TW202332712A - 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 compositions, resin composition coatings, resin composition films, cured films, and electronic parts

The present invention relates to a resin composition, a resin composition film, a resin composition film, a cured film, and electronic parts. More specifically, the present invention relates to a resin composition suitable for use in surface protection films, interlayer insulating films, structures of microelectromechanical systems (MEMS), etc. of semiconductor elements or inductor devices.

In the past, polyimide-based materials or polybenzoxazole-based materials that are excellent in heat resistance, electrical insulation, and mechanical properties have been widely used for surface protection films or interlayer insulating films of semiconductor devices. With recent demands 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, in order to adapt to various packaging structures of semiconductor devices or MEMS in recent years, photosensitive materials are required to be processed with a high aspect ratio. In order to meet such demands, a chemically amplified photocationic polymerization-based photosensitive material has been disclosed (for example, Patent Document 1). In addition, a photocationic polymerization system material is disclosed, which is intended to improve mechanical properties or thermal properties by including an epoxy resin with a specific structure in a chemically amplified photocationic polymerization system (for example, Patent Document 2). [Prior art documents] [Patent Document]

[Patent Document 1] International Publication No. 2008/007764 [Patent Document 2] Japanese Patent Application Publication No. 2019-38964

[Problem to be solved by the invention]

However, in the photocationic polymerization-based material as described above, when pattern processing is performed on a substrate with a rough surface such as ceramics, the irradiation light transmitted through the interior of the resin composition during exposure is diffusely reflected on the substrate surface, resulting in unexposed surfaces. Parts also undergo photocationic polymerization, making it difficult to form fine patterns.

In view of the above situation, the author and others conducted in-depth research and found that by including a sensitizer in a photocationic polymerization-based material, fine pattern processing can be performed even on a substrate with a rough surface such as ceramics. [Means to solve the problem]

The present invention to solve the above-mentioned problems is as follows.

A resin composition contains: (A) a cationic polymerizable compound, and (B) a photocationic polymerization initiator, and the resin composition is characterized by further containing (C) a sensitizer. [Effects of the invention]

The resin composition of the present invention provides a resin composition, a resin composition film, a resin composition film, a cured film, and a resin composition having fine pattern processability under low-temperature curing conditions even on a substrate with a rough surface such as ceramics. and electronic parts.

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

The resin composition of the present invention is preferably a negative-type photosensitizer in which (B) the photocationic polymerization starting material generates an acid by light irradiation, and (A) the cationically polymerizable compound undergoes a polymerization reaction and becomes insoluble in the developer. A negative photosensitive resin composition.

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

(A) Examples of cationic polymerizable compounds include: cyclic ether compounds (epoxy compounds, oxetane compounds, etc.), ethylenically unsaturated compounds (vinyl ethers, styrenes, etc.), bicyclic orthoesters, spiro esters, etc. Cyclic orthocarbonates and spirocyclic orthoesters, etc.

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 monovalent or polyvalent phenols (compounds of phenol, bisphenol A, phenol novolac, and alkylene oxide adducts of these) having at least one aromatic ring. wait.

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.).

Examples of aliphatic epoxy compounds include polyglycidyl ethers of aliphatic polyols or alkylene oxide adducts (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Glyceryl ether, etc.), polyglycidyl ethers of aliphatic polybasic acids (tetrahydrophthalic acid diglycidyl ester, etc.), epoxides of long-chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.) ).

As the oxetane compound, well-known compounds can be used, and examples thereof include: 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl(3-ethyl-3-oxetane), etc. Cyclobutylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, 1, 4-bi[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, oxetanylsesquioxetane, phenol novolak oxetane, etc.

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

Examples of aliphatic monovinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, and the like.

Examples of aromatic monovinyl ethers include 2-phenoxyethyl vinyl ether, phenyl vinyl ether, p-methoxyphenyl vinyl ether, and the like.

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

Examples of styrenes include styrene, a-methylbenzene, p-methoxystyrene, p-tert-butoxystyrene, and the like.

Examples of the cationically polymerizable nitrogen-containing monomer include N-vinylcarbazole, N-vinylpyrrolidone, and the like.

Examples of bicyclic orthoesters include: 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane and 1-ethyl-4-hydroxymethyl-2, 6,7-trioxaheterocycle-[2.2.2]octane, etc.

Examples of spirocyclic orthocarbonates include: 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro Cycl[5.5]undecane, etc.

Examples of spirocyclic orthoesters include: 1,4,6-trioxaspiro[4.4]nonane, 2-methyl-1,4,6-trioxaspiro[4.4]nonane, and 1 ,4,6-trioxaspiro[4.5]decane, etc.

Among these cationically polymerizable compounds, epoxy compounds, oxetane compounds and vinyl ethers are preferred, epoxy compounds and oxetane compounds are further preferred, and epoxy compounds are particularly preferred. Among them, a polyfunctional epoxy compound that is liquid at normal temperature (20° C.) is preferred, and the epoxy equivalent of the polyfunctional epoxy compound is preferably 80 g/eq. or more and 160 g/eq. or less. By making the polyfunctional epoxy compound liquid at normal temperature, as will be described later, the resin composition of the present invention preferably contains more of the (D) polymer compound, but due to the compatibility with the (D) polymer compound It has improved properties and can obtain fine pattern processability, so it is better. On the other hand, it is preferable that the epoxy equivalent of the polyfunctional epoxy compound is 80 g/eq. or more and 160 g/eq. or less because the heat resistance and chemical resistance of the cured film are improved.

