JP2012114313A - Semiconductor element substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a semiconductor element substrate having excellent low dielectric constant characteristics, low leak current characteristics, and high dielectric breakdown voltage, and provided with a highly transparent resin film.SOLUTION: The semiconductor element substrate comprises a resin film composed of a resin composition containing a binder resin (A), a compound having an acid group (B), and a crosslinking agent (C). The binder resin (A) has a weight-average molecular weight (Mw) of 10,000 or higher, and a water absorption of 0.03 wt% or higher. The ratio of the molecular weight of the crosslinking agent (C) to the weight-average molecular weight (Mw) of the binder resin (A) is 0.05 or lower, and the content of the crosslinking agent (C) is 21-150 pts.wt for 100 pts.wt. of the binder resin (A). The resin film is formed in contact with the surface of a semiconductor element mounted on the semiconductor element substrate, or in contact with a semiconductor layer included in the semiconductor element.

Description

  The present invention relates to a semiconductor element substrate, and more particularly to a semiconductor element substrate having a resin film that is excellent in low dielectric constant characteristics, low leakage current characteristics, and high dielectric breakdown voltage characteristics, and also has high transparency.

  Semiconductor element substrates of electronic components such as display elements, integrated circuit elements, and solid-state imaging elements, protective films for preventing deterioration and damage, flattening films for flattening unevenness derived from elements and wiring, and Various resin films are provided as an electrical insulating film or the like for maintaining electrical insulation. In particular, in a thin film transistor (TFT) as an example of such a semiconductor element substrate, it is necessary to form a protective film in order to prevent its deterioration and damage.

  Conventionally, thermosetting resin materials such as epoxy resins have been widely used as resin materials for forming these resin films. In recent years, with the increase in the density of wiring and devices, development of new resin materials excellent in electrical characteristics such as low dielectric properties has been demanded for these resin materials.

  In order to meet these requirements, for example, Patent Document 1 discloses a binder resin, a compound having one acidic group selected from the group consisting of an aliphatic compound, an aromatic compound, and a heterocyclic compound, and an organic solvent. And a compound having a hydrocarbyloxy group or a hydroxy group bonded to a silicon atom, a titanium atom, an aluminum atom, or a zirconium atom is disclosed. However, the protective film obtained by using the resin composition described in Patent Document 1 does not necessarily have a low leakage current characteristic when used as a protective film of a thin film transistor (TFT). Improvement was desired.

International Publication No. 2009/133384

  An object of the present invention is to provide a semiconductor element substrate having a resin film that is excellent in low dielectric constant characteristics, low leakage current characteristics, and high dielectric breakdown voltage characteristics, and also has high transparency.

  As a result of earnest research to achieve the above object, the inventor has developed a resin film used in contact with a semiconductor element surface mounted on a semiconductor element substrate or a semiconductor layer included in the semiconductor element with a specific molecular weight and It is formed using a composition containing a binder resin having a specific water absorption rate, a compound having an acidic group, and a crosslinking agent. The crosslinking agent contained in the composition has a molecular weight of the binder resin. The inventors have found that the above object can be achieved by using a material having a specific range in relation to the molecular weight, and completed the present invention.

  That is, according to the present invention, a semiconductor element substrate having a resin film comprising a resin composition comprising a binder resin (A), a compound (B) having an acidic group, and a crosslinking agent (C), The binder resin (A) has a weight average molecular weight (Mw) of 10,000 or more, a water absorption of 0.03% by weight or more, and the crosslinking agent with respect to the weight average molecular weight (Mw) of the binder resin (A). The ratio of the molecular weight of (C) is 0.05 or less, the content of the crosslinking agent (C) is 21 to 150 parts by weight with respect to 100 parts by weight of the binder resin (A), A semiconductor element substrate is provided which is formed in contact with a semiconductor element surface mounted on the semiconductor element substrate or a semiconductor layer included in the semiconductor element.

Preferably, the resin composition further contains a radiation sensitive compound (D).
Preferably, the inorganic ion content in the resin film is 1-1000 ppb.
Preferably, the semiconductor element substrate is an active matrix substrate or an organic EL element substrate.

  According to the present invention, a resin film used in contact with a semiconductor element surface mounted on a semiconductor element substrate or a semiconductor layer included in a semiconductor element is formed by using a binder resin having a specific molecular weight and a specific water absorption rate, and an acidity. A composition containing a group-containing compound and a crosslinking agent, and having a molecular weight in a specific range in relation to the molecular weight of the binder resin as the crosslinking agent contained in the composition Therefore, the semiconductor element substrate has excellent low dielectric constant characteristics, low leakage current characteristics, and high breakdown voltage characteristics, and the resin film included in the semiconductor element substrate has high transparency. As a result, it is possible to provide a semiconductor element substrate having excellent electrical characteristics and high performance.

The semiconductor element substrate of the present invention comprises a resin composition comprising a binder resin (A) having a specific molecular weight and water absorption, a compound (B) having an acidic group, and a crosslinking agent (C) having a specific molecular weight. The resin film is formed in contact with a semiconductor element surface mounted on the semiconductor element substrate or a semiconductor layer included in the semiconductor element.
In the following, first, the resin composition used in the present invention will be described.

(Resin composition)
The resin composition used in the present invention is a resin composition for forming a resin film formed in contact with a semiconductor element surface mounted on a semiconductor element substrate of the present invention or a semiconductor layer included in the semiconductor element. A binder resin (A) having a specific molecular weight and water absorption, a compound (B) having an acidic group, and a crosslinking agent (C) having a specific molecular weight.

(Binder resin (A))
The binder resin (A) used in the present invention is a resin having a weight average molecular weight Mw of 10,000 or more and a water absorption of 0.03% by weight or more. Such a binder resin (A) is not particularly limited, and examples thereof include acrylic resins, acrylamide resins, polyimide resins, and polyamideimide resins. Among these, it is preferable to include at least one selected from the group consisting of an acrylic resin and a polyimide resin, and among these, a polyimide resin is particularly preferable.
These binder resins (A) may be used alone or in combination of two or more.

  The acrylic resin used in the present invention is not particularly limited, but a homopolymer having at least one selected from a carboxylic acid having an acrylic group, a carboxylic acid anhydride having an acrylic group, or an epoxy group-containing acrylate compound as an essential component or A copolymer is preferred.

Specific examples of the carboxylic acid having an acrylic group include (meth) acrylic acid [meaning acrylic acid and / or methacrylic acid. The same applies to methyl (meth) acrylate. ], Maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid and the like.
Specific examples of the carboxylic acid anhydride having an acrylic group include maleic anhydride and citraconic anhydride.
Specific examples of the epoxy group-containing acrylate compound include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylate 3,4. -Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, etc. .
Of these, (meth) acrylic acid, maleic anhydride, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl and the like are preferable.

  The acrylic resin is a copolymer of at least one selected from an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, and an epoxy group-containing unsaturated compound and another acrylate monomer or a copolymerizable monomer other than an acrylate. It may be a polymer.

Other acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl ( (Meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, ethylhexyl (meth) Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) Acrylate, stearyl (meth) acrylate, alkyl (meth) acrylates such as isostearyl (meth) acrylate;
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) Hydroxyalkyl (meth) acrylates such as acrylates;
Phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate;
Alkoxyalkyl such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-methoxybutyl (meth) acrylate, etc. ) Acrylate;
Polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene Polyalkylene glycol (meth) acrylates such as glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate;
Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl ( Cycloalkyl (meth) acrylates such as (meth) acrylate and tricyclodecanyl (meth) acrylate;
Benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like.
Among these, butyl (meth) acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and the like are preferable.

The copolymerizable monomer other than the acrylate is not particularly limited as long as it is a compound copolymerizable with the carboxylic acid having an acrylic group, a carboxylic acid anhydride having an acrylic group, or an epoxy group-containing acrylate compound. And vinyl group-containing radical polymerizable compounds such as vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, α-methyl styrene, butadiene, and isoprene.
These compounds may be used alone or in combination of two or more.
The monomer polymerization method may be in accordance with a conventional method, and for example, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like are employed.

