WO2023148996A1 - Resin composition, resin composition coating, resin composition film, cured film, and electronic component - Google Patents

Abstract

Provided are a resin composition that enables fine pattern processing even on a rough-surfaced substrate made of a ceramic or the like, a resin composition film, and a semiconductor device in which these are used. A resin composition containing (A) a cationic polymerizable compound and (B) a photocationic polymerization initiator, wherein the resin composition is characterized by furthermore containing (C) a sensitizer.

Description

Resin composition, resin composition coating, resin composition film, cured film, and electronic component

The present invention relates to resin compositions, resin composition coatings, resin composition films, cured films, and electronic components. More particularly, the present invention relates to resin compositions suitably used for surface protective films of semiconductor elements and inductor devices, interlayer insulating films, structures of MEMS (Micro Electro Mechanical Systems), and the like.

Conventionally, polyimide-based materials and polybenzoxazole-based materials, which have excellent heat resistance, electrical insulation, and mechanical properties, have been widely used for surface protective films and interlayer insulating films of semiconductor devices. With the recent demand for higher density and higher performance of semiconductor devices, photosensitive materials are required for surface protective films and interlayer insulating films from the viewpoint of production efficiency.

On the other hand, photosensitive materials are required to process various packaging structures for semiconductor devices in recent years and high aspect ratio processing for MEMS. In order to meet such demands, a chemically amplified photo-cationically polymerizable photosensitive material has been disclosed (for example, Patent Document 1). Further, in a chemically amplified cationic photopolymerization system, a photocationic polymerizable material intended to improve mechanical properties and thermal properties by containing an epoxy resin with a specific structure has been disclosed (for example, Patent Document 2. ).

WO2008/007764 JP 2019-38964 A

However, in the above-mentioned photo-cationically polymerizable materials, during pattern processing on a substrate with a rough surface such as ceramics, the irradiation light transmitted through the inside of the resin composition during exposure is diffusely reflected on the substrate surface. However, photocationic polymerization proceeds even in unexposed areas, making it difficult to form fine patterns.

In view of this situation, the authors have conducted extensive research and found that fine pattern processing is possible even on substrates with rough surfaces such as ceramics by including a sensitizer in the photo-cationically polymerized material.

The present invention for solving the above problems is as follows.

A resin composition containing (A) a cationically polymerizable compound and (B) a photocationic polymerization initiator, and further containing (C) a sensitizer.

The resin composition of the present invention is a resin composition, a resin composition film, a resin composition film, a cured film, a resin composition coating, a resin composition film, a resin composition film, a resin composition film, a resin composition film, a resin composition film, a resin composition film, a resin composition film, a resin composition film, a resin composition film, a resin composition film, a resin composition film, a resin composition film, a resin composition film, a resin composition film, a resin composition film, or a cured film. and electronic components.

The present invention provides a resin composition containing (A) a cationically polymerizable compound and (B) a photocationic polymerization initiator, and further containing (C) a sensitizer. is.

In the resin composition of the present invention, when irradiated with light, (B) the photocationic polymerization initiator generates an acid, and (A) the cationic polymerizable compound undergoes a polymerization reaction to cause a negative photosensitive property that becomes insoluble in a developer. is preferably a negative photosensitive resin composition.

(A) Cationic polymerizable compound The resin composition of the present invention contains (A) a cationic polymerizable compound.

(A) Cationic polymerizable compounds include cyclic ether compounds (epoxy compounds, oxetane compounds, etc.), ethylenically unsaturated compounds (vinyl ethers, styrenes, etc.), bicycloorthoesters, spiroorthocarbonates, spiroorthoesters, and the like.

As the epoxy compound, known ones can be used, including aromatic epoxy compounds, alicyclic epoxy compounds and aliphatic epoxy compounds.

Examples of aromatic epoxy compounds include glycidyl ethers of monohydric or polyhydric phenols (phenol, bisphenol A, phenol novolak, and alkylene oxide adducts thereof) having at least one aromatic ring.

Examples of alicyclic epoxy compounds include compounds obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, etc. ).

Aliphatic epoxy compounds include aliphatic polyhydric alcohols or polyglycidyl ethers of alkylene oxide adducts thereof (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.), aliphatic polybasic acids polyglycidyl esters (diglycidyl tetrahydrophthalate, etc.), and epoxidized long-chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.).

As the oxetane compound, known ones can be used. -oxetanylmethyl)ether, 2-hydroxypropyl(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, oxetanylsilsesquioxetane and phenol novolac oxetane etc.

As the ethylenically unsaturated compound, known cationic polymerizable monomers can be used, including aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrene and cationic polymerizable nitrogen-containing monomers.

The aliphatic monovinyl ethers include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether.

　Aromatic monovinyl ethers include 2-phenoxyethyl vinyl ether, phenyl vinyl ether and p-methoxyphenyl vinyl ether.

Examples of polyfunctional vinyl ethers include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.

Styrenes include styrene, α-methylstyrene, p-methoxystyrene and ptert-butoxystyrene.

Examples of cationic polymerizable nitrogen-containing monomers include N-vinylcarbazole and N-vinylpyrrolidone.

Bicycloorthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane and 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo - [2.2.2] octane and the like.

Examples of spiro orthocarbonates include 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]undecane. be done.

Spiro orthoesters include 1,4,6-trioxaspiro[4.4]nonane, 2-methyl-1,4,6-trioxaspiro[4.4]nonane and 1,4,6-trioxas pyro[4.5]decane and the like.

Among these cationically polymerizable compounds, epoxy compounds, oxetane compounds and vinyl ethers are preferred, epoxy compounds and oxetane compounds are more preferred, and epoxy compounds are particularly preferred. Among them, a polyfunctional epoxy compound that is liquid at normal temperature (20° C.) is preferable, and the polyfunctional epoxy compound has an epoxy equivalent of 80 g/eq. above, 160 g/eq. The following are preferable. Since the polyfunctional epoxy compound is liquid at room temperature, the resin composition of the present invention preferably further contains (D) a polymer compound, as described later. It is preferable because the solubility is improved and fine pattern workability can be obtained. On the other hand, the epoxy equivalent of the polyfunctional epoxy compound is 80 g/eq. above, 160 g/eq. It is preferable from the viewpoint that the heat resistance and chemical resistance of the cured film are improved by being below.