Examples of polyfunctional epoxy compounds that are liquid at normal temperature and have an epoxy equivalent of 80 g/eq. or more and 160 g/eq. or less include TEPIC-VL (trade name, Nissan Chemical Co., Ltd.) Manufactured), bisphenol A type epoxy compound, bisphenol F type epoxy compound, SHOFREE-BATG, SHOFREE-PETG (trade name, all manufactured by Showa Denko Co., Ltd.), etc. .

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

In order to exhibit sufficient cationic curability and improve pattern processability, when the (D) polymer compound is 100 parts by mass, the (A) cationically polymerizable compound is preferably 30 parts by mass or more. , more preferably 50 parts by mass or more. On the other hand, when it is formed into a film form, that is, when the resin composition film is coated, the surface of the resin composition film is non-sticky and easy to handle, or the strong elongation of the cured film is improved. When D) the polymer compound is 100 parts by mass, the (A) cationically polymerizable compound is preferably 200 parts by mass or less, more preferably 150 parts by mass or less.

(B) Photocationic polymerization initiator The resin composition of the present invention contains (B) photocationic polymerization initiator.

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

Specific examples of the (B) photocationic polymerization initiator include aromatic iodonium salts, aromatic erium salts, aromatic boric acid salts, aromatic gallic acid salts, and the like. Specific examples of aromatic iodonium salts include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, Bis(4-nonylphenyl)iodonium hexafluorophosphate, etc. These (B) photocationic polymerization initiators may be used alone, or two or more types may be used in combination.

When the (A) cationic polymerizable compound is 100 parts by mass, the content of the (B) photocationic polymerization initiator is preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, and further Preferably, it is 0.7 parts by mass or more. Thereby, the cationic polymerizable compound exhibits sufficient hardening property, and pattern processability can be improved. On the other hand, from the viewpoint of improving the storage stability of the resin composition before curing, it is preferably 10 parts by weight or less, more preferably 8 parts by weight or less.

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

(C) The sensitizer is a compound that can absorb light and provide the absorbed light energy to (B) the photocationic polymerization initiator to generate acid to produce cationic polymerization. The sensitizer absorbs light at the irradiation wavelength during pattern processing, thereby reducing the transmittance of the resin composition film formed of 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.

The sensitizer is not particularly limited, but the (C) sensitizer is preferably an anthracene compound, and more preferably an anthracene compound (9,10-dialkoxy group) having an alkoxy group at the 9- and 10-positions. -Anthracene derivatives). Examples of the alkoxy group include C1 to C4 alkoxy groups such as methoxy group, ethoxy group, and propoxy group. The 9,10-dialkoxy-anthracene derivative may further have a substituent. Examples of substituents in 9,10-dialkoxy-anthracene derivatives include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and C1 to C4 alkanes such as methyl, ethyl, and propyl groups. group or sulfonic acid alkyl ester group, carboxylic acid alkyl ester group, etc. Examples of the alkyl group in the sulfonate alkyl ester group or carboxylic acid alkyl ester include C1 to C4 alkyl groups such as methyl, ethyl, and propyl. The substitution position of these substituents is preferably the 2-position.

In the resin composition of the present invention, when the entire resin composition is taken as 100 mass %, the total amount of the (C) sensitizer is preferably 0.1 mass % or more and 5.0 mass % or less, and the (C) ) The content of the sensitizer is not particularly limited, but is preferably 0.05 mass% or more, more preferably 0.1 mass% or more. This can reduce the transmittance of the resin composition film, suppress light reflection from the substrate surface even on a substrate with a rough surface such as ceramics, and facilitate the processing of fine patterns. On the other hand, in order to suppress the reduction in the mechanical properties or thermal properties of the cured film of the resin composition film formed of the resin composition, when the mass of the entire resin composition is 100 mass %, ( C) The content of the sensitizer is preferably 10 mass% or less, and more preferably 5 mass% or less.

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

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

The resin composition of the present invention preferably has a structure in which (D) the end of the molecular chain of the polymer compound is derived from a carboxylic acid residue. As long as the resin composition of the present invention contains the polymer compound (D) in which the end of the molecular chain has a structure derived from a carboxylic acid residue, it may also contain a polymer compound in which the end of the molecular chain does not have a structure derived from a carboxylic acid residue. In the resin composition of the present invention, when it contains a polymer compound whose molecular chain terminal is not derived from a structure of a carboxylic acid residue, the smaller the content, the better. Specifically, it is preferable that the molecular chain terminal becomes the source of the polymer compound. A total of 100 parts by mass of the (D) polymer compound having a structure derived from a carboxylic acid residue, and the content of the (D) polymer compound having a structure not derived from a carboxylic acid residue at the end of the molecular chain is preferably 0 parts by mass or more and 10 parts by mass parts by mass or less, more preferably 0 parts by mass or more and 5 parts by mass or less, particularly preferably 0 parts by mass or more and 2 parts by mass or less.