  Although the acrylamide resin used by this invention is not specifically limited, The homopolymer of acrylamide or the copolymer with the monomer copolymerizable with acrylamide is mentioned.

  Examples of the copolymerizable monomer include anionic monomers such as carboxylic acid having an acrylic group described above; dimethylaminoethyl (meth) acrylate, diallyldimethylammonium chloride, diallyldiethylammonium chloride, (meth) acryloyloxyethyltrimethyl And cationic monomers such as ammonium methyl sulfate, (meth) acryloyloxyethyltrimethylammonium methyl chloride, (meth) acrylamidopropyltrimethylammonium chloride; and the like.

The polyimide resin used by this invention can be obtained by heat-processing the polyimide precursor obtained by making tetracarboxylic anhydride and diamine react. Examples of the precursor for obtaining the polyimide resin include polyamic acid, polyamic acid ester, polyisoimide, and polyamic acid sulfonamide.
Specific examples of the acid dianhydride that can be used as a raw material for obtaining a polyimide resin include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3 , 3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxy) Phenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4 -Dicarboxyphenyl) methane Water, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1, 2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4, Aromatic tetracarboxylic dianhydrides such as 9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, butanetetracarboxylic dianhydride And aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride. These acid dianhydrides can be used alone or in combination of two or more.

  Specific examples of diamines that can be used as raw materials for obtaining a polyimide resin include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenylmethane. 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, Benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4- Aminophenoxy) bife Bis (4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3'-tetra Methyl-4,4′-diaminobiphenyl, 3,3 ′, 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl Or compounds in which the aromatic ring of these compounds is substituted with an alkyl group or a halogen atom; and aliphatic cyclohexyldiamine, methylenebiscyclohexylamine; and the like. These diamines can be used alone or in combination of two or more.

  The polyimide resin used in the present invention is synthesized by a known method. That is, a tetracarboxylic dianhydride and a diamine are selectively combined, and these are combined with N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphorotriamide, It is synthesized by a known method such as reacting in a polar solvent such as γ-butyrolactone or cyclopentanone.

  The polyamideimide resin used in the present invention is not particularly limited. For example, it can be obtained by reacting a diisocyanate compound or a diamine compound with a tribasic acid anhydride or tribasic acid anhydride chloride in a basic polar solvent. it can.

Examples of the diisocyanate compound include 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3′-diphenylmethane diisocyanate, 3,3′-dimethoxybiphenyl-4,4′-diisocyanate, biphenyl-3,4′-diisocyanate, 2 2,2'-diethylbiphenyl-4,4'-diisocyanate, phenylene diisocyanate and the like.
Examples of the diamine include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylpropane, 3,3 ′. -Diaminodiphenyl sulfone, 4,4'-diaminodiphenylhexafluoropropane, xylylenediamine, phenylenediamine and the like.
Examples of tribasic acid anhydrides include trimellitic acid anhydride.
Examples of the tribasic acid anhydride chloride include trimellitic acid anhydride chloride.

  The weight average molecular weight (Mw) of binder resin (A) used by this invention is 10,000 or more, Preferably it is 10,000-100,000, More preferably, it is 12,000-75,000, More preferably, it is 15 , 50,000 to 50,000. If the weight average molecular weight (Mw) of the binder resin (A) is too small, the adhesion of the resin film to the semiconductor element substrate may be reduced.

The molecular weight distribution of the binder resin (A) is usually 4 or less, preferably 3 or less, and more preferably 2.5 or less, as a weight average molecular weight / number average molecular weight (Mw / Mn) ratio.
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the binder resin (A) are values determined as polystyrene equivalent values by gel permeation chromatography (GPC) using a solvent such as tetrahydrofuran as an eluent. It is.

  The water absorption of the binder resin (A) used in the present invention is 0.03% by weight or more, preferably 0.03 to 0.20% by weight, more preferably 0.03 to 0.15% by weight, More preferably, it is 0.03-0.10 weight%. If the water absorption of the binder resin (A) is too high, the electric resistance of the resin film may be reduced. In addition, the water absorption rate of binder resin (A) can be calculated | required from the weight change after being immersed in 23 degreeC water for 24 hours according to JISK7209, for example.

(Compound (B) having an acidic group)
The compound (B) having an acidic group used in the present invention is not particularly limited as long as it has an acidic group, but is preferably an aliphatic compound, an aromatic compound, or a heterocyclic compound, and more preferably an aromatic compound. Compounds and heterocyclic compounds.
These compounds (B) having an acidic group can be used alone or in combination of two or more. The acidic group may be heat latent.

The number of acidic groups in the compound (B) having an acidic group is not particularly limited, but those having two or more acidic groups are preferable, and those having two acidic groups are particularly preferable. The acidic groups may be the same as or different from each other.
The acidic group may be any acidic functional group, and specific examples thereof include strongly acidic groups such as sulfonic acid group and phosphoric acid group; weak acidic groups such as carboxy group, thiol group and carboxymethylenethio group; Can be mentioned. Among these, a carboxy group, a thiol group, or a carboxymethylenethio group is preferable, and a carboxy group is particularly preferable. Among these acidic groups, those having an acid dissociation constant pKa in the range of 3.5 to 5.0 are preferred. When there are two or more acidic groups, it is preferable that the first dissociation constant pKa1 is an acid dissociation constant and the first dissociation constant pKa1 is in the above range. The pKa is determined according to pKa = −logKa by measuring the acid dissociation constant Ka = [H ₃ O ⁺ ] [B ⁻ ] / [BH] under dilute aqueous solution conditions. Here, BH represents an organic acid, and B ⁻ represents a conjugate base of the organic acid.
Moreover, the measurement method of pKa can measure hydrogen ion concentration, for example using a pH meter, and can calculate it from the density | concentration of a applicable substance, and hydrogen ion concentration.
In the present invention, by using the compound (B) having an acidic group as described above, the resin film formed from the resin composition can be made excellent in low leakage current characteristics. Chemical resistance and heat resistance can be further improved.

Moreover, the compound (B) which has an acidic group may have substituents other than an acidic group.
As such substituents, in addition to hydrocarbon groups such as alkyl groups and aryl groups, halogen atoms; alkoxy groups, aryloxy groups, acyloxy groups, heterocyclic oxy groups; substituted with alkyl groups, aryl groups, or heterocyclic groups Polar groups having no proton such as amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group; alkylthio group, arylthio group, heterocyclic thio group; Examples thereof include a hydrocarbon group substituted with a polar group having no proton.

  Specific examples of the compound (B) having such an acidic group include methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, Decanoic acid, glycolic acid, glyceric acid, ethanedioic acid (also referred to as “oxalic acid”), propanedioic acid (also referred to as “malonic acid”), butanedioic acid (also referred to as “succinic acid”), pentanedioic acid Acid, hexanedioic acid (also referred to as “adipic acid”), 1,2-cyclohexanedicarboxylic acid, 2-oxopropanoic acid, 2-hydroxybutanedioic acid, 2-hydroxypropanetricarboxylic acid, mercaptosuccinic acid, dimercaptosuccinic acid 2,3-dimercapto-1-propanol, 1,2,3-trimercaptopropane, 2,3,4-trimercapto-1-butanol 2,4-dimercapto-1,3-butanediol, 1,3,4-trimercapto-2-butanol, 3,4-dimercapto-1,2-butanediol, 1,5-dimercapto-3-thiapentane, etc. Aliphatic compounds of

  Benzoic acid, p-hydroxybenzenecarboxylic acid, o-hydroxybenzenecarboxylic acid, 2-naphthalenecarboxylic acid, methylbenzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, 3-phenylpropanoic acid, 2-hydroxybenzoic acid, dihydroxybenzoic acid , Dimethoxybenzoic acid, benzene-1,2-dicarboxylic acid (also referred to as “phthalic acid”), benzene-1,3-dicarboxylic acid (also referred to as “isophthalic acid”), benzene-1,4-dicarboxylic acid ( Also referred to as “terephthalic acid”), benzene-1,2,3-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, benzenehexacarboxylic acid, biphenyl-2 , 2'-dicarboxylic acid, 2- (carboxymethyl) benzoic acid, 3- (carboxymethyl) benzoic acid 4- (carboxymethyl) benzoic acid, 2- (carboxycarbonyl) benzoic acid, 3- (carboxycarbonyl) benzoic acid, 4- (carboxycarbonyl) benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, 2- Mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,4-naphthalenedithiol, 1 , 5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercapto) Chill) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris Aromatic compounds such as (mercaptoethyl) benzene;