A polyfunctional epoxy compound that is liquid at room temperature and has an epoxy equivalent of 80 g/eq. above, 160 g/eq. Examples of the following epoxy compounds include TEPIC-VL (trade name, manufactured by Nissan Chemical Industries, Ltd.), bisphenol A type epoxy compound, bisphenol F type epoxy compound, SHOWFREE BATG, SHOWFREE PETG (trade name, all of which are manufactured by Showa Denko K.K.) and the like.

(A) The cationically polymerizable compound may be used alone, or two or more of them may be used in combination.

From the viewpoint of exhibiting sufficient cationic curability and improving pattern processability, when the polymer compound (D) is 100 parts by mass, the content of the cationic polymerizable compound (A) is preferably 30 parts by mass or more, More preferably, it is 50 parts by mass or more. On the other hand, when it is made into a film form, that is, the resin composition film, the surface of the resin composition film does not have tackiness, and from the viewpoint of easy handling and the improvement of the strength and elongation of the cured film, (D) polymer When the compound is 100 parts by mass, the content of the cationic polymerizable compound (A) is preferably 200 parts by mass or less, more preferably 150 parts by mass or less.

(B) Cationic Photopolymerization Initiator The resin composition of the present invention contains (B) a cationic photopolymerization initiator.

(B) The photocationic polymerization initiator is one that generates acid by light and causes cationic polymerization. (B) As the cationic photopolymerization initiator, a known compound can be used without particular limitation, but an onium salt is preferred.

(B) Specific examples of photocationic polymerization initiators include aromatic iodonium complex salts, aromatic sulfonium complex salts, aromatic borate complex salts, and aromatic gallate complex salts. Specific examples of aromatic iodonium complex salts include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di(4-nonylphenyl)iodonium hexafluorophosphate, and the like. These (B) photocationic polymerization initiators may be used alone, or two or more of them may be used in combination.

The content of the photocationic polymerization initiator (B) is preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, when the cationically polymerizable compound (A) is 100 parts by mass. .7 parts by mass or more is more preferable. Thereby, the cationically polymerizable compound exhibits sufficient curability, and the pattern workability can be improved. On the other hand, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, from the viewpoint of improving the storage stability of the resin composition before curing.

(C) Sensitizer The resin composition of the present invention contains (C) a sensitizer.

The (C) sensitizer is a compound that can absorb light, donate the absorbed light energy to the (B) photocationic polymerization initiator, generate an acid, and cause cationic polymerization. Since the sensitizer absorbs light with respect to the irradiation wavelength during patterning, it is possible to reduce the transmittance of the resin composition film formed from the resin composition. Therefore, the transmittance of the resin composition film can be arbitrarily controlled by the content of the sensitizer in the resin composition.

Although the sensitizer is not particularly limited, the sensitizer (C) is preferably an anthracene compound. ) is more preferred. Examples of alkoxy groups include C1-C4 alkoxy groups such as methoxy, ethoxy and propoxy groups. The 9,10-dialkoxy-anthracene derivative may further have a substituent. Examples of substituents in the 9,10-dialkoxy-anthracene derivative include halogen atoms such as fluorine, chlorine, bromine and iodine atoms; C1-C4 alkyl groups such as methyl, ethyl and propyl; A sulfonic acid alkyl ester group, a carboxylic acid alkyl ester group, and the like are included. Examples of the alkyl in the sulfonic acid alkyl ester group and carboxylic acid alkyl ester include C1-C4 alkyl such as methyl, ethyl and propyl. The substitution position of these substituents is preferably 2-position.

In the resin composition of the present invention, when the entire resin composition is 100% by mass, the total amount of the (C) sensitizer is preferably 0.1% by mass or more and 5.0% by mass or less, and the above (C) increase The content of the sensitizing agent is not particularly limited, but is preferably 0.05% by mass or more, more preferably 0.1% by mass or more. This makes it possible to reduce the transmittance of the resin composition film, suppress light reflected from the substrate surface even on a substrate with a rough surface such as ceramics, and facilitate processing of fine patterns. On the other hand, from the viewpoint of suppressing the deterioration of the mechanical properties and thermal properties of the cured film of the resin composition film formed from the resin composition, when the mass of the entire resin composition is 100% by mass, (C) a sensitizer The content of is preferably 10% by mass or less, more preferably 5% by mass or less.

The resin composition of the present invention contains (D) a polymer compound, and the (D) polymer compound is preferably at least one compound selected from the group consisting of polyamide, polyimide, polyamideimide, and polybenzoxazole. . In the present invention, the polyimide precursor and the polybenzoxazole precursor respectively correspond to the above polyamides.

By containing this (D) polymer compound, the resin composition of the present invention has excellent film-forming properties when it is formed into a film-like resin composition coating, and the cured film has excellent tensile strength and tensile elongation. . The weight-average molecular weight of (D) the polymer compound is not particularly limited, but the weight-average molecular weight is preferably 1,000 or more and 200,000 or less. (D) The polymer compound may be used alone or in combination of two or more. The weight average molecular weight of the (D) polymer compound in the present invention is measured by a gel permeation chromatography method (GPC method) and calculated in terms of polystyrene.

In the resin composition of the present invention, the molecular chain end of the (D) polymer compound preferably has a structure derived from a carboxylic acid residue. The resin composition of the present invention does not have a structure in which the molecular chain end is derived from a carboxylic acid residue, including the (D) polymer compound in which the molecular chain end is derived from a carboxylic acid residue. It is also possible to include polymeric compounds. When the resin composition of the present invention contains a polymer compound whose molecular chain end does not have a structure derived from a carboxylic acid residue, the content is preferably as small as possible. With respect to a total of 100 parts by mass of the (D) polymer compound having a structure derived from a carboxylic acid residue, the molecular chain end does not have a structure derived from a carboxylic acid residue (D) polymer compound is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass, and particularly preferably 0 to 2 parts by mass.

The content of the (D) polymer compound whose molecular chain end has a structure derived from a carboxylic acid residue is not particularly limited, but it may be contained in an amount of 20% by mass or more and 95% by mass or less in 100% by mass of the resin composition. It is preferably contained in an amount of 30% by mass or more and 85% by mass or less, and particularly preferably in an amount of 30% by mass or more and 70% by mass or less. By containing 20% by mass or more of the polymer compound (D) having a structure derived from a carboxylic acid residue at the molecular chain end, the strength of the cured film is improved. On the other hand, by setting the content of the polymer compound (A) having a structure derived from a carboxylic acid residue to 95% by mass or less in the resin composition, the cationic polymerization reaction proceeds more easily. The chemical resistance of the cured film is improved.