The content of the (D) polymer compound having a structure derived from a carboxylic acid residue at the end of the molecular chain is not particularly limited, but it is preferably 20 mass% or more and 95 mass% or less in 100 mass% of the resin composition, and more preferably Preferably, it contains 30 mass % or more and 85 mass % or less, and especially preferably, it contains 30 mass % or more and 70 mass % or less. By including 20 mass % or more of the (D) polymer compound in which the end of the molecular chain has a structure derived from a carboxylic acid residue in the resin composition, the film strength of the cured film is improved. On the other hand, when the content of the (D) polymer compound in which the end of the molecular chain has a structure derived from a carboxylic acid residue is 95% by mass or less in the resin composition, the cationic polymerization reaction proceeds easily, and the cured film Improved chemical resistance.

(D) Since the molecular chain terminal of the polymer compound has a structure derived from the carboxylic acid residue, the molecular chain terminal can be formed into a molecular structure that does not have an amine terminal structure that can serve as a functional group that inhibits cationic polymerization. As a result, even if Polyamide, polyimide, and polyamideimide are preferred in that they can exhibit sufficient cationic polymerizability.

Here, (D) the structure derived from the carboxylic acid residue at the molecular chain end of the polymer compound means a structure derived from the carboxylic acid residue that can constitute polyamide, polyamideimine or polyamideimide. Organic groups, and structures derived from monocarboxylic acid, dicarboxylic acid, monochloride compound, dichloride compound, tetracarboxylic acid or acid anhydride, acid dianhydride, etc. Among the above, it is particularly preferable that (D) the structure derived from the carboxylic acid residue at the molecular chain terminal of the polymer compound is a structure derived from tetracarboxylic dianhydride. When the end of the molecular chain has a structure derived from tetracarboxylic dianhydride, it is preferable because the storage stability of the resin composition before thermosetting is improved. On the other hand, as a cured film, the terminal carboxylic acid anhydride group becomes a reactive functional group, which is preferable in terms of improved heat resistance and chemical resistance after thermal curing.

(D) The polymer compound is preferably alkali-soluble. If it is alkali-soluble, it is preferable because an alkali aqueous solution can be used for development during pattern processing without using an organic solvent that is a major cause of environmental load. The alkali solubility mentioned here means that 100 g of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide can dissolve 0.1 g or more at 25°C. In order to express alkali solubility, the (D) polymer compound preferably has an alkali-soluble functional group. The alkali-soluble functional group is an acidic functional group, and specific examples thereof 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 problems such as storage stability of the resin composition and corrosion of copper wiring as a conductor. (D) The polymer compound is preferably a compound having a phenolic hydroxyl group in the molecular chain.

(D) The structure (organic group) whose molecular chain terminal of the polymer compound is derived from a carboxylic acid residue includes aromatic dicarboxylic acid, aromatic acid dianhydride, alicyclic dicarboxylic acid, and alicyclic acid dianhydride. Anhydrides, aliphatic dicarboxylic acids, aliphatic acid dianhydrides, etc., but are not limited to these. In addition, these are used individually or in combination of 2 or more types.

Among these, organic resins derived from alicyclic carboxylic acid residues are preferred from the viewpoint that a transparent resin can be designed for the wavelength used for pattern formation, and as a result, a thick film can exhibit fine pattern processability. base.

In the present invention, the (D) polymer compound is preferably the polyamide, the polyamide imine and the polyamide imine, and these preferably have a compound selected from the group consisting of the general formula (1 ) and a compound with at least one or more structures among the structures represented by general formula (2).

[Chemical 1]

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

Y ¹ and Y ² in the general formula (1) and general formula (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 alkali developer can be obtained. Therefore, high contrast between exposed and unexposed areas can be obtained, and a desired pattern can be formed.

Specific examples of the diamine having a phenolic hydroxyl group include bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)trine, bis( 3-Amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amine hydroxy-4-hydroxy)biphenyl, 2,2'-bis-trifluoromethyl-5,5'-dihydroxy-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxy) Phenyl) fluorene, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine and other aromatic diamines, or some of the hydrogen atoms of these aromatic rings or hydrocarbons are replaced with carbon numbers. Examples of compounds substituted by 1 to 10 alkyl groups, fluoroalkyl groups, halogen atoms, and the like, and diamines having the structures shown below, are not limited to these. Other copolymerized diamines can be used directly or as corresponding diisocyanate compounds or trimethylsilylated diamines. In addition, these two or more diamine components may be used in combination.

[Chemicalization 2]

[Chemical 3]

Y ¹ and Y ² in the general formula (1) and the general formula (2) may contain aromatic diamine residues other than those mentioned above. By copolymerizing these, heat resistance can be improved. Specific examples of the aromatic diamine residue include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl ether. methylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diamino diphenyl sulfide Diphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, petroleum ether (benzine), m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)terine, bis(3-aminophenoxyphenyl)terine, bis(4-amino) Phenoxy)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 and other aromatic diamines, Or a compound in which a part of the hydrogen atoms of the aromatic rings or hydrocarbons is substituted with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, etc., but is not limited to these. Other copolymerized diamines can be used directly or as corresponding diisocyanate compounds or trimethylsilylated diamines. In addition, these two or more diamine components may be used in combination.