Nicotinic acid, isonicotinic acid, 2-furoic acid, pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole Five-membered nitrogen atoms such as 2,4-dicarboxylic acid, imidazole-2,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-dicarboxylic acid Heterocyclic compounds;
Thiophene-2,3-dicarboxylic acid, thiophene-2,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole-2,5 -Dicarboxylic acid, thiazole-4,5-dicarboxylic acid, isothiazole-3,4-dicarboxylic acid, isothiazole-3,5-dicarboxylic acid, 1,2,4-thiadiazole-2,5-dicarboxylic acid, 3,4-thiadiazole-2,5-dicarboxylic acid, 3-amino-5-mercapto-1,2,4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 3,5-dimercapto -1,2,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, 3- (5-mercapto-1,2,4-thiadiazole Zol-3-ylsulfanyl) succinic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylsulfanyl) succinic acid, (5-mercapto-1,2,4-thiadiazol-3-ylthio) Acetic acid, (5-mercapto-1,3,4-thiadiazol-2-ylthio) acetic acid, 3- (5-mercapto-1,2,4-thiadiazol-3-ylthio) propionic acid, 2- (5-mercapto- 1,3,4-thiadiazol-2-ylthio) propionic acid, 3- (5-mercapto-1,2,4-thiadiazol-3-ylthio) succinic acid, 2- (5-mercapto-1,3,4) Thiadiazol-2-ylthio) succinic acid, 4- (3-mercapto-1,2,4-thiadiazol-5-yl) thiobutanesulfonic acid, 4- (2-mercapto-1) 3,4-thiadiazol-5-yl) five-membered heterocyclic compound containing nitrogen atom and sulfur atom, such as thio butanoic acid;

Pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5 -Dicarboxylic acid, pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-dicarboxylic acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine -2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, pyridine-2,6- Dicarboxylic acid, triazine-2,4-dicarboxylic acid, 2-diethylamino-4,6-dimercapto-s-triazine, 2-dipropyl Mino-4,6-dimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine, 2,4,6-trimercapto- 6-membered heterocyclic compounds containing a nitrogen atom such as s-triazine.
Among these, from the viewpoint that the low leakage current characteristics of the obtained resin film can be further improved, the number of acidic groups is preferably 2 or more, and particularly preferably 2.

Examples of the compound having two acidic groups include aliphatic compounds having two acidic groups such as ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, and 1,2-cyclohexanedicarboxylic acid; benzene -1,2-dicarboxylic acid (also referred to as “phthalic acid”), benzene-1,3-dicarboxylic acid (also referred to as “isophthalic acid”), benzene-1,4-dicarboxylic acid (also referred to as “terephthalic acid”) ), Biphenyl-2,2′-dicarboxylic acid, 2- (carboxymethyl) benzoic acid, 3- (carboxymethyl) benzoic acid, 4- (carboxymethyl) benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid. Acid, 2-mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dimercaptobe Aromatic compounds having two acidic groups such as benzene, 1,4-dimercaptobenzene, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol;
Pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole-2,4-dicarboxylic acid-, imidazole-2, 5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-dicarboxylic acid, thiophene-2,3-dicarboxylic acid, thiophene-2,4-dicarboxylic acid, Thiophene-2,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole-2,5-dicarboxylic acid, thiazole-4,5-dicarboxylic acid, isothiazole-3, 4-dicarboxylic acid, isothiazole-3,5-dicarboxylic acid, 1,2,4-thiadiazole-2,5-dicarboxylic acid 1,3,4-thiadiazole-2,5-dicarboxylic acid, (5-mercapto-1,2,4-thiadiazol-3-ylthio) acetic acid, (5-mercapto-1,3,4-thiadiazole-2- Ylthio) acetic acid, pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine 3,5-dicarboxylic acid, pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-dicarboxylic acid, pyrimidine-2,4- Dicarboxylic acid, pyrimidine-2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3- Carboxylic acid, pyrazine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, heterocyclic compounds having two acidic groups of the triazine-2,4-dicarboxylic acid; are preferred.
By using these compounds, the low leakage current characteristics of the resin film formed from the resin composition can be further enhanced.

  In the present invention, a latent acid generator can be used as the compound (B) having an acidic group because the same effect as described above can be obtained. Examples of the potential acid generator include sulfonium salts, benzothiazolium salts, ammonium salts, phosphonium salts, block carboxylic acids (trade names “Nofcure TN1”, “Nofcure TN2”, which are cationic polymerization catalysts that generate acid by heating. NOF Corporation). Among these, block carboxylic acid is preferable.

  Content of the compound (B) which has an acidic group in the resin composition used by this invention is 0.1-50 weight part normally with respect to 100 weight part of binder resin (A), Preferably it is 1-45. Parts by weight, more preferably 2 to 40 parts by weight, still more preferably 3 to 30 parts by weight. By making the usage-amount of the compound (B) which has an acidic group into the said range, a resin composition can be made excellent in liquid stability.

(Crosslinking agent (C))
The crosslinking agent (C) used in the present invention has a molecular weight of 0.05 or less in terms of the ratio to the weight average molecular weight (Mw) of the binder resin (A) described above. That is, “molecular weight of crosslinking agent (C)” / “weight average molecular weight (Mw) of binder resin (A)” = 0.05 or less. A resin film formed from the resin composition by using a crosslinking agent (C) having a molecular weight of 0.05 or less relative to the weight average molecular weight (Mw) of the binder resin (A), Excellent low leakage current characteristics can be obtained. On the other hand, when a crosslinking agent (C) having a ratio of the weight average molecular weight (Mw) of the binder resin (A) to a molecular weight exceeding 0.05 is used, the low leakage current characteristics of the resulting semiconductor element substrate, particularly In addition, low leakage current characteristics under high temperature and high humidity conditions are deteriorated. In addition, when a crosslinking agent (C) is a polymeric material, a weight average molecular weight (Mw) should just be in the said range.

  The molecular weight of the crosslinking agent (C) may be a ratio of 0.05 or less to the weight average molecular weight (Mw) of the binder resin (A), preferably 0.002 to 0.05, more preferably It is 0.025-0.33, More preferably, it is 0.033-0.25. In addition, although the molecular weight of a crosslinking agent (C) should just be the said range in relation to the weight average molecular weight (Mw) of binder resin (A), the molecular weight of a crosslinking agent (C) becomes like this. Preferably it is 100-500. More preferably, it is 120-450, More preferably, it is 150-300. If the molecular weight of the crosslinking agent (C) is too low, the flatness of the resulting resin film may be reduced.

Moreover, as a crosslinking agent (C), in addition to having the molecular weight whose ratio with respect to the weight average molecular weight (Mw) of binder resin (A) is 0.05 or less, that SP value exists in the following ranges. Is preferred. That is, when the SP value of the cross-linking agent (C) is SP ₁ , the difference (SP ₁ -SP _{2) from} SP ₂ which is the SP value of allyl glycidyl ether having an SP value of 19620 (J / CUM) ^1/2. ) Is in the range of -1900 to 5400 (J / CUM) ^1/2 , preferably in the range of -1900 to 4000 (J / CUM) ^1/2 , more preferably in the range of -1900 to 3000 (J / CUM) ¹ A range of ^{/ 2} is preferable. By using the difference (SP ₁ -SP ₂ ) within the above range, the low leakage current characteristics of the resin film formed from the resin composition can be further enhanced.

  Examples of such a crosslinking agent (C) include those having one or more, preferably two or more, more preferably three or more functional groups capable of reacting with the binder resin (A) in the molecule. The crosslinking agent (C) is not particularly limited as long as it has a functional group capable of reacting with a functional group or an unsaturated bond group in the binder resin (A), and in particular, reacts with a protic polar group. Those having a functional group that can be used are preferred. Examples of such a functional group include an amino group, a hydroxyl group, an epoxy group, and an isocyanate group, and among these, an amino group, an epoxy group, and an isocyanate group are preferable, and an epoxy group is particularly preferable.