(D) Since the molecular chain end of the polymer compound has a structure derived from a carboxylic acid residue, the molecular chain end can be a functional group that inhibits cationic polymerization and has a molecular structure that does not possess an amine terminal structure. As a result, even when polyamide, polyimide, and polyamideimide are used, sufficient cationic polymerizability can be expressed, which is preferable.

Here, (D) the structure derived from a carboxylic acid residue at the molecular chain end of the polymer compound is an organic group derived from a carboxylic acid residue that can constitute a polyamide, a polyimide, or a polyamideimide. A structure derived from an acid, a dicarboxylic acid, a monoacid chloride compound, a diacid chloride compound, a tetracarboxylic acid or an acid anhydride, an acid dianhydride, or the like. Among the above, it is particularly preferable that (D) the structure derived from the carboxylic acid residue at the molecular chain end of the polymer compound is a structure derived from tetracarboxylic dianhydride. A structure in which the molecular chain end is derived from a tetracarboxylic dianhydride is preferable in terms of improving the storage stability of the resin composition before heat curing. On the other hand, as a cured film, the terminal carboxylic anhydride group becomes a reactive functional group, which is preferable in that the heat resistance and chemical resistance after thermosetting are improved.

(D) The polymer compound is preferably alkali-soluble. Alkali-soluble is preferable because development can be carried out with an alkaline aqueous solution without using an organic solvent, which is a factor of environmental load, in development during pattern processing. The term “alkali-soluble” as used herein means that 0.1 g or more of a tetramethylammonium hydroxide solution dissolves in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25°C. In order to exhibit alkali solubility, (D) the polymer compound desirably has an alkali-soluble functional group. The alkali-soluble functional group is a functional group having acidity, and specific examples include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and the like. Among the above-mentioned alkali-soluble functional groups, the alkali-soluble functional group is preferably a phenolic hydroxyl group in view of storage stability of the resin composition, corrosion of copper wiring as a conductor, and the like. (D) The polymer compound is preferably a compound having a phenolic hydroxyl group in the molecular chain.

(D) The structure (organic group) in which the molecular chain end of the polymer compound is derived from a carboxylic acid residue includes aromatic dicarboxylic acids, aromatic dianhydrides, alicyclic dicarboxylic acids, and alicyclic dianhydrides. compounds, aliphatic dicarboxylic acids, aliphatic dianhydrides, and the like, but are not limited to these. Moreover, these are used individually or in combination of 2 or more types.

Among these, alicyclic carboxylic acid is preferred because it is possible to design a transparent resin with respect to the wavelength used for patterning, and as a result, it is possible to express fine pattern processability with a thick film. Organic groups derived from residues are preferred.

In the present invention, the (D) polymer compound is preferably the polyamide, polyimide, and polyamideimide, but at least Compounds having one or more structures are preferred.

(In general formulas (1) and (2), X ¹ and X ² independently represent a divalent to ^{10-valent organic group, X 2 represents} a 4- to 10-valent organic group, Y ¹ and Y ² each independently represents a divalent to tetravalent organic group, R represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, q is an integer of 0 to 2, r, s, t and u are Each is independently an integer from 0 to 4.)
Y ¹ and Y ² in general formulas (1) and (2) each represent a divalent to tetravalent organic group, and represent an organic group derived from diamine.

Y ¹ and Y 2 in general formulas (1) and ( ² ) of the polymer compound (D) preferably contain a diamine residue having a phenolic hydroxyl group. By containing a diamine residue having a phenolic hydroxyl group, moderate solubility of the resin in an alkaline developer can be obtained, so a high contrast between exposed and unexposed areas can be obtained, and a desired pattern can be formed.

Specific examples of diamines having a phenolic hydroxyl group include bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino- 4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, 2,2'- Ditrifluoromethyl-5,5'-dihydroxyl-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, 2,2'-bis(trifluoromethyl)-5,5'- Aromatic diamines such as dihydroxybenzidine, compounds in which some of the hydrogen atoms of these aromatic rings or hydrocarbons are substituted with alkyl groups having 1 to 10 carbon atoms, fluoroalkyl groups, halogen atoms, etc., and the following Examples include, but are not limited to, diamines having the structures shown. Other diamines to be copolymerized can be used as they are or as corresponding diisocyanate compounds, trimethylsilylated diamines. Moreover, you may use combining these 2 or more types of diamine components.

Y ¹ and Y ² in general formulas (1) and (2) may contain a diamine residue having an aromatic group other than those mentioned above. Heat resistance can be improved by copolymerizing these. Specific examples of aromatic diamine residues include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4 '-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 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)biphenyl , 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'-tetramethyl -4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, etc. and aromatic diamines, and compounds in which some of the hydrogen atoms of these aromatic rings or hydrocarbons are substituted with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, or the like. It is not limited to these. Other diamines to be copolymerized can be used as they are or as corresponding diisocyanate compounds, trimethylsilylated diamines. Moreover, you may use combining these 2 or more types of diamine components.

In the general formula (1) and general formula (2) in the present invention, X ¹ and X ² are preferably carboxylic acid residues, and ^{X 1 is} a ^divalent to decavalent organic group. is preferred, and X ² is preferably a tetravalent to decavalent organic group.

The carboxylic acid residue preferably has a structure derived from an alicyclic tetracarboxylic dianhydride. That is, it is preferable that the polymer compound (D) is at least one compound selected from the group consisting of polyamide, polyimide, and polyamideimide, and further has a structure derived from an alicyclic tetracarboxylic dianhydride. . When the carboxylic acid residue has a structure derived from an alicyclic tetracarboxylic dianhydride, the light transmittance of the resin composition with respect to the exposure wavelength is increased, and processing into a thick film of 20 μm or more is facilitated. . Furthermore, although the reason is not clear, the (D) polymer compound has a structure derived from an alicyclic tetracarboxylic dianhydride, so that the reactivity of cationic polymerization is higher than that of an aromatic dianhydride. It is preferable in that it increases and the chemical resistance of the cured film is improved.

Among the alicyclic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides having a polycyclic structure improve chemical resistance when cured and improve ion migration resistance. is preferred.

The (D) polymer compound in the present invention preferably has a structure derived from a compound represented by at least one of the following general formula (3) or (4).