In the general formula (1) or the general formula (2) of the present invention, X ¹ and X ² are independent, X ¹ and X ² are preferably carboxylic acid residues, and X ¹ is preferably divalent to 10 valent organic group, X ² is preferably a 4- to 10-valent organic group.

The carboxylic acid residue preferably has a structure derived from an alicyclic tetracarboxylic dianhydride. That is, (D) the polymer compound is at least one compound selected from the group consisting of polyamide, polyamide imine, and polyamide imine, and preferably has a compound derived from an alicyclic tetracarboxylic acid The structure of acid dianhydride. Since 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 becomes high, and processing of thick films of 20 μm or more becomes easy. Furthermore, although the reason is not yet certain, since the polymer compound (D) has a structure derived from an alicyclic tetracarboxylic dianhydride, it is more reactive in cationic polymerization than an aromatic acid dianhydride and hardens. It is preferable to improve the chemical resistance of the membrane.

Among alicyclic tetracarboxylic dianhydrides, an alicyclic tetracarboxylic dianhydride having a polycyclic structure is preferred from the viewpoint of improved chemical resistance and improved ion migration resistance when it is made into a cured product.

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

[Chemical 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 the general formula (4) , so that the resin skeleton has flexibility, so that as a resin composition before curing, it has high solubility in organic solvents, resin precipitation is unlikely to occur in the composition, and storage stability is excellent, so it is preferred.

Specific examples of the organic group derived from alicyclic tetracarboxylic dianhydride having a polycyclic structure include: 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4 -Tetralin-1,2-dicarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-4methyl-1,2,3,4-tetralin-1, 2-dicarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-7methyl-1,2,3,4-tetralin-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.

As the carboxylic acid residue, acid dianhydrides other than the alicyclic tetracarboxylic dianhydride having a polycyclic structure may be included. Specific examples 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'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride Carboxylic dianhydride, 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-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)teric dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6 -Naphthalene tetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorenic acid dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl} Fluorene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, Aromatic tetracarboxylic dianhydride such as 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 3,3',4,4'-diphenyltetracarboxylic 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 acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, etc., but are not limited to these. In addition, these are used individually or in combination of 2 or more types.

The molar ratio of the structure represented by the general formula (1) and the general formula (2) of the present invention can be calculated based on the molar ratio of the monomers used in the polymerization, or by using a nuclear magnetic resonance (NMR) device. Confirmation is carried out by detecting the peaks of the polyamide structure, the amide imine precursor structure, and the amide imine structure in the obtained resin, resin composition, and cured film.

(D) The polymer compound having a structure derived from a carboxylic acid residue at the end of the molecular chain. For example, in the case of a polyimide having a carboxylic acid residue at the end of the molecular chain, the diamine used for polymerization can be obtained by increasing the anhydride content. At this time, when the total amount of carboxylic acid residues of 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 polymerized so that the total amount of amine residues is 60 to 98 mol%, assuming that the total amount of carboxylic acid residues is 100 mol%. obtained compound. When the total amount of amine residues is 60 mol% or more, the weight average molecular weight easily reaches 1,000 or more, and the film-forming property is excellent when it is formed into a film. When the total amount is 98 mol% or less, the terminal becomes a polymer with amine residues. The content ratio of the compound becomes smaller, the cationic polymerization reaction proceeds easily, and the chemical resistance of the cured film improves.

As another method of obtaining the polymer compound (D) in which the terminal end of the molecular chain has a structure derived from a carboxylic acid residue, a specific compound among compounds generally used as an end sealant can be used. Specifically, acid anhydride, It is obtained from monocarboxylic acid, monochloride compound and monoactive ester compound.

By sealing the end of the molecular chain of the (D) polymer compound with an end sealant of carboxylic acid or acid anhydride having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group or an allyl group, it is possible to easily The dissolution rate of the above-mentioned (D) polymer compound in the alkali aqueous solution or the mechanical properties of the obtained cured film are adjusted to a preferred range. In addition, a variety of terminal sealants can also be reacted to introduce a variety of different terminal groups.

As for the acid anhydride, monocarboxylic acid, monochloride compound, and monoactive ester compound used as the terminal sealant, preferred ones are phthalic anhydride, maleic anhydride, cyclohexanedicarboxylic anhydride, cyclohexanedicarboxylic anhydride, and 3- Anhydrides such as hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene , 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid Monochloride compounds formed by chlorination of monocarboxylic acids and their carboxyl groups, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1 , Monochloride compounds formed by chlorination of only one carboxyl group of dicarboxylic acids such as 6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene. By combining the monochloride compound with Active ester compounds obtained by the reaction of N-hydroxybenzotriazole or imidazole, N-hydroxy-5-norbornene-2,3-dicarboxylimide, etc. Two or more of these may be used.

The polymer compound introduced with these terminal sealants becomes a (D) polymer compound in which the end of the molecular chain has a structure derived from a carboxylic acid residue. In addition, the terminal sealant that can be used to obtain the (D) polymer compound in which the terminal end of the molecular chain has a structure derived from a carboxylic acid residue can be easily detected by the following method. For example, the (D) polymer compound into which the terminal sealant is introduced is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component as constituent units, and then a gas chromatography (GC) or Nuclear Magnetic Resonance (NMR) can easily detect the end sealant used in the present invention. Instead of directly measuring the resin component into which the end sealant is introduced, it can be easily detected by using pyrolysis gas chromatograph (PGC) or infrared spectroscopy and 13C-NMR spectroscopy.