  Specific examples of the crosslinking agent (C) include 1,2,8,9-diepoxy limonene (trade name “Celoxide 3000”, manufactured by Daicel Chemical Industries), (3 ′, 4′-epoxycyclohexane) methyl 3, 4-epoxycyclohexanecarboxylate (trade name “Celoxide 2021P”, manufactured by Daicel Chemical Industries), trimethylolpropane polyglycidyl ether (trade name “SR-TMP”, manufactured by Sakamoto Pharmaceutical Co., Ltd.), glycerin polyglycidyl ether (trade name) “SR-GLG” (manufactured by Sakamoto Pharmaceutical Co., Ltd.), 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene (trade name “Aron oxetane OXT-121”, manufactured by Toagosei Co., Ltd.) , Etc. Among these, 1,2,8,9-diepoxylimonene and (3 ′, 4′-epoxycyclohexane) methyl 3,4-epoxycyclohexanecarboxylate are more effective in improving the low leakage current characteristics. Is preferred. These can be used alone or in combination of two or more.

  In the present invention, the following crosslinking agents may be used in combination with the crosslinking agent (C). Examples of the crosslinking agent used in combination with the crosslinking agent (C) include compounds having two or more reactive groups. Examples of such a reactive group include an amino group, a carboxy group, a hydroxyl group, an epoxy group, and an isocyanate group, more preferably an amino group, an epoxy group, and an isocyanate group, and further preferably an amino group and an epoxy group. It is a group. Moreover, as an epoxy group, a terminal epoxy group and an alicyclic epoxy group are preferable, and an alicyclic epoxy group is more preferable.

  Specific examples include aliphatic polyamines such as hexamethylenediamine; aromatic polyamines such as 4,4′-diaminodiphenyl ether and diaminodiphenylsulfone; 2,6-bis (4′-azidobenzal) cyclohexanone, 4,4 ′. Azides such as diazide diphenyl sulfone; polyamides such as nylon, polyhexamethylenediamine terephthalamide, polyhexamethylene isophthalamide; N, N, N ′, N ′, N ″, N ″ — (hexa (Alkoxyalkyl) Melamines having a methylol group such as melamine or an imino group (trade names “Cymel 303, Cymel 325, Cymel 370, Cymel 350, Cymel 232, Cymel 235, Cymel 272, Cymel 212, Myel Coat 506 "{End Cymel series such as INDUSTRIES}, My Coat series); N, N ′, N ″, N ′ ″-(tetraalkoxyalkyl) glycoluril and other methylol groups and imino groups Good glycolurils (trade name “Cymel 1170” {Cytech series manufactured by Cytec Industries, Inc.}); acrylate compounds such as ethylene glycol di (meth) acrylate; hexamethylene diisocyanate polyisocyanate, isophorone diisocyanate polyisocyanate , Isocyanate compounds such as tolylene diisocyanate polyisocyanate and hydrogenated diphenylmethane diisocyanate; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxymethyl) norbornane; 1 3,4-trihydroxycyclohexane; bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, polyphenol type epoxy resin, cyclic aliphatic epoxy resin, aliphatic glycidyl ether, epoxy acrylate Examples thereof include epoxy compounds such as polymers; fluorene-based epoxy resins; and triazine nucleus-containing epoxies.

  Specific examples of the epoxy compound include a trifunctional epoxy compound having a dicyclopentadiene skeleton (trade name “XD-1000”, manufactured by Nippon Kayaku Co., Ltd.), 2,2-bis (hydroxymethyl) 1-butanol. 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct (15-functional alicyclic epoxy resin having a cyclohexane skeleton and a terminal epoxy group, trade name “EHPE3150”, manufactured by Daicel Chemical Industries, Ltd.), epoxidation 3-cyclohexene-1,2-dicarboxylate bis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic trifunctional epoxy resin, trade name “Epolide GT301”, manufactured by Daicel Chemical Industries), epoxidized butane Tetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone (fat An epoxy compound having an alicyclic structure such as an aliphatic cyclic tetrafunctional epoxy resin, trade name “Epolide GT401” manufactured by Daicel Chemical Industries, Ltd .;

  Bisphenol A type polyfunctional epoxy compound (trade names: Composeran “E103” “E103A” “E102” “E102B” “E201” “E202C” “SQ506” “SQ502-8”, manufactured by Arakawa Chemical Industries, Ltd.); Product name Oncoat "EX-1010" "EX-1011" "EX-1012" "EX-1020" "EX-1030" "EX-1040" "EX-1050" "EX-1051" "EX-1060" (Manufactured by Nagase ChemteX Corporation), (trade names “Ogsol PG100”, “Ogsol EG-200”, manufactured by Osaka Gas Chemical Co., Ltd.), heterocyclic-containing epoxy compounds (trade name “TEPIC”, manufactured by Nissan Chemical Industries, Ltd.), aromatic amine Type polyfunctional epoxy compound (trade name “H-434”, manufactured by Tohto Kasei Kogyo Co., Ltd.), Crezo Novolac polyfunctional epoxy compound (trade name “EOCN-1020”, manufactured by Nippon Kayaku Co., Ltd.), phenol novolac polyfunctional epoxy compound (Epicoat 152, 154, manufactured by Japan Epoxy Resin Co., Ltd.), polyfunctional epoxy compound having a naphthalene skeleton (Trade name EXA-4700, manufactured by Dainippon Ink Chemical Co., Ltd.), chain alkyl polyfunctional epoxy compound (trade name “SR-MK3”, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), polyfunctional epoxy polybutadiene (trade name “Epolide PB3600”) , Daicel Chemical Industries, Ltd.), Glycerin glycidyl polyether compound (trade name “SR-GLG”, Sakamoto Pharmaceutical Co., Ltd.), diglycerin polyglycidyl ether compound (trade name “SR-DGE”, Sakamoto Pharmaceutical Co., Ltd.) Company-made, polyglycerin polyglycidyl ether compound And epoxy compounds having no alicyclic structure such as products (trade name “SR-4GL”, manufactured by Sakamoto Pharmaceutical Co., Ltd.).

  The content of the crosslinking agent (C) in the resin composition used in the present invention is 21 to 150 parts by weight, preferably 25 to 140 parts by weight, more preferably 100 parts by weight of the binder resin (A). Is 28 to 130 parts by weight. If the content of the crosslinking agent (C) is too small, the resulting resin film has a low film density, which may increase the leakage current of the semiconductor element substrate. On the other hand, if the content is too large, the resin film There is a possibility that the stress increases and the adhesion to the semiconductor element substrate decreases.

(Radiation sensitive compound (D))
The resin composition used in the present invention preferably further contains a radiation sensitive compound (D) in addition to the binder resin (A), the compound (B) having an acidic group and the crosslinking agent (C).

  The radiation sensitive compound (D) used in the present invention is a compound capable of causing a chemical reaction by irradiation with radiation such as ultraviolet rays and electron beams. In the present invention, the radiation sensitive compound (D) is preferably one that can control the alkali solubility of the resin film formed from the resin composition, and it is particularly preferable to use a photoacid generator.

  Examples of such a radiation sensitive compound (D) include azide compounds such as acetophenone compounds, triarylsulfonium salts, and quinonediazide compounds, with azide compounds being preferred, and quinonediazide compounds being particularly preferred.

As the quinonediazide compound, for example, an ester compound of a quinonediazidesulfonic acid halide and a compound having a phenolic hydroxyl group can be used. Specific examples of the quinone diazide sulfonic acid halide include 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-benzoquinone diazide-5-sulfonic acid chloride, and the like. Can be mentioned. Typical examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1. -[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and the like. Other compounds having a phenolic hydroxyl group include 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, tris (4- Hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolac resin oligomer, phenolic hydroxyl group Examples thereof include oligomers obtained by copolymerizing one or more compounds and dicyclopentadiene.
Among these, a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and a compound having a phenolic hydroxyl group is preferable, and 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl)- A condensate of 3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.9 mol) is more preferred.