(In the formula, R ¹ , R ² and R ₃ each independently represent a hydrogen atom or a methyl group.)
(D) The polymer compound has a structure derived from the compound represented by the general formula (3) or (4), and the resin skeleton has flexibility, so that the resin composition before curing has an organic It is preferable because it has high solubility in a solvent, hardly causes precipitation of the resin in the composition, and is excellent in storage stability.

A specific example of the organic group derived from an alicyclic tetracarboxylic dianhydride having a polycyclic structure is 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4 -tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-4methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-7-methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, norbornane-2-spiro- 2′-Cyclopentanone-5′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride, norbornane-2-spiro-2′-cyclohexanone-6′ -spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride.

The carboxylic acid residue may include an acid dianhydride other than the alicyclic tetracarboxylic dianhydride having the polycyclic structure. Specifically, 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 product, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4- dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-di carboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluoric acid dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluoric acid dianhydride, 2 ,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2 - aromatic tetracarboxylic dianhydrides such as bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 1,2 ,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 5-(2 ,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic dianhydride, 2,3,4 ,5-tetrahydrofurantetracarboxylic dianhydride and the like, but are not limited thereto. Moreover, these are used individually or in combination of 2 or more types.

The molar ratio of the structures represented by the general formulas (1) and (2) in the present invention is obtained by a method of calculating from the molar ratio of the monomers used for polymerization or by using a nuclear magnetic resonance spectrometer (NMR). It can be confirmed by a method for detecting peaks of a polyamide structure, an imide precursor structure, or an imide structure in a resin, a resin composition, or a cured film.

The (D) polymer compound having a structure derived from a carboxylic acid residue at the molecular chain end is, for example, in the case of a polyimide having a carboxylic acid residue at the molecular chain end, an acid anhydride with respect to the diamine used during polymerization. It can be obtained by increasing the content of the substance. At that time, when the total amount of carboxylic acid residues in the polymer compound (D) is 100 mol %, the total amount of amine residues is preferably 60 mol % or more and 98 mol % or less. That is, the polymer compound (D) is preferably a compound obtained by polymerizing 60 to 98 mol % of amine residues in total with respect to 100 mol % of carboxylic acid residues in total. When the total amount of amine residues is 60 mol% or more, the weight average molecular weight tends to be 1,000 or more, and the film-forming property is excellent. The content ratio of the polymer compound becomes smaller, the cationic polymerization reaction proceeds more easily, and the chemical resistance of the cured film is improved.

As another method for obtaining the (D) polymer compound whose molecular chain end is a structure derived from a carboxylic acid residue, a specific compound, specifically, an acid anhydride, among compounds generally used as a terminal blocking agent It can also be obtained by using a compound, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.

(D) blocking the molecular chain ends of the polymer compound with a carboxylic acid or acid anhydride terminal blocker having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group, or an allyl group; Therefore, the dissolution rate of the (D) polymer compound in an alkaline aqueous solution and the mechanical properties of the resulting cured film can be easily adjusted within a preferable range. Also, a plurality of terminal blocking agents may be reacted to introduce a plurality of different terminal groups.

Acid anhydrides, monocarboxylic acids, monoacid chloride compounds as terminal blocking agents, and monoactive ester compounds as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic acid Acid anhydrides such as anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1- Monomers such as hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid and 4-carboxybenzenesulfonic acid Carboxylic acids and monoacid chloride compounds in which these carboxyl groups are acid chlorides, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7- Mono-acid chloride compounds in which only one carboxyl group of dicarboxylic acids such as dicarboxynaphthalene and 2,6-dicarboxynaphthalene is acid-chlorinated, mono-acid chloride compounds and N-hydroxybenzotriazole, imidazole, N-hydroxy-5- Active ester compounds obtained by reaction with norbornene-2,3-dicarboximide are preferred. You may use 2 or more types of these.

Polymer compounds into which these terminal blocking agents are introduced are (D) polymer compounds whose molecular chain ends are derived from carboxylic acid residues. A terminal blocking agent that can be used to obtain the (D) polymer compound having a structure derived from a carboxylic acid residue at the molecular chain end can be easily detected by the following method. For example, the (A) polymer compound into which a terminal blocker has been introduced is dissolved in an acidic solution, decomposed into the amine component and the acid anhydride component, which are structural units, and analyzed by gas chromatography (GC) or NMR. can easily detect the terminal blocking agent used in the present invention. Apart from this, it can be easily detected by directly measuring the resin component into which the end blocking agent has been introduced by pyrolysis gas chromatography (PGC), infrared spectrum and 13C-NMR spectrum.

In the present invention, the (D) polymer compound is synthesized, for example, by the following method, but is not limited to this. The polyimide structure is formed by replacing part of the diamine with a primary monoamine as a terminal blocker, or by replacing tetracarboxylic dianhydride with a dicarboxylic anhydride as a terminal blocker by a known method. synthesized. For example, a method of reacting a tetracarboxylic dianhydride, a diamine compound and a monoamine at a low temperature, a method of reacting a tetracarboxylic dianhydride, a dicarboxylic anhydride and a diamine compound at a low temperature, and a method of reacting a tetracarboxylic dianhydride with a diamine compound. A polyimide precursor is obtained by using a method such as a method of obtaining a diester with an alcohol, and then reacting a diamine, a monoamine, and a condensing agent. After that, a polyimide can be synthesized using a known imidization reaction method.

In the present invention, it is preferable that the polymer compound (D) is polymerized by the above method, then poured into a large amount of water or a mixture of methanol and water, etc., precipitated, filtered, dried, and isolated. . The drying temperature is preferably 40-100°C, more preferably 50-80°C. By this operation, unreacted monomers and oligomer components such as dimers and trimers are removed, and the film properties after thermal curing can be improved.

The imidization rate in the present invention can be easily determined, for example, by the following method. First, the infrared absorption spectrum of the polymer is measured to confirm the presence of absorption peaks (near 1780 cm ⁻¹ and 1377 cm ⁻¹ ) of the imide structure due to polyimide. Next, the polymer was heat-treated at 350 ° C. for 1 hour ^, and the infrared absorption spectrum was measured as a sample with an imidization rate of 100%. The imidization rate is obtained by calculating the content of imide groups in the pre-resin. The imidization rate is preferably 50% or more, more preferably 80% or more, in order to suppress the change in the ring closure rate during thermosetting and to obtain the effect of reducing the stress.

The resin composition of the present invention may contain a thermal cross-linking agent, preferably a compound having an alkoxymethyl group or a methylol group.