In the present invention, (D) the polymer compound is synthesized by, for example, the following method, but is not limited thereto. The polyimide structure is synthesized by a known method by replacing part of the diamine with a primary monoamine as a terminal sealant, or by replacing a tetracarboxylic dianhydride with a dicarboxylic anhydride as a terminal sealant. For example, the polyimide precursor is obtained by using the following methods: a method of reacting tetracarboxylic dianhydride, a diamine compound, and a monoamine at a low temperature; and a method of reacting a tetracarboxylic dianhydride, a dicarboxylic anhydride, and a diamine compound at a low temperature. Methods; methods of obtaining diester by tetracarboxylic dianhydride and alcohol, and then reacting in the presence of diamine, monoamine and condensing agent, etc. Then, the polyimide can be synthesized using a known imidization reaction method.

In the present invention, the polymer compound (D) is preferably polymerized by the above method, then added to a large amount of water or a mixed solution of methanol and water, and precipitated, followed by filtration, drying, and separation. The drying temperature is preferably 40°C to 100°C, more preferably 50°C to 80°C. By this operation, unreacted monomers or oligomer components such as dimers or trimers are removed, thereby improving the film properties after thermal curing.

The imidization rate of the present invention can be easily determined by, for example, the following method. First, the infrared absorption spectrum of the polymer was measured to confirm the presence of absorption peaks (around 1780 cm ^-1 and 1377 cm ^-1 ) of the amide imine structure due to polyamide imide. Next, the imidization rate of the polymer obtained by heat treatment at 350°C for 1 hour was taken as a sample of 100%, and the infrared absorption spectrum was measured, and the peak intensity of the resin before and after heat treatment at approximately 1377 cm ^-1 was measured. By comparison, the content of the acyl imine group in the resin before heat treatment was calculated, and the acyl imine ratio was determined. In order to suppress changes in the loop closure rate during thermal hardening and obtain a stress-lowering effect, the imidization rate is preferably 50% or more, and more preferably 80% or more.

The resin composition of the present invention may also contain a thermal crosslinking agent, preferably a compound having an alkoxymethyl group or a hydroxymethyl group.

Examples of those having an alkoxymethyl group or a hydroxymethyl group include: 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, DMOM-PC, DMOM-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 (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalak ( NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MW-100LM, NIKALAC MX-750LM (the above are trade names, Sanwa Co., Ltd. chemical manufacturing).

The resin composition of the present invention may further contain a silane compound. By containing a silane compound, the adhesion of the heat-resistant resin film is improved. Specific examples of the silane compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyl Triethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyl Trimethoxysilane, p-styrenetrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, etc.

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

The resin composition of the present invention has a moderate transmittance, thereby suppressing the reflected light that is diffusely reflected on the surface of the ceramic substrate. Therefore, it is preferably used for pattern processing on the surface of the ceramic substrate.

The resin composition of the present invention preferably has a transmittance of 20% or more and 65% or less of a resin composition film with a thickness of 20 μm formed from the resin composition, and the above-mentioned (C) sensitization is removed from the resin composition. The transmittance of the resin composition C film with a thickness of 20 μm formed by using the resin composition C of the agent is 70% or more and 100% or less.

If the transmittance of a 20 μm resin composition film formed using resin composition C is 70% or more and 100% or less, the irradiated light will reach deep parts even when pattern processing is performed using the resin composition of the present invention. Furthermore, since the transmittance of the 20 μm resin composition film formed of the resin composition of the present invention is 65% or less, when pattern processing is performed on a substrate with a rough surface such as ceramics, the penetration of the resin composition film can be suppressed, and the substrate can be The reflected light is diffusely reflected on the surface to obtain subtle patterns. On the other hand, by setting the transmittance to 20% or more, the irradiated light reaches the deep part, and even at the bottom of the resin composition film, the (C) sensitizer absorbs the light and provides the absorbed light energy to ( B) Photocationic polymerization initiator generates acid to perform cationic polymerization and can form fine isolated patterns without peeling off.

Resin composition C is a resin composition prepared simply by removing only the sensitizer (C). For example, in the case of the resin composition of the present invention containing (A) 50 parts by mass of a cationically 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 refers to a resin composition containing (A) 50 parts by mass of a cationically polymerizable compound and (B) 50 parts by mass of a photocationic polymerization initiator. For example, a composition containing 30 parts by mass of (A) a cationically polymerizable compound and (B) In the case of the resin composition of the present invention containing B) 30 parts by mass of photocationic polymerization initiator, 30 parts by mass of (C) sensitizer, 30 parts by mass of (D) polymer compound, and 30 parts by mass of other components, the resin Composition C refers to a resin composition containing (A) 30 parts by mass of a cationically polymerizable compound, (B) 30 parts by mass of a photocationic polymerization initiator, (D) 30 parts by mass of a polymer compound, and 30 parts by mass of other components.