In addition to quinonediazide compounds, photoacid generators include onium salts, halogenated organic compounds, α, α′-bis (sulfonyl) diazomethane compounds, α-carbonyl-α′-sulfonyldiazomethane compounds, sulfone compounds, Known compounds such as organic acid ester compounds, organic acid amide compounds, and organic acid imide compounds can be used.
These may be used alone or in combination of two or more.

  The content of the radiation sensitive compound (D) in the resin composition used in the present invention is preferably 10 to 100 parts by weight, more preferably 15 to 70 parts by weight, more preferably 100 parts by weight of the binder resin (A). Preferably it is the range of 20-50 weight part. If the content of the radiation sensitive compound (D) is within this range, when patterning the resin film made of the resin composition, the difference in solubility in the developer between the radiation irradiated part and the radiation non-irradiated part becomes large, The radiation sensitivity is also high, and it is preferable because patterning by development is easy.

(Other ingredients)
Furthermore, the resin composition used in the present invention may contain a solvent. The solvent is not particularly limited, and is known as a solvent for the resin composition, for example, acetone, methyl ethyl ketone, cyclopentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2- Linear ketones such as octanone, 3-octanone and 4-octanone; alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and cyclohexanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and dioxane Alcohol alcohols such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate Esters such as methyl butyrate, ethyl butyrate, methyl lactate and ethyl lactate; cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl Propylene glycols such as ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether; diety such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether Glycols; saturated γ-lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-caprolactone; halogenated hydrocarbons such as trichloroethylene; aromatic hydrocarbons such as toluene and xylene; Examples include polar solvents such as dimethylacetamide, dimethylformamide, and N-methylacetamide. These solvents may be used alone or in combination of two or more. The content of the solvent is preferably in the range of 10 to 10,000 parts by weight, more preferably 50 to 5000 parts by weight, and still more preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the binder resin (A). In addition, when making a resin composition contain a solvent, a solvent will be normally removed after resin film formation.

  In addition, the resin composition used in the present invention is a surfactant, an acidic compound, a coupling agent or a derivative thereof, a sensitizer, a latent acid generator, if desired, as long as the effects of the present invention are not impaired. Other compounding agents such as an antioxidant, a light stabilizer, an antifoaming agent, a pigment, a dye, and a filler;

  The surfactant is used for the purpose of preventing striation (after application stripes) and improving developability. Specific examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Polyoxyethylene aryl ethers; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Fluorine surfactants; Silicone surfactants; Methacrylic acid copolymer System surfactants; acrylic acid copolymer system surfactants; and the like.

  The coupling agent or derivative thereof has an effect of further improving the adhesion between the resin film made of the resin composition and each layer including the semiconductor layer constituting the semiconductor element substrate. As the coupling agent or derivative thereof, a compound having one atom selected from a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom and having a hydrocarbyloxy group or a hydroxy group bonded to the atom can be used.

As a coupling agent or a derivative thereof, for example,
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane,
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, p-styryl Trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyl Nyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyl Limethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyl Triethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ethyl (trimethoxysilylpropoxymethyl) oxetane, 3-ethyl (triethoxysilylpropoxymethyl) Kisetan, 3-triethoxysilyl-N-(1,3-dimethyl - butylidene) propylamine, trialkoxysilanes such as bis (triethoxysilylpropyl) tetrasulfide,
Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxy Silane, di-n-butyldimethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyl Dimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, Diphenyldie Xysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldiethoxysilane In addition to dialkoxysilanes such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane,
Silicon atoms such as methyltriacetyloxysilane, dimethyldiacetyloxysilane, trade names X-12-414, KBP-44 (manufactured by Shin-Etsu Chemical Co., Ltd.), 217FLAKE, 220FLAKE, 233FLAKE, z6018 (manufactured by Toray Dow Corning Co., Ltd.) Containing compound: Phenol such as phenol resin-silica hybrid (trade names “COMPOCERAN P501”, “COMPOCELAN P502”, manufactured by Arakawa Chemical Industries), silsesquioxane (trade names “COMPOCELAN SQ-506”, manufactured by Arakawa Chemical Industries) A compound having a group and a silanol group;

(Tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate, di-i-propoxybis (acetylacetonato) titanium, propanedi Oxytitanium bis (ethylacetoacetate), tri-n-butoxytitanium monostearate, di-i-propoxytitanium distearate, titanium stearate, di-i-propoxytitanium diisostearate, (2-n-butoxycarbonyl Titanium atom-containing compounds such as benzoyloxy) tributoxytitanium, di-n-butoxy bis (triethanolaminato) titanium, as well as the preneact series (manufactured by Ajinomoto Fine Techno Co., Ltd.);
Aluminum atom-containing compounds such as (acetoalkoxyaluminum diisopropylate);
(Tetranormal propoxyzirconium, tetranormalbutoxyzirconium, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium butoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate), zirconium tetraacetyl Zirconium atom-containing compounds such as acetonate and zirconium tributoxy systemate).

  Specific examples of the sensitizer include 2H-pyrido- (3,2-b) -1,4-oxazin-3 (4H) -ones, 10H-pyrido- (3,2-b) -1,4. -Benzothiazines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides and the like.

  As the antioxidant, there can be used phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, lactone antioxidants and the like used in ordinary polymers. For example, as phenols, 2,6-di-t-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4 '-Hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl-2' -Hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 4,4'-thio-bis (3-methyl-6-tert-butylphenol) ), Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], alkylated bisphenols, etc. Can. Examples of the phosphorus-based antioxidant include triphenyl phosphite and tris (nonylphenyl) phosphite. Examples of the sulfur-based antioxidant include dilauryl thiodipropionate.

  Examples of light stabilizers include ultraviolet absorbers such as benzophenone-based, salicylic acid ester-based, benzotriazole-based, cyanoacrylate-based, and metal complex-based salts, hindered amine-based (HALS), and the like that capture radicals generated by light. Either is acceptable. Among these, HALS is a compound having a piperidine structure and is preferable because it is less colored with respect to the resin composition and has good stability. Specific compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl 1,2,3,4 -Butanetetracarboxylate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.

The preparation method of the resin composition used by this invention is not specifically limited, What is necessary is just to mix each component which comprises a resin composition by a well-known method.
The mixing method is not particularly limited, but it is preferable to mix a solution or dispersion obtained by dissolving or dispersing each component constituting the resin composition in a solvent. Thereby, a resin composition is obtained with the form of a solution or a dispersion liquid.

  A method for dissolving or dispersing each component constituting the resin composition used in the present invention in a solvent may be in accordance with a conventional method. Specifically, stirring using a stirrer and a magnetic stirrer, a high-speed homogenizer, a disper, a planetary stirrer, a twin-screw stirrer, a ball mill, a three-roll, etc. can be used. Further, after each component is dissolved or dispersed in a solvent, it may be filtered using, for example, a filter having a pore size of about 0.5 μm.

  The solid content concentration of the resin composition used in the present invention is usually 1 to 70% by weight, preferably 5 to 60% by weight, and more preferably 10 to 50% by weight. If the solid content concentration is within this range, dissolution stability, coating properties, film thickness uniformity of the formed resin film, flatness, and the like can be highly balanced.

(Semiconductor element substrate)
Next, the semiconductor element substrate of the present invention will be described. The semiconductor element substrate of the present invention has a resin film made of the above-described resin composition, and the resin film is in contact with a semiconductor element surface mounted on the semiconductor element substrate or a semiconductor layer included in the semiconductor element. It is formed.

  The semiconductor element substrate of the present invention is not particularly limited as long as it has a configuration in which a semiconductor element is mounted on the substrate, but is not limited to an active matrix substrate, an organic EL element substrate, an integrated circuit element substrate, and a solid-state imaging element. An active matrix substrate and an organic EL element substrate are preferred from the viewpoint that the effect of improving the characteristics by forming the resin film made of the resin composition described above is particularly remarkable.