Examples having an alkoxymethyl group or a methylol group include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMO-PC, DMO-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290 , NIKALAC MX-280, NIKALAC MW-100LM, and NIKALAC MX-750LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.).

The resin composition of the present invention can further contain a silane compound. By containing the silane compound, the adhesion of the heat-resistant resin coating is improved. Specific examples of silane compounds include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltriethoxysilane. methoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltri Methoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and the like can be mentioned.

The resin composition of the present invention may optionally contain surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone and methyl for the purpose of improving wettability with the support. Ketones such as isobutyl ketone and ethers such as tetrahydrofuran and dioxane may be included. In addition, for the purpose of suppressing the thermal expansion coefficient, increasing the dielectric constant, or decreasing the dielectric constant, inorganic particles such as silicon dioxide or titanium dioxide, polyimide powder, or the like may be contained.

Because the resin composition of the present invention has an appropriate transmittance, it suppresses diffusely reflected light from the surface of the ceramic substrate, so it is preferably used for pattern processing on the surface of the ceramic substrate.

In the resin composition of the present invention, the transmittance of a resin composition film having a thickness of 20 μm formed from the resin composition is 20% or more and 65% or less, and the (C) sensitizer is excluded from the resin composition. It is preferable that the transmittance of the resin composition C film having a thickness of 20 μm formed using the resin composition C is 70% or more and 100% or less.

When the transmittance of a 20 μm resin composition film formed using the resin composition C is 70% or more and 100 or less, when patterning is performed using such a resin composition of the present invention, even in deep parts Irradiation light arrives. Furthermore, since the transmittance of the resin composition film of 20 μm formed from the resin composition of the present invention is 65% or less, the resin composition film can be used for pattern processing on a substrate with a rough surface such as ceramics. can be transmitted through the surface of the substrate, and the reflected light diffusely reflected on the substrate surface can be suppressed to obtain a fine pattern. On the other hand, when the transmittance is 20% or more, the irradiated light reaches a deep portion, and the sensitizer (C) absorbs light even at the bottom of the resin composition film, and the absorbed light energy is transferred to (B ) by donating to a photo-cationic polymerization initiator to generate acid, cationic polymerization proceeds, and a fine isolated pattern can be formed without exfoliation.

Resin composition C is a resin composition that is simply remixed by removing only (C) the sensitizer. For example, in the case of the resin composition of the present invention containing (A) 50 parts by mass of a cationic polymerizable compound, (B) 50 parts by mass of a photocationic polymerization initiator, and (C) 50 parts by mass of a sensitizer, the resin Composition C means a resin composition containing (A) 50 parts by mass of a cationic polymerizable compound and (B) 50 parts by mass of a cationic photopolymerization initiator, for example, (A) 30 parts by mass of a cationic polymerizable compound , (B) 30 parts by weight of a photocationic polymerization initiator, (C) 30 parts by weight of a sensitizer, (D) 30 parts by weight of a polymer compound, and 30 parts by weight of other components of the resin composition of the present invention In the case, the resin composition C contains (A) 30 parts by weight of a cationic polymerizable compound, (B) 30 parts by weight of a photocationic polymerization initiator, (D) 30 parts by weight of a polymer compound, and 30 parts by weight of other components means a resin composition containing

The transmittance of a resin composition film having a thickness of 20 μm formed from the resin composition of the present invention is the transmittance measured by forming a resin composition film having a thickness of 20 μm using the resin composition of the present invention. means. Similarly, the transmittance of a resin composition C film having a thickness of 20 μm means the transmittance measured by blending the resin composition C and using it to form a resin composition film having a thickness of 20 μm. .

A method for producing a 20 μm thick resin composition film formed from the resin composition of the present invention and a method for producing a 20 μm thick resin composition C film are as follows. That is, the resin composition of the present invention or resin composition C is applied onto a polyethylene terephthalate (sometimes referred to as PET) film having a thickness of 50 μm using a comma roll coater and dried at 120° C. for 8 minutes. After that, a polypropylene (sometimes referred to as PP) film having a thickness of 30 μm is laminated as a protective film to obtain a resin composition film having a resin composition coating.

The method for measuring the transmittance is as described in the section on the resin composition coating described later.

The transmittance of a 20 μm resin composition film may be obtained by forming a resin composition film having a film thickness of 15 μm or more and 25 μm or less, and correcting the measurement result of one of them to a thickness of 20 μm. The details are as described in the section of the resin composition coating described later.

The shape of the resin composition of the present invention before curing is not limited, and examples thereof include a varnish shape and a film shape. Here, the film-shaped resin composition of the present invention is also referred to as the resin composition coating of the present invention. The resin composition film of the present invention comprises a film-like form of the resin composition of the present invention and a support. A resin composition film having a resin composition coating and a support. Therefore, the resin composition film of the present invention is in the form of a film formed on a support, that is, a resin composition film having a resin composition film formed from the resin composition of the present invention on a support. When used in the form of a varnish, a solution obtained by dissolving components (A) to (C) and optional components in an organic solvent can be used. Also, the resin composition film can be obtained, for example, by applying the resin composition of the present invention onto a support and then drying it if necessary.

The film-shaped resin composition of the present invention, that is, the resin composition coating formed from the resin composition of the present invention preferably has a transmittance of 20% or more and 65% or less regardless of its thickness. More preferably, the transmittance at a thickness of 20 μm is 20% or more and 65% or less. When the transmittance of the resin composition film is 65% or less, when pattern processing is performed on a substrate with a rough surface such as ceramics, the reflected light that passes through the resin composition film and diffusely reflects on the substrate surface is suppressed. , fine patterns can be obtained. On the other hand, when the transmittance is 20% or more, the irradiated light reaches a deep portion, and the sensitizer (C) absorbs the light even at the bottom of the resin composition film, and the absorbed light energy ( B) By donating to a photocationic polymerization initiator, an acid is generated, cationic polymerization proceeds, and a fine isolated pattern can be formed without exfoliation.

In the present invention, the transmittance of the resin composition coating and the transmittance at a thickness of 20 μm of the resin composition coating are transmittances at the wavelength of the light used for pattern processing. Preferably, the transmittance is measured at any wavelength of i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp, and at least one measurement wavelength is 20% or more and 65% or less. Good to have.