The transmittance of a 20 μm-thick resin composition film formed from the resin composition of the present invention refers to the transmittance measured by forming a 20 μm-thick resin composition film using the resin composition of the present invention. Similarly, the transmittance of a film of the resin composition C having a thickness of 20 μm refers to the transmittance when the resin composition C is prepared and used to form a film of the resin composition C of 20 μm and measured.

The method for producing a 20 μm resin composition film formed from the resin composition of the present invention and the method for producing a 20 μm resin composition C film are as follows. That is, the resin composition or resin composition C of the present invention is coated on a polyethylene terephthalate (sometimes referred to as PET (Polyethylene Terephthalate, PET)) film with a thickness of 50 μm using a notch roller coater. After drying at 120°C for 8 minutes, a polypropylene (sometimes called PP (Polypropylene, PP)) film with a thickness of 30 μm is laminated as a protective film to obtain a resin composition having a resin composition film. material film.

The method for measuring the transmittance is as described in the resin composition film section described below.

The transmittance of a 20 μm resin composition film can be obtained by forming a resin composition film with a film thickness of 15 μm or more and 25 μm or less, and correcting any of the measurement results to a thickness of 20 μm. The details are as described in the method described in the resin composition coating section described below.

The shape of the resin composition of the present invention before curing is not limited, and examples thereof include varnish shape, film shape, and the like. Here, the resin composition of the present invention formed into a film is also called a resin composition film of the present invention. Furthermore, the resin composition film of the present invention has a film and a support in which the resin composition of the present invention is formed into a film-like form. That is, the resin composition film of the present invention has a resin composition formed from the resin composition of the present invention. The coating film and the resin composition film of the support body. 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 of the resin composition of the present invention on the support. When used in the form of a varnish, what was obtained by dissolving the components (A) to (C) and optionally added components in an organic solvent can be used. In addition, the resin composition film is obtained, for example, by applying the resin composition of the present invention on a support and then drying it if necessary.

The resin composition of the present invention formed into a film, that is, the resin composition film 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. Furthermore, the transmittance at a thickness of 20 μm is more preferably 20% or more and 65% or less. By setting the transmittance of the resin composition film to 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 is diffusely reflected on the substrate surface can be suppressed, thereby obtaining a fine pattern. . On the other hand, by setting the transmittance to 20% or more, the irradiated light reaches the deep part, and even at the bottom of the resin composition film, the (C) sensitizer absorbs the light and provides the absorbed light energy to ( B) Photocationic polymerization initiator generates acid to perform cationic polymerization and can form fine isolated patterns without peeling off.

The transmittance of the resin composition film and the transmittance at a thickness of 20 μm of the resin composition film are the transmittance at the wavelength of light used for pattern processing in the present invention. Preferably, the transmittance when measured at any one of the wavelengths of i-ray (365 nm), h-ray (405 nm), and g-ray (436 nm) of a mercury lamp, as long as it is 20% or more and 65% at at least one measurement wavelength. % or less is sufficient.

The transmittance when the thickness of the resin composition film is 20 μm can be obtained by correcting the measurement results of the resin composition film with a film 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 set to 『T ₂₀ 』%, the transmittance at the actual measured film thickness is set to 『T _t 』%, and the actual measured film thickness is set to 『t』μm. , the corrected value can be calculated using the following equation (1). In addition, the measurement method of film thickness refers to the thickness measurement method A using mechanical scanning based on Japanese Industrial Standards (JIS) K7130 (1999) Plastic Film and Sheet Thickness Measurement Method. film thickness (average film thickness).

Formula (1) T ₂₀ = (T _t /100) ^{( 20/t )} ×100 Next, a method of 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 to a support and then drying it as necessary. The resin composition varnish is obtained by adding an organic solvent to the resin composition. The organic solvent used here may be any solvent that dissolves the resin composition.

Specific examples of the organic solvent 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. Class, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methyl acetate Acetates such as oxybutyl ester, methyl lactate, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, 2-heptanone and other ketones, butanol, isobutanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl- Alcohols such as 3-methoxybutanol and diacetone alcohol, and aromatic hydrocarbons such as toluene and xylene. In addition, examples include: N-methyl-2-pyrrolidinone, N-cyclohexyl-2- Pyrrolidinone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, etc.

The resin composition varnish can also 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 that retains a particle size of 4 μm to 10 μm is preferred.

The resin composition film of the present invention is formed on a support and used. The support is not particularly limited, and various commonly commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. In order to improve the adhesion and peelability, surface treatment with silicone, silane coupling agent, aluminum chelating agent, polyurea, etc. can be performed on the joint surface between the support and the resin composition film. In addition, the thickness of the support is not particularly limited, but from the viewpoint of workability, the thickness is preferably in the range of 10 μm to 100 μm.

In order to protect the surface, the resin composition film of the present invention may also have a protective film on the film. Thereby, the surface of the resin composition film can be protected from contamination by dust or dust and other pollutants in the atmosphere. Examples of protective films include polyolefin films, polyester films, and the like. The protective film preferably has a small adhesive force with the resin composition film.

Examples of 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, and calender coating. Cloth coater, meniscus coater, rod coater, roller coater, notch wheel roller coater, gravure coater, screen coater, slot die coater and other methods. In addition, the coating film thickness varies depending on the coating method, the solid content concentration and viscosity of the composition, but it is generally preferable that the film thickness after drying is 0.5 μm or more and 100 μm or less.