  The active matrix substrate as an example of the semiconductor element substrate of the present invention is not particularly limited, but switching elements such as thin film transistors (TFTs) are arranged in a matrix on the substrate, and for driving the switching elements. Examples include a configuration in which a gate signal line for supplying a gate signal and a source signal line for supplying a display signal to the switching element are provided so as to cross each other. As a thin film transistor as an example of a switching element, a structure in which a gate electrode, a gate insulating layer, a semiconductor layer, a source electrode, and a drain electrode are provided over a substrate is exemplified.

  Furthermore, the organic EL element substrate as an example of the semiconductor element substrate of the present invention includes, for example, an anode, a hole injection transport layer, an organic light emitting layer as a semiconductor layer, an electron injection layer, and a cathode on the substrate. Examples include those having a structure having a light emitting body portion and a pixel separation film for separating the light emitting body portion.

  The resin film constituting the semiconductor element substrate of the present invention is made of the resin composition described above, and is formed in contact with the surface of the semiconductor element mounted on the semiconductor element substrate or the semiconductor layer included in the semiconductor element. The resin film is not particularly limited, and when the semiconductor element substrate of the present invention is an active matrix substrate or an organic EL element substrate, it can be configured as follows. That is, for example, when the semiconductor element substrate of the present invention is an active matrix substrate, the resin film made of the resin composition described above constitutes a protective film formed on the surface of the active matrix substrate or an active matrix substrate. It can be a gate insulating film formed in contact with a semiconductor layer (for example, an amorphous silicon layer) of a thin film transistor. Alternatively, when the semiconductor element substrate of the present invention is an organic EL element substrate, a sealing film formed on the surface of the organic EL element substrate or a light emitter part (usually an anode, A pixel separation film for separating a hole injection transport layer, an organic light emitting layer as a semiconductor layer, an electron injection layer, and a cathode).

  The resin film constituting the semiconductor element substrate of the present invention preferably has an inorganic ion content of 1 to 1000 ppb, more preferably 1 to 500 ppb, and still more preferably 1 to 300 ppb. By setting the inorganic ion content in the above range, the semiconductor element substrate can be excellent in low leakage current characteristics. If the content of inorganic ions in the resin film is too large, the leakage current due to inorganic ions in the semiconductor element substrate becomes large, resulting in poor low leakage current characteristics.

  Inorganic ions include halogen ions such as fluoride ions, chloride ions, bromide ions, and iodide ions; metal ions such as sodium ions, potassium ions, calcium ions, magnesium ions, iron ions, and bell ions; Can be mentioned.

  In the present invention, among the inorganic ions contained in the resin film, the content of halogen ions is more preferably in the range of 1 to 500 ppb, and more preferably in the range of 1 to 300 ppb. preferable. By setting the content of inorganic ions within the above range and, particularly among the inorganic ions, the content of halogen ions within the above range, it is possible to further improve the low leakage current characteristics.

In the present invention, the metal ion content in the inorganic ions can be measured, for example, by measuring the content of each atom in the resin film using an ICP mass spectrometer.
The halogen ion content can be determined from the known halogen ion amount contained in each of the crosslinking agent (C) used in the present invention and the crosslinking agent that can be used in combination.

The resin film constituting the semiconductor element substrate of the present invention has a film density of preferably 1.0 to 3.0 g / cm ³ , more preferably 1.1 to 3.0 g / cm ³ . If the film density of the resin film is too low, the leakage current of the semiconductor element substrate may be increased. On the other hand, if the film density is too high, the adhesion between the resin film and the substrate may be insufficient. . The film density of the resin film can be measured by, for example, XRR (X-ray reflectivity method).

  In the semiconductor element substrate of the present invention, the method for forming the resin film is not particularly limited, and for example, a coating method, a film lamination method, or the like can be used.

  The application method is, for example, a method of removing a solvent by applying a resin composition and then drying by heating. As a method for applying the resin composition, for example, various methods such as a spray method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a spin coating method, a bar coating method, and a screen printing method may be adopted. Can do. The heating and drying conditions vary depending on the type and blending ratio of each component, but are usually 30 to 150 ° C., preferably 60 to 120 ° C., usually 0.5 to 90 minutes, preferably 1 to 60 minutes, and more. Preferably it may be performed in 1 to 30 minutes.

  In the film lamination method, the resin composition is applied onto a B-stage film-forming substrate such as a resin film or a metal film, and then the solvent is removed by heating and drying to obtain a B-stage film. It is a method of laminating. The heating and drying conditions can be appropriately selected according to the type and mixing ratio of each component, but the heating temperature is usually 30 to 150 ° C., and the heating time is usually 0.5 to 90 minutes. . Film lamination can be performed using a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like.

  The thickness of the resin film is not particularly limited and may be appropriately set depending on the application. However, when the resin film is a protective film for an active matrix substrate or a sealing film for an organic EL element substrate. The thickness of the resin film is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, and still more preferably 0.5 to 30 μm.

  Moreover, since the resin composition used by this invention contains a crosslinking agent (C), it can perform a crosslinking reaction about the resin film formed by the above-mentioned coating method or film lamination method. Such crosslinking may be appropriately selected depending on the type of the crosslinking agent (C), but is usually performed by heating. The heating method can be performed using, for example, a hot plate or an oven. The heating temperature is usually 180 to 250 ° C., and the heating time is appropriately selected according to the area and thickness of the resin film, the equipment used, and the like. For example, when using a hot plate, the oven is usually used for 5 to 60 minutes. When used, it is usually in the range of 30 to 90 minutes. Heating may be performed in an inert gas atmosphere as necessary. Any inert gas may be used as long as it does not contain oxygen and does not oxidize the resin film. Examples thereof include nitrogen, argon, helium, neon, xenon, and krypton. Among these, nitrogen and argon are preferable, and nitrogen is particularly preferable. In particular, an inert gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less, particularly nitrogen is suitable. These inert gases can be used alone or in combination of two or more.

  In addition, if the resin film made of the resin composition described above is formed in a predetermined pattern, such as a protective film for an active matrix substrate or a sealing film for an organic EL element substrate, it is patterned. Also good. As a method for patterning a resin film, for example, a resin composition is made to contain a radiation sensitive compound (D), and a resin film before patterning is formed using the resin composition containing the radiation sensitive compound (D). In addition, there is a method in which a latent image pattern is formed by irradiating the resin film before patterning with actinic radiation, and then the developer is brought into contact with the resin film having the latent image pattern, thereby revealing the pattern.

The actinic radiation is not particularly limited as long as it can activate the radiation-sensitive compound (D) contained in the resin composition and change the alkali solubility of the resin composition containing the radiation-sensitive compound (D). Specifically, ultraviolet rays, ultraviolet rays having a single wavelength such as g-line or i-line, light rays such as KrF excimer laser light and ArF excimer laser light; particle beams such as electron beams; As a method for selectively irradiating these actinic radiations in a pattern to form a latent image pattern, a conventional method may be used. For example, ultraviolet, g-line, i-line, KrF excimer is used by a reduction projection exposure apparatus or the like. A method of irradiating a light beam such as a laser beam or an ArF excimer laser beam through a desired mask pattern, a method of drawing with a particle beam such as an electron beam, or the like can be used. When light is used as the active radiation, it may be single wavelength light or mixed wavelength light. Irradiation conditions may be appropriately selected depending on the active radiation to be used, for example, when using a light beam of wavelength 200 to 450 nm, the amount of irradiation is usually 10~1,000mJ / cm ^2, preferably 50 to 500 mJ / It is a range of cm ² and is determined according to irradiation time and illuminance. After irradiation with actinic radiation in this manner, the resin film is heat-treated at a temperature of about 60 to 130 ° C. for about 1 to 2 minutes as necessary.

  Next, the latent image pattern formed on the resin film before patterning is developed and made visible. As the developer, an aqueous solution of an alkaline compound is usually used. As the alkaline compound, for example, an alkali metal salt, an amine, or an ammonium salt can be used. The alkaline compound may be an inorganic compound or an organic compound. Specific examples of these compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and sodium metasilicate; ammonia water; primary amines such as ethylamine and n-propylamine; diethylamine Secondary amines such as di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and choline Alcohol alcohols such as dimethylethanolamine and triethanolamine; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5 -En, N-Me Cyclic amines such as Rupiroridon; and the like. These alkaline compounds can be used alone or in combination of two or more.