The transmittance of the resin composition film having a thickness of 20 μm may be obtained by correcting the measurement result of the resin composition film having a thickness of 15 μm or more and 25 μm or less to a thickness of 20 μm. That is, when the transmittance at a thickness of 20 μm is “T ₂₀ ”%, the transmittance at the measured film thickness is “T _t ”%, and the measured film thickness is “t” um, the value corrected by the following formula (1) is can be calculated. The method for measuring the film thickness is JIS K7130 (1999) Plastics - film and sheet - thickness measurement method A method by mechanical scanning in thickness measurement method (average film thickness). Say things.

Formula (1) T ₂₀ =(T _t /100) ^(20/t) ×100
Next, a method for producing a resin composition film using the resin composition of the present invention will be described. The resin composition film of the present invention is obtained by applying a solution (varnish) of the resin composition onto a support and then drying it if necessary. A resin composition varnish is obtained by adding an organic solvent to a resin composition. Any organic solvent that dissolves the resin composition may be used as the organic solvent.

Specific examples of organic solvents include ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether, Acetates such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate and butyl lactate , acetone, methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, ketones such as 2-heptanone, butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, alcohols such as diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, and others, N-methyl-2-pyrrolidone, N-cyclohexyl- 2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone and the like.

The resin composition varnish may be filtered using filter paper or a filter. The filtration method is not particularly limited, but a method of filtering by pressure filtration using a filter having a retained particle size of 0.4 μm to 10 μm is preferred.

The resin composition film of the present invention is used by being formed on a support. The support is not particularly limited, but various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. The bonding surface between the support and the resin composition film may be surface-treated with silicone, a silane coupling agent, an aluminum chelating agent, polyurea, or the like in order to improve adhesion and releasability. The thickness of the support is not particularly limited, but from the viewpoint of workability, it is preferably in the range of 10 to 100 μm.

The resin composition film of the present invention may have a protective film on the film in order to protect the surface. Thereby, the surface of the resin composition film can be protected from contaminants such as dirt and dust in the atmosphere. Examples of protective films include polyolefin films and polyester films. The protective film preferably has a small adhesive force to the resin composition film.

Methods for applying the resin composition varnish to the support include spin coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, and comma roll coater. , gravure coater, screen coater, slit die coater and the like. In addition, although the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., it is generally preferable that the film thickness after drying is 0.5 μm or more and 100 μm or less.

Ovens, hot plates, infrared rays, etc. can be used for drying. The drying temperature and drying time may be within a range in which the organic solvent can be volatilized, and it is preferable to appropriately set a range such that the resin composition film is in an uncured or semi-cured state. Specifically, it is preferable to carry out at a temperature in the range of 40° C. to 120° C. for 1 minute to several tens of minutes. Further, these temperatures may be combined and the temperature may be raised stepwise, for example, heat treatment may be performed at 70° C., 80° C., and 90° C. for 1 minute each.

Next, a method for patterning the varnish of the resin composition or the resin composition film of the present invention and a method for thermocompression bonding to other members will be described with examples.

First, a method for forming a resin composition film on a substrate using the resin composition or resin composition film of the present invention will be described.

When using a resin composition varnish, the varnish is first applied to the substrate. Examples of coating methods include spin coating using a spinner, spray coating, roll coating, and screen printing. The coating film thickness varies depending on the coating method, the solid content concentration and viscosity of the resin composition, etc., but it is usually preferable to apply the coating so that the film thickness after drying is 0.5 μm or more and 100 μm or less. Next, the substrate coated with the resin composition varnish is dried to obtain a resin composition film. Ovens, hot plates, infrared rays, etc. can be used for drying. The drying temperature and drying time may be within a range in which the organic solvent can be volatilized, and it is preferable to appropriately set a range such that the resin composition film is in an uncured or semi-cured state. Specifically, it is preferable to carry out at a temperature in the range of 50 to 150° C. for 1 minute to several hours.

On the other hand, when a resin composition film is used, if it has a protective film, it is peeled off, and the resin composition film and the substrate are opposed to each other and bonded together by thermocompression to obtain a resin composition coating. Thermocompression bonding can be performed by heat press treatment, heat lamination treatment, heat vacuum lamination treatment, or the like. The bonding temperature is preferably 40° C. or higher from the viewpoint of adhesion to the substrate and embedding. In addition, the bonding temperature is preferably 150° C. or less in order to prevent the resin composition film from hardening during bonding and the resolution of pattern formation in the exposure and development steps from deteriorating.

In any case, the substrates to be used include silicon wafers, ceramics, gallium arsenide, organic circuit substrates, inorganic circuit substrates, and circuit-constituting materials arranged on these substrates. It is not limited to these. Examples of organic circuit boards include glass-based copper-clad laminates such as glass cloth and epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven fabrics and epoxy copper-clad laminates, polyetherimide resin substrates, and polyetherimide resin substrates. Examples include heat-resistant/thermoplastic substrates such as etherketone resin substrates and polysulfone resin substrates, and flexible substrates such as polyester copper-clad film substrates and polyimide copper-clad film substrates. Examples of inorganic circuit substrates include ceramic substrates such as alumina substrates, aluminum nitride substrates and silicon carbide substrates, and metal substrates such as aluminum base substrates and iron base substrates. Examples of circuit constituent materials include conductors containing metals such as silver, gold, and copper; resistors containing inorganic oxides; low dielectric materials containing glass materials and/or resins; Examples include high dielectric materials containing dielectric inorganic particles and the like, and insulators containing glass-based materials and the like.

Next, the resin composition film formed by the above method is exposed to actinic rays through a mask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc. In the present invention, it is preferable to use i-ray (365 nm), h-ray (405 nm) and g-ray (436 nm) of a mercury lamp. . In the resin composition film, when the support is made of a material transparent to these light rays, the exposure may be performed without peeling the support from the resin composition film.

To form a pattern, remove the exposed area with a developer after exposure. As a developer, aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol , dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, and other alkaline compounds. In some cases, these alkaline aqueous solutions are added with a polar solvent such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be contained alone or in combination. good.

Development can be carried out by a method such as spraying the above developer onto the film surface, heaping the developer onto the film surface, immersing in the developer, or immersing and applying ultrasonic waves. Developing conditions such as the developing time and the temperature of the developer in the developing step may be any conditions as long as the exposed portion can be removed and the pattern can be formed.

It is preferable to rinse with water after development. Also here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing.

Baking may be performed before development if necessary. This may improve the resolution of the pattern after development and increase the allowable range of development conditions. The baking temperature is preferably in the range of 50 to 180°C, more preferably in the range of 60 to 120°C. The time is preferably 5 seconds to several hours.