Ovens, heating plates, infrared rays, etc. can be used for drying. The drying temperature and drying time only need to be within a range that can volatilize the organic solvent, and are preferably appropriately set in a range such that the resin composition film becomes an unhardened or semi-hardened state. Specifically, it is preferable to conduct it in the range of 40°C to 120°C for 1 minute to several tens of minutes. In addition, these temperatures may be combined and the temperature may be increased stepwise. For example, heat treatment may be performed at 70°C, 80°C, and 90°C for 1 minute each.

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

First, a method of 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, screen printing, and the like. In addition, the coating film thickness varies depending on the coating method, the solid content concentration and viscosity of the resin composition, etc., but it is generally preferable to apply 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. Drying can use oven, heating plate, infrared, etc. The drying temperature and drying time only need to be within a range that volatilizes the organic solvent, and are preferably appropriately set within a range in which the resin composition film becomes an unhardened or semi-hardened state. Specifically, it is preferable to perform it in the range of 50°C to 150°C for 1 minute to several hours.

On the other hand, when using a resin composition film, if it has a protective film, it is peeled off, the resin composition film and the substrate are made to face each other, and they are bonded by thermocompression bonding to obtain a resin composition film. Thermal compression bonding can be performed by heat pressing treatment, heat lamination treatment, heat vacuum lamination treatment, etc. In terms of adhesion and embedding properties to the substrate, the bonding temperature is preferably 40°C or higher. In addition, in order to prevent the resin composition film from hardening during lamination and deterioration of the resolution of pattern formation in the exposure and development steps, the lamination temperature is preferably 150° C. or lower.

In any case, examples of the substrate used include silicon wafers, ceramics, gallium arsenide, organic circuit substrates, inorganic circuit substrates, and those with circuit constituent materials arranged on these substrates. However, It is not limited to these. Examples of organic circuit boards include glass-based copper foil laminated boards such as glass cloth-epoxy copper foil laminated boards, composite copper foil laminated boards such as glass nonwoven fabric-epoxy copper foil laminated boards, polyetherimide Heat-resistant thermoplastic substrates such as resin substrates, polyetherketone resin substrates, and polyester resin substrates, and flexible substrates such as polyester copper foil film substrates and polyimide copper foil 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-based substrates and iron-based substrates. Examples of materials constituting the circuit include: conductors containing metals such as silver, gold, and copper, resistors containing inorganic oxides, etc., low dielectric materials containing glass-based materials and/or resins, etc., and conductors containing resins or high dielectric materials. High dielectric materials such as electric constant inorganic particles, insulators containing glass-based materials, etc.

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

In order to form a pattern, the exposed portion is removed with a developer after exposure. As the developer, preferred are: an aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylamine ethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, and diethylamine. , methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine Aqueous solutions of alkaline compounds such as amines. In addition, depending on the situation, these alkaline aqueous solutions may also contain N-methyl-2-pyrrolidinone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl Polar solvents such as tyrene, γ-butyrolactone, dimethylacrylamide, alcohols such as methanol, ethanol, isopropyl alcohol, esters such as ethyl lactate, propylene glycol monomethyl ether acetate, cyclopentanone, Ketones such as cyclohexanone, isobutyl ketone, methyl isobutyl ketone, etc., or a combination of a plurality of them are contained.

Development can be performed by spraying the developer onto the film surface, filling the film surface with the developer, immersing it in the developer, or immersing it and applying ultrasonic waves. The development conditions such as the development time and the temperature of the developer in the development step may be such that the exposed portion is removed and the pattern can be formed.

After development, it is preferable to use water for rinsing treatment. Here, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, etc. may also be added to the water to perform elution processing.

If necessary, baking processing can also be performed before development. This may improve the resolution of the pattern after development and increase the allowable range of development conditions. The baking treatment temperature is preferably in the range of 50°C to 180°C, particularly preferably in the range of 60°C to 120°C. The preferred time is 5 seconds to several hours.

After the pattern is formed, unreacted cationic polymerizable compound or photocationic polymerization initiator remains in the resin composition film. Therefore, they sometimes thermally decompose to produce gas when they are thermally crimped or hardened. In order to avoid this situation, it is preferable to irradiate the entire surface of the resin composition film after pattern formation with the exposure light to cause the photocationic polymerization initiator to generate acid. In this way, during thermocompression bonding or hardening, the reaction of the unreacted cationic polymerizable compound proceeds, and the generation of gas due to thermal decomposition can be suppressed.

After development, a temperature of 150°C to 500°C is applied to proceed the thermal cross-linking reaction. Through cross-linking, heat resistance and chemical resistance can be improved. The heat treatment method can be selected: a method of selecting a temperature and raising the temperature stepwise, or a method of selecting a certain temperature range, continuously raising the temperature, and performing it simultaneously for 5 minutes to 5 hours. An example of the former is a method of performing heat treatment at 130°C and 200°C for 30 minutes each. An example of the latter includes 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 of the present invention or the resin composition film of the resin composition film of the present invention. The cured film of the present invention can be used for electronic components such as semiconductor devices. That is, the electronic component of the present invention includes the cured film of the present invention.