As an aqueous medium of the alkaline aqueous solution, water; water-soluble organic solvents such as methanol and ethanol can be used. The alkaline aqueous solution may have a surfactant added in an appropriate amount.
As a method of bringing the developer into contact with the resin film having the latent image pattern, for example, a paddle method, a spray method, a dipping method, or the like is used. The development is usually appropriately selected in the range of 0 to 100 ° C, preferably 5 to 55 ° C, more preferably 10 to 30 ° C, and usually 30 to 180 seconds.

The resin film on which the target pattern is formed in this manner can be rinsed with a rinsing liquid in order to remove the development residue, if necessary. After the rinse treatment, the remaining rinse liquid is removed with compressed air or compressed nitrogen.
Furthermore, in order to deactivate the radiation-sensitive compound (D) contained in the resin composition as necessary, the entire surface of the semiconductor element substrate can be irradiated with actinic radiation. For irradiation with actinic radiation, the method exemplified in the formation of the latent image pattern can be used. The resin film may be heated simultaneously with irradiation or after irradiation. Examples of the heating method include a method of heating the semiconductor element substrate in a hot plate or an oven. The temperature is usually in the range of 100 to 300 ° C, preferably 120 to 200 ° C.

  In the present invention, the resin film can be subjected to a crosslinking reaction after being patterned. Crosslinking may be performed according to the method described above.

According to the semiconductor element substrate of the present invention, the resin film used in contact with the semiconductor element surface mounted on the semiconductor element substrate or the semiconductor layer included in the semiconductor element is bonded to the binder having a specific molecular weight and a specific water absorption rate. It is formed by using a composition containing a resin, a compound having an acidic group, and a crosslinking agent, and the crosslinking agent contained in the composition has a specific molecular weight in relation to the molecular weight of the binder resin. In order to use those in the range, the semiconductor element substrate is excellent in low dielectric constant characteristics, low leakage current characteristics, and high breakdown voltage characteristics, and the resin film contained in the semiconductor element substrate is transparent. Can be high. Therefore, according to the present invention, it is possible to provide a semiconductor element substrate that is excellent in electrical characteristics and capable of high performance.
In particular, when the semiconductor element substrate of the present invention is an active matrix substrate, the current between the source electrode and the drain electrode rises linearly as the voltage of the gate electrode increases. In addition, even if it is kept for a long time in a high temperature and high humidity environment, the leakage current characteristics and threshold voltage do not change. Therefore, the active matrix substrate has long life, low power consumption, and high contrast. It can be.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. Parts and% in each example are based on weight unless otherwise specified.
In addition, the definition and evaluation method of each characteristic are as follows.

<Water absorption of binder resin>
The water absorption rate of the binder resin was determined from the change in weight after being immersed in 23 ° C. water for 24 hours in accordance with JIS K7209.

<Development residue, unexposed surface roughness>
The resin composition was spin coated on a silicon wafer and then pre-baked at 100 ° C. for 2 minutes using a hot plate to form a 2.5 μm thick resin film. Next, the resin film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5 mW / cm ² in the air for 40 seconds through a mask having a hole pattern of 5 μm × 5 μm. Next, a development process was performed at 23 ° C. for 60 seconds using a 0.4 wt% tetramethylammonium hydroxide aqueous solution, followed by rinsing with ultrapure water for 30 seconds to form a contact hole pattern.
And about the resin film which has the pattern of the contact hole obtained in this way, using a scanning electron microscope (SEM), the presence or absence of the melt | dissolution residue in a contact hole and the presence or absence of the roughness of an unexposed part surface Evaluation was performed. It is preferable that neither the dissolution residue nor the roughness of the surface of the unexposed area is observed because the pattern forming property by development is excellent.

<Hall state during firing>
The resin film having the contact hole pattern obtained in the same manner as described above was irradiated with ultraviolet rays having a light intensity at 365 nm of 5 mW / cm ² in air for 90 seconds, and then at 230 ° C. using an oven. Post-baking was performed for 1 hour. And the contact hole was observed with the optical microscope about the obtained resin film after the post-baking, and the hole state at the time of baking was evaluated according to the following references | standards.
○: Buried contact hole and distortion of contact hole shape are not observed.
X: The contact hole is buried or the shape of the contact hole is distorted.

<Inorganic ion content in resin film>
-Metal ion content The resin composition was diluted 20 times with diethylene glycol ethyl methyl ether, and the metal ion content in the resin film was measured using an ICP mass spectrometer.
-Halogen ion content The halogen ion content in a resin film was calculated | required by the halogen ion content in each used crosslinking agent and its usage-amount. In addition, MSDS etc. were used for halogen ion content of each crosslinking agent.

  Regarding the metal ion content and the halogen ion content, the case of 1,000 ppb or less was designated as “◯”, and the case of exceeding 1,000 ppb was designated as “x”.

<Leakage current>
A voltage of 20V is applied between the source electrode and the drain electrode of the active matrix substrate, the voltage applied to the gate electrode is changed to -20 to + 30V, and the current flowing between the source electrode and the drain electrode is changed to a manual prober. And the leakage current was measured by measuring using a semiconductor parameter analyzer (manufactured by Agilent, 4156C). The measurement was performed in an active matrix substrate in an initial state (before being held in a high temperature and high humidity environment), and in a high temperature and high humidity environment of 60 ° C. and 90% RH, and the leakage current was 1 × 10 ⁻¹¹ A / The time (unit: time) until it became cm ³ was measured. It can be said that the longer the time until the leakage current reaches 1 × 10 ⁻¹¹ A / cm ³ , the better the low leakage current characteristics.

<< Synthesis Example 1 >>
<Synthesis of polyimide resin (A1)>
In a four-necked flask under a dry air stream, 9.61 parts of 4,4′-diaminodiphenyl ether, 17.3 parts of bis [4- (4-aminophenoxy) phenyl] sulfone, bis (3-aminopropyl) tetramethyl 1.24 parts of disiloxane and 102.5 parts of cyclopentanone were charged and dissolved at 40 ° C. Then, pyromellitic anhydride 6.54 parts, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride 9.67 parts, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride 12.41 parts and 30 parts of cyclopentanone were added and reacted at 50 ° C. for 3 hours. And the solution of the polyimide resin (A1) with a solid content concentration of 35% was obtained by concentrating the obtained reaction solution with a rotary evaporator. The resulting polyimide resin (A1) had a weight average molecular weight (Mw) of 20,000 and a water absorption of 0.04% by weight.

<< Synthesis Example 2 >>
<Synthesis of polyimide resin (A2)>
Synthetic Example 1 except that the amount of 4,4′-diaminodiphenyl ether used was changed to 17.3 parts and the amount of bis [4- (4-aminophenoxy) phenyl] sulfone used was changed to 9.61 parts. Similarly, a solution of a polyimide resin (A2) having a solid content concentration of 35% was obtained. The obtained polyimide resin (A2) had a weight average molecular weight (Mw) of 20,000 and a water absorption rate of 0.16% by weight.

<< Synthesis Example 3 >>
<Synthesis of acrylic resin (A3)>
In a reaction vessel, 20 parts of styrene, 25 parts of butyl methacrylate, 25 parts of 2-ethylhexyl acrylate, 30 parts of methacrylic acid, 0.5 part of 2,2-azobisisobutyronitrile, and 300 parts of propylene glycol monomethyl ether acetate. The reaction was carried out at 80 ° C. for 5 hours with stirring in a nitrogen stream. And the solution of the acrylic resin (A3) with a solid content concentration of 35% was obtained by concentrating the obtained reaction solution with a rotary evaporator. The obtained acrylic resin (A3) had a weight average molecular weight (Mw) of 15,000 and a water absorption rate of 0.05% by weight.

<< Synthesis Example 4 >>
<Synthesis of acrylic resin (A4)>
A solution of an acrylic resin (A4) having a solid content concentration of 35% was obtained in the same manner as in Synthesis Example 3 except that the amount of butyl methacrylate used was changed to 40 parts and the amount of methacrylic acid used was changed to 20 parts. . The obtained acrylic resin (A4) had a weight average molecular weight (Mw) of 15,000 and a water absorption rate of 0.26% by weight.

