cured film was measured, and the film thickness change due to immersion was measured. The rate {(t1-T1) / T1} × 100 [%] was calculated. The measurement results are shown in Table 1. If there is no difference of 2% or more in solvent resistance under the two kinds of post-bake temperature conditions, it can be judged that a cured film having excellent solvent resistance is obtained even at a temperature of 150 ° C.

[Evaluation of pencil hardness (surface hardness)]
In the same manner as in the above [Evaluation of solvent resistance], a cured film was formed under two temperature conditions (in the case of 30 minutes at 150 ° C. and in the case of 30 minutes at 230 ° C.). The pencil hardness (surface hardness) of the cured film was measured by the 8.4.1 pencil scratch test of -5400-1990. The measurement results are shown in Table 1. When there is no difference of 1H or more in pencil hardness under two kinds of post-bake temperature conditions, it can be determined that a cured film having excellent surface hardness is obtained even at a temperature of 150 ° C.

[Evaluation of electrical characteristics]
After applying the above composition using a spinner on a soda glass substrate on which a SiO2 film for preventing elution of sodium ions is formed on the surface and further depositing an ITO (indium-tin oxide alloy) electrode in a predetermined shape, 90 Prebaking was performed for 2 minutes on a hot plate at 0 ° C. to form a coating film having a thickness of 2.0 μm. Development was carried out by a dip method in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds. Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an integrated dose of 3,000 J / m 2 without using a photomask. Next, this substrate was heated in a clean oven under two kinds of post-bake temperature conditions. The two types of post-baking temperature conditions are 150 ° C. for 30 minutes and 230 ° C. for 30 minutes. Heat treatment was performed under each post-baking temperature condition to form a cured film.
Next, after spraying a 5.5 μm diameter bead spacer on the substrate having the cured film, the liquid crystal injection port is placed in a state where this is opposed to a soda glass substrate on which the ITO electrode is deposited in a predetermined shape. The remaining four sides were bonded using a sealing agent mixed with 0.8 mm glass beads, and liquid crystal MLC6608 (trade name) manufactured by Merck was injected, and then the liquid crystal injection port was sealed to produce a liquid crystal cell. did.

This liquid crystal cell is placed in a constant temperature layer of 60 ° C., and a liquid crystal voltage holding ratio measurement system VHR-1A (trade name) manufactured by Toyo Technica is used to form a square wave with an applied voltage of 5.5 V and a measurement frequency of 60 Hz. The voltage holding ratio of the cell was measured. The results are shown in Table 1.
When there is no difference of 2% or more in the voltage holding ratio under the two kinds of post-bake temperature conditions, it can be determined that a cured film having an excellent voltage holding ratio is obtained even at a temperature of 150 ° C.
Here, the voltage holding ratio is a value obtained by the following formula. The lower the value of the voltage holding ratio of the liquid crystal cell, the higher the possibility of causing a problem called “burn-in” when forming the liquid crystal panel. On the other hand, it can be said that the higher the value of the voltage holding ratio, the lower the possibility of occurrence of “burn-in” and the higher the reliability of the liquid crystal panel.
Voltage holding ratio (%) = (liquid crystal cell potential difference after 16.7 milliseconds from the reference time) / (voltage applied at 0 milliseconds [reference time]) × 100

In Table 1, [B] 1,2-quinonediazide compound, [C] compound having at least one epoxy group in the molecule, [D] polymerization having at least one ethylenically unsaturated double bond. The abbreviations of the functional compound, [E] surfactant, and [F] adhesion assistant each represent the following.
B-1: 4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate B-2 with sulfonic acid chloride (3.0 mol): 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid Condensate with chloride (3.0 mol) C-1: 1,6-hexanediol diglycidyl ether C-2: Compound C-3 of formula (31): Compound D-1 of formula (35) D-1: Pentaerythritol Tetraacrylate E-1: Silicone surfactant ("SH 8400 FLUID" manufactured by Toray Dow Corning Co., Ltd.)
F-1: γ-Glycidoxypropyltrimethoxysilane “-” in Table 1 indicates that no addition was made.

Claims (4)

[A] a polymer selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine compound, and a polyimide obtained by dehydrating and ring-closing this, [B] 1,2-quinonediazide compound ,
[C] a compound having at least one epoxy group in the molecule ,
[A] The positive radiation sensitive resin composition, wherein the diamine compound in the component is a diamine compound having a steroid skeleton. The tetracarboxylic dianhydride in the component [A] of claim 1 is a compound represented by the following formula (1), a compound represented by the following formula (2), pyromellitic dianhydride, 1,2 , 4-Tricarboxycyclopentylacetic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride and 1,2,4,5- The positive radiation sensitive resin composition according to claim 1, comprising at least one selected from the group consisting of cyclohexanetetracarboxylic dianhydride.

(In the formula (1), ^{R 1} each independently represent a hydrogen atom, a chlorine atom or an alkyl group having 1 to 6 carbon atoms.)

(In the formula (2), ^{R 2} is, independently, an alkyl group having 1 to 6 carbon atoms, n is an integer from 0-4.) The positive-tone radiation-sensitive resin composition according to any one of claims 2 to claim 1 used to form an interlayer insulating film of the display device. (1) The process of forming the coating film of the positive radiation sensitive resin composition of Claim 3 on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) Formation of an interlayer insulating film for a display element including a step of developing the coating film irradiated with radiation in step (2), and a step of (4) baking the coating film developed in step (3) by heating. Method.