After pattern formation, unreacted cationic polymerizable compounds and photocationic polymerization initiators remain in the resin composition film. For this reason, they may be thermally decomposed to generate gas during thermocompression bonding or curing. In order to avoid this, it is preferable to irradiate the entire surface of the resin composition film after pattern formation with the above-described exposure light to generate acid from the photocationic polymerization initiator. By doing so, the reaction of the unreacted cationic polymerizable compound proceeds during thermocompression bonding or curing, and generation of gas due to thermal decomposition can be suppressed.

After development, a temperature of 150°C to 500°C is applied to advance the thermal cross-linking reaction. Crosslinking can improve heat resistance and chemical resistance. As a method for this heat treatment, a method of selecting a temperature and increasing the temperature stepwise, or a method of selecting a certain temperature range and continuously increasing the temperature for 5 minutes to 5 hours can be selected. As an example of the former, there is a method of heat-treating at 130° C. and 200° C. for 30 minutes each. An example of the latter is a method of linearly raising the temperature from room temperature to 400° C. over 2 hours.

The cured film of the present invention is a cured film obtained by curing the resin composition coating of the resin composition of the present invention or the resin composition film of the present invention. The cured film of the present invention can be used for electronic parts such as semiconductor devices. That is, the electronic component of the present invention includes the cured film of the present invention.

A semiconductor device, which is one of electronic components, refers to all devices that can function by using the characteristics of semiconductor elements. An electro-optical device in which a semiconductor element is connected to a substrate, a semiconductor circuit board, a stack of a plurality of semiconductor elements, and an electronic device including these are all included in the semiconductor device. Semiconductor devices also include electronic parts such as multilayer wiring boards for connecting semiconductor elements. Specifically, semiconductor passivation films, surface protective films of semiconductor elements, interlayer insulating films between semiconductor elements and wiring, interlayer insulating films between a plurality of semiconductor elements, and interlayer insulation between wiring layers in multi-layer wiring for high-density mounting. Although it is suitably used for applications such as insulating films and insulating layers of organic electroluminescence elements, it is not limited thereto and can be used for various applications.

The present invention will be specifically described below based on examples, but the present invention is not limited to these.

<Evaluation of transmittance at a thickness of 20 μm>
If there is a protective film of the resin composition film prepared in each example and comparative example, it is peeled off, and the peeled surface is placed on a 5 cm square borosilicate glass substrate with a vacuum diaphragm laminator (Co., Ltd.). Meiki Seisakusho, MVLP-500/600), the upper and lower heating plate temperature is 80 ° C., the vacuum time is 20 seconds, the vacuum press time is 30 seconds, and the lamination pressure is 0.5 MPa. A 20 μm thick resin composition film was formed. Then, if there was a support film, after peeling it off, the transmittance of the resin composition film at 365 nm was measured with an ultraviolet-visible spectrophotometer.

<Evaluation of Transmittance in Resin Composition C Coating with Thickness of 20 μm Formed Using Resin Composition Excluding Component (C)>
Resin composition C having a thickness of 20 μm was prepared in the same manner as in the evaluation of the transmittance of the resin composition coating having a thickness of 20 μm, using the resin composition C coating prepared in each example and comparative example. The transmittance in the coating was measured.

<Evaluation of pattern workability>
If there is a protective film of the resin composition film produced in each example and comparative example, it is peeled off, and the peeled surface is placed on a 5 cm square alumina substrate with a vacuum diaphragm laminator (Meiki Seisakusho Co., Ltd.). (manufactured by MVLP-500/600), laminated under the conditions of upper and lower heating plate temperatures of 80 ° C, vacuum drawing time of 20 seconds, vacuum press time of 30 seconds, and lamination pressure of 0.5 MPa, and coated with a resin composition on an alumina substrate. formed. Then, if there is a support film, after peeling it off, patterns with via sizes of 30 μmφ, 20 μmφ, and 10 μmφ, and patterns with line/space widths of 60 μm/30 μm, 40 μm/20 μm, and 20 μm/10 μm are formed in the exposure device. A mask was set, and an exposure amount of 200 mJ/cm ² , 300 mJ/cm ² , and 400 mJ/cm was applied using an ultra-high pressure mercury lamp equipped with an i-line bandpass filter under the condition of an exposure gap of 100 μm between the mask and the resin composition film. ² , exposure was performed at 500 mJ/cm ² (i-line conversion). After exposure, post-exposure heating was performed on a hot plate at 90° C. for 10 minutes. After that, in dip development, remove the unexposed areas using propylene glycol monomethyl ether acetate (PGMEA) or a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), then isopropanol (IPA) or water. was rinsed. The development time was twice the time required for the unexposed areas to completely dissolve. The pattern thus obtained was observed with an optical microscope, and the minimum size when there was no abnormality such as clogging in the pattern was used as the evaluation of resolution. In addition, 0 (defective) was given when the pattern was not resolved. Table 1 shows the developer and rinse solution used in each example.

Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound (a) 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) (18.3 g, 0.05 mol) was added to 100 mL of acetone. , propylene oxide (17.4 g, 0.3 mol) and cooled to -15°C. A solution of 3-nitrobenzoyl chloride (20.4 g, 0.11 mol) dissolved in 100 mL of acetone was added dropwise thereto. After completion of the dropwise addition, the mixture was allowed to react at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was separated by filtration and vacuum dried at 50°C.

30 g of the resulting white solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon, and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated after confirming that the balloon did not deflate any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration and concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound (a) represented by the following formula. The obtained individual was used for the reaction as it was.

Synthesis Example 2 Synthesis of polyimide (D-1) Under a dry nitrogen stream, BAHF (29.30 g, 0.08 mol) was added to 80 g of γ-butyrolactone (hereinafter referred to as GBL), and stirred and dissolved at 120°C. Next, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride (hereinafter referred to as TDA-100) (30 0.03 g, 0.1 mol) was added with 20 g of GBL and stirred at 120° C. for 1 hour and then at 200° C. for 4 hours to obtain a reaction solution. Next, the reaction solution was poured into 3 L of water to collect a white precipitate. This precipitate was collected by filtration, washed with water three times, and dried in a vacuum dryer at 80° C. for 5 hours.