Example 1
<Preparation of resin composition>
As binder resin (A), 100 parts of polyimide resin (A1) obtained in Synthesis Example 1, compound (B) having an acidic group, 2 parts of pyrazine-2,3-dicarboxylic acid, as crosslinking agent (C), 30 parts of (3 ′, 4′-epoxycyclohexane) methyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Chemical Industries, trade name “Celoxide 2021P”, molecular weight 250), radiation sensitive compound (D), (1,1 , 3-Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane) (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) ( Toyo Gosei Co., Ltd., “TS200 (product name)” 35 parts, as an anti-aging agent, pentaerythritol tetrakis [3- (3,5-di-tert Butyl-4-hydroxyphenyl) propionate] and 3 parts of a silicone surfactant (trade name “KP341”, manufactured by Shin-Etsu Chemical Co., Ltd.), diethylene glycol ethyl methyl ether as an organic solvent, It added so that a density | concentration might be 24%, and mixed and stirred. After stirring for 30 minutes, the mixture became a homogeneous solution. And the obtained solution was filtered with the filter made from a polytetrafluoroethylene with the hole diameter of 0.45 micrometer, and the resin composition was obtained.

<Production of active matrix substrate>
On a glass substrate (trade name “Corning 1737”, manufactured by Corning), chrome is formed with a film thickness of 200 nm using a sputtering apparatus, re-patterning is performed by photolithography, and a gate electrode, a gate signal line, and a gate A terminal part was formed. Next, the gate electrode and the gate electrode are covered with a CVD apparatus, the silicon nitride film serving as the gate insulating film is 450 nm thick, the a-Si layer (amorphous silicon layer) serving as the semiconductor layer is 250 nm thick, ohmic An n + Si layer to be a contact layer was continuously formed with a thickness of 50 nm, and the n + Si layer and the a-Si layer were patterned in an island shape. Further, chromium is formed to a thickness of 200 nm on the gate insulating film and the n + Si layer by a sputtering apparatus, and a source electrode, a source signal line, a drain electrode, and a data terminal portion are formed by photolithography. An unnecessary n + Si layer between the electrodes was removed to form a back channel, thereby obtaining an array substrate in which a plurality of thin film transistors were formed on a glass substrate.

And after spin-coating the resin composition obtained above to the obtained array substrate, it prebaked at 90 ° C. for 2 minutes using a hot plate to form a resin film having a thickness of 1.2 μm. . Next, the resin film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5 mW / cm ² in the air for 40 seconds through a 10 μm × 10 μm hole pattern mask. Next, after developing for 90 seconds at 25 ° C. using a 0.4 wt% tetramethylammonium hydroxide aqueous solution, rinsing with ultrapure water for 30 seconds to form a contact hole pattern, 230 ° C. The array substrate on which the protective film (resin film) was formed was obtained by performing post-baking by heating for 15 minutes.

  Then, the array substrate on which the protective film (resin film) is formed as described above is transferred to a vacuum chamber, and a mixed gas of argon and oxygen (volume ratio 100: 4) is used as the sputtering gas, pressure 0.3 Pa, DC output 400 W. Then, by performing DC sputtering through a mask, an In—Sn—O amorphous transparent conductive layer (pixel electrode) having a film pressure of 200 nm was formed so as to be in contact with the drain electrode to obtain an active matrix substrate.

  And using the resin composition obtained above, each evaluation of the residue at the time of development, the roughness of the surface of the unexposed portion, the hole state at the time of firing, and the inorganic ion content in the resin film, and the active matrix substrate The leakage current was evaluated. The results are shown in Table 1.

Example 2
A resin composition and an active matrix substrate are obtained in the same manner as in Example 1 except that the acrylic resin (A3) obtained in Synthesis Example 3 is used as the binder resin (A) instead of the polyimide resin (A1). The same evaluation was performed. The results are shown in Table 1.

<< Comparative Example 1 >>
As binder resin (A), instead of polyimide resin (A1), polyimide resin (A2) obtained in Synthesis Example 2 is used, and pyrazine-2,3-dicarboxylic acid as compound (B) having an acidic group is used. A resin composition and an active matrix substrate were obtained and evaluated in the same manner as in Example 1 except that was not used. The results are shown in Table 1.

<< Comparative Example 2 >>
As the binder resin (A), the polyimide resin (A2) obtained in Synthesis Example 2 is used in place of the polyimide resin (A1), and (3 ′, 4′-epoxycyclohexane) methyl as the crosslinking agent (C) is used. Instead of 30 parts of 3,4-epoxycyclohexanecarboxylate, epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic tetrafunctional epoxy resin, trade name “Epolide GT401”, A resin composition and an active matrix substrate were obtained and evaluated in the same manner as in Example 1 except that 30 parts by weight manufactured by Daicel Chemical Industries, Ltd. and weight average molecular weight (Mw) 1130) were used. The results are shown in Table 1.

<< Comparative Example 3 >>
As binder resin (A), instead of acrylic resin (A3), acrylic resin (A4) obtained in Synthesis Example 4 is used, and pyrazine-2,3-dicarboxylic acid as compound (B) having an acidic group is used. A resin composition and an active matrix substrate were obtained and evaluated in the same manner as in Example 2 except that was not used. The results are shown in Table 1.

<< Comparative Example 4 >>
As the binder resin (A), the acrylic resin (A4) obtained in Synthesis Example 4 was used instead of the acrylic resin (A3), and (3 ′, 4′-epoxycyclohexane) methyl as the crosslinking agent (C) was used. Instead of 30 parts of 3,4-epoxycyclohexanecarboxylate, epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic tetrafunctional epoxy resin, trade name “Epolide GT401”, A resin composition and an active matrix substrate were obtained and evaluated in the same manner as in Example 2 except that 30 parts by weight manufactured by Daicel Chemical Industries, Ltd. and weight average molecular weight (Mw) 1130) were used. The results are shown in Table 1.

  As shown in Table 1, from the results of Examples 1 and 2, the resin film was divided into a binder resin (A) having a specific molecular weight and a specific water absorption rate, a compound (B) having an acidic group, and a crosslinking agent ( C) and a crosslinker contained in the composition, the molecular weight of the composition is in a specific range in relation to the molecular weight of the binder resin. The (active matrix substrate) can suppress an increase in leakage current when held in a high temperature and high humidity environment for a long time, and has excellent low leakage current characteristics. In addition, the resin film is a good result in all of the residue at the time of development, the roughness of the surface of the unexposed portion, and the hole state at the time of baking, and has excellent pattern formability at the time of development, and can be patterned with high accuracy. It can also be confirmed that it is.

On the other hand, from the results of Comparative Examples 1 and 3, when the compound (B) having an acidic group was not used, the leakage current was reduced in a relatively short time when kept in a high temperature and high humidity environment. As a result, the low leakage current characteristics were inferior.
Further, from the results of Comparative Examples 2 and 4, even when a cross-linking agent having a molecular weight exceeding 0.05 in terms of the weight average molecular weight (Mw) of the binder resin (A) is used, When held in an environment, the leakage current increased in a relatively short time, resulting in poor low leakage current characteristics.

Claims (4)

A semiconductor element substrate having a resin film comprising a resin composition comprising a binder resin (A), a compound having an acidic group (B), and a crosslinking agent (C),
The binder resin (A) has a weight average molecular weight (Mw) of 10,000 or more and a water absorption of 0.03% by weight or more.
The ratio of the molecular weight of the crosslinking agent (C) to the weight average molecular weight (Mw) of the binder resin (A) is 0.05 or less,
The content of the crosslinking agent (C) with respect to 100 parts by weight of the binder resin (A) is 21 to 150 parts by weight,
The semiconductor element substrate, wherein the resin film is formed in contact with a semiconductor element surface mounted on the semiconductor element substrate or a semiconductor layer included in the semiconductor element.   The semiconductor element substrate according to claim 1, wherein the resin composition further contains a radiation sensitive compound (D).   3. The semiconductor element substrate according to claim 1, wherein an inorganic ion content in the resin film is 1-1000 ppb.   The semiconductor element substrate according to claim 1, which is an active matrix substrate or an organic EL element substrate.