Synthesis Example 3 Synthesis of polyamideimide (D-2) Hydroxyl group-containing diamine compound (a) (15.72 g, 0.04 mol) and BAHF (14.65 g, 0.04 mol) were added to 100 g of GBL under a dry nitrogen stream. added and stirred at 120°C. Next, TDA-100 (30.03 g, 0.1 mol) was added together with 20 g of GBL and stirred at 120° C. for 1 hour and then at 200° C. for 4 hours to obtain a reaction solution. Next, the reaction solution was poured into 3 L of water to collect a white precipitate. This precipitate was collected by filtration, washed with water three times, and dried in a vacuum dryer at 80° C. for 5 hours.

Example 1
(A) component TEPIC-VL (trade name, manufactured by Nissan Chemical Industries, Ltd.) 10 g, (B) component CPI-310FG (trade name, San-Apro Co., Ltd.) 0.6 g, (C) component UVS- 1331 (trade name, manufactured by Kawasaki Kasei Co., Ltd.) 0.1 g, 1007 (trade name, manufactured by Mitsubishi Chemical Corporation) as a BisA type epoxy resin, 10 g, KBM-403 as a silane compound (trade name, Shin-Etsu Chemical Co., Ltd. ( Co., Ltd.) was dissolved in GBL. The amount of the solvent added was adjusted so that the solid content concentration was 60% by weight, with the additives other than the solvent being the solid content. Thereafter, pressure filtration was performed using a filter having a retained particle size of 1 μm to obtain a resin composition varnish.

The resulting resin composition varnish was applied on a 50 μm thick PET film using a comma roll coater, dried at 120° C. for 8 minutes, and then laminated with a 30 μm thick PP film as a protective film. to obtain a resin composition film. The thickness of the resin composition film was adjusted to 20 μm. Using the obtained resin composition film, the transmittance and pattern workability were evaluated as described above.

Further, 10 g of TEPIC-VL as component (A), 0.6 g of CPI-310FG as component (B), 10 g of 1007 as BisA type epoxy, and 0.8 g of KBM-403 as silane compound were used in the same manner as above. A resin composition film was prepared in 1, and the transmittance of the resin composition film excluding the component (C) was evaluated. Table 1 shows the results.

Examples 2-11
A resin composition film was prepared in the same manner as in Example 1 except that the components (A) to (C) and other components were changed to compounds having the following structures and the mixing ratios thereof were changed as shown in Table 1. were produced, and the transmittance and pattern workability were evaluated as described above. Table 1 shows the results.

Comparative Examples 1-2
A resin composition film was prepared in the same manner as in Example 1 except that the components (A) to (C) and other components were changed to compounds having the following structures and the mixing ratios thereof were changed as shown in Table 1. were produced, and the transmittance and pattern workability were evaluated as described above. Table 1 shows the results.

In the table, "transmittance (%)" means the transmittance of a resin composition film having a thickness of 20 µm formed from the resin compositions of Examples and Comparative Examples.

In the table, "Transmittance (%) when component (C) is removed" is a resin composition C film having a thickness of 20 μm formed from the resin compositions of Examples and Comparative Examples using Resin Composition C. means the transmittance of
The structures of the compounds used in each Synthesis Example, Examples and Comparative Examples are shown below.

(A) Cationic polymerizable compound TEPIC-VL (manufactured by Nissan Chemical Industries, Ltd.), liquid at room temperature, epoxy equivalent = 128 g/eq.
PETG (manufactured by Showa Denko KK), liquid at room temperature, epoxy equivalent = 90 g/eq.
BATG (manufactured by Showa Denko KK), liquid at room temperature, epoxy equivalent = 113 g/eq. .

(B) cationic polymerization initiator CPI-210S (onium salt-based photoacid generator, manufactured by San-Apro Co., Ltd.)
CPI-310FG (an onium salt-based photoacid generator, manufactured by San-Apro Co., Ltd.).

(C) Sensitizer UVS-1331 (anthracene compound, manufactured by Kawasaki Chemical Industry Co., Ltd.).

(D) Polymer compounds D-1: Polyimide having a carboxylic acid residue at the molecular chain end D-2: Polyamideimide having a carboxylic acid residue at the molecular chain end.

Polymer compound other than (D) 1007 (BisA type phenoxy resin, manufactured by Mitsubishi Chemical Corporation)
Silane compound KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.).

Claims (15)

1. A resin composition containing (A) a cationically polymerizable compound and (B) a photocationic polymerization initiator, and further containing (C) a sensitizer.
2. The resin composition according to claim 1, wherein the total amount of the sensitizer (C) is 0.1% by mass or more and 5.0% by mass or less when the entire resin composition is 100% by mass.
3. The transmittance of a resin composition film having a thickness of 20 μm formed from the resin composition is 20% or more and 65% or less,
   2. The transmittance of the resin composition C film having a thickness of 20 μm formed using the resin composition C obtained by removing the (C) sensitizer from the resin composition is 70% or more and 100% or less. 2. The resin composition according to 2.
4. Claims 1 to 3, further comprising (D) a polymer compound, wherein the (D) polymer compound is at least one compound selected from the group consisting of polyamide, polyimide, polyamideimide, and polybenzoxazole. The resin composition according to any one of.
5. The resin composition according to claim 4, wherein the molecular chain end of the (D) polymer compound has a structure derived from a carboxylic acid residue.
6. The resin composition according to claim 4 or 5, wherein the (A) cationically polymerizable compound is 30 parts by mass or more and 200 parts by mass or less when the (D) polymer compound is 100 parts by mass.
7. The resin composition according to any one of claims 1 to 6, wherein the (C) sensitizer is an anthracene compound.
8. The above-mentioned (D) polymer compound is at least one compound selected from the group consisting of polyamide, polyimide, and polyamideimide, and further has a structure derived from an alicyclic tetracarboxylic dianhydride. The resin composition according to any one of 4 to 7.
9. The resin composition according to any one of claims 1 to 8, which is a negative photosensitive resin composition.
10. The resin composition according to any one of claims 1 to 9, which is used for pattern processing on the surface of a ceramic substrate.
11. A resin composition film formed from the resin composition according to any one of claims 1 to 10.
12. The resin composition film according to claim 11, which has a transmittance of 20% or more and 65% or less.
13. A resin composition film comprising the resin composition coating according to claim 11 or 12 and a support.
14. A cured film obtained by curing the resin composition according to any one of claims 1 to 10 or the resin composition coating according to claim 11 or 12.
15. An electronic component comprising the cured film according to claim 14.