A semiconductor device, one of electronic components, refers to an entire device that can function by utilizing the characteristics of semiconductor elements. An electro-optical device in which a semiconductor element is connected to a substrate, a laminated semiconductor circuit substrate, a device in which a plurality of semiconductor elements are formed, and an electronic device including these are all included in the semiconductor device. In addition, electronic components such as multilayer wiring boards for connecting semiconductor elements are also included in semiconductor devices. Specifically, it is suitable for use as a semiconductor passivation film, a surface protective film for semiconductor elements, an interlayer insulating film between a semiconductor element and wiring, an interlayer insulating film between a plurality of semiconductor elements, and between wiring layers of multilayer wiring for high-density mounting. It can be used as an interlayer insulating film, an insulating layer of an organic electroluminescent element, etc., but is not limited to these and can be used for various purposes. [Example]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

<Evaluation of transmittance at a thickness of 20 μm> When the resin composition film produced in each of the Examples and Comparative Examples has a protective film, it is peeled off, and a vacuum diaphragm laminator (MVLP-500/600, manufactured by Meiki Seisakusho Co., Ltd.) is used. Under the conditions of an upper and lower hot plate temperature of 80°C, a vacuum suction time of 20 seconds, a vacuum pressing time of 30 seconds, and a sticking pressure of 0.5 MPa, the peeling surface was laminated to a 5 cm square borosilicate glass substrate. A resin composition film with a thickness of 20 μm was formed on the substrate. Then, if there is a support film, it is peeled off, and then the transmittance of the resin composition film at 365 nm is measured using a UV-visible spectrophotometer.

<Evaluation of the transmittance of a 20 μm-thick resin composition C film formed using a resin composition excluding component (C)> Using the resin composition C film produced in each of the Examples and Comparative Examples, a resin composition with a thickness of 20 μm using the resin composition C was measured in the same manner as the evaluation of the transmittance of the resin composition film with a thickness of 20 μm. C film transmittance.

<Evaluation of pattern processability> When the resin composition film produced in each Example and Comparative Example had a protective film, it was peeled off and used a vacuum diaphragm laminator (manufactured by Meiki Seisakusho Co., Ltd.). MVLP-500/600), under the conditions of upper and lower hot plate temperature of 80°C, vacuum suction time of 20 seconds, vacuum pressing time of 30 seconds, and sticking pressure of 0.5 MPa, laminate the peeling surface to 5 cm square alumina On the substrate, a resin composition film is formed on the alumina substrate. Then, if there is a support film, after peeling off the support film, patterns with through hole sizes of 30 μmϕ, 20 μmϕ, and 10 μmϕ and a line/space width of 60 μm/30 are set on the exposure device. For masks with patterns of μm, 40 μm/20 μm, and 20 μm/10 μm, use an ultra-high-pressure mercury lamp equipped with an i-ray bandpass filter under the condition that the exposure gap between the mask and the resin composition film is 100 μm. Exposure was performed at exposure amounts of 200 mJ/cm ² , 300 mJ/cm ² , 400 mJ/cm ² , and 500 mJ/cm ² (i-ray conversion). After exposure, post-exposure heating was performed at 90° C. for 10 minutes using a hot plate. Then, by immersion development, the unexposed portion is removed using propylene glycol monomethyl ether acetate (PGMEA) or a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH), and then, isopropyl alcohol (IPA) or water is used. Rinse treatment. The development time was set to twice the time required for the unexposed portion to be completely dissolved. The pattern thus obtained is observed with an optical microscope, and the minimum size when there is no abnormality such as clogging in the pattern is evaluated as the resolution. In addition, if the pattern is not analyzed, it is set as 0 (defective). The developing solutions and eluents used in each example are shown in Table 1.

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

Put 30 g of the white solid obtained into a 300 mL stainless steel autoclave, disperse it in 250 mL of cellulose methyl, and add 2 g of 5% palladium-carbon. Hydrogen is introduced into it using a balloon, and the reduction reaction proceeds at room temperature. After about 2 hours, it was confirmed that the balloon was no longer shrinking and the reaction was completed. After the reaction is completed, the palladium compound as a catalyst is removed by filtration and concentrated using a rotary evaporator to obtain a hydroxyl-containing diamine compound (a) represented by the following formula. The solid obtained was used directly in the reaction.

[Chemistry 5]

Synthesis Example 2 Synthesis of Polyimide (D-1) Under a dry nitrogen flow, BAHF (29.30 g, 0.08 mol) was added to 80 g of gamma-butyrolactone (hereinafter referred to as GBL (GBL)), and the mixture was stirred and dissolved at 120°C. Next, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetralin-1,2-dicarboxylic dianhydride (hereinafter referred to as TDA-100) (30.03 g, 0.1 mol), stirred at 120°C for 1 hour, and then stirred at 200°C for 4 hours to obtain a reaction solution. Then, the reaction solution was put into 3 L of water to collect the white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 5 hours.

Synthesis Example 3 Synthesis of polyamide imine (D-2) Under a dry nitrogen flow, hydroxyl-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, and the mixture was stirred at 120°C. Next, TDA-100 (30.03 g, 0.1 mol) was added together with 20 g of GBL, and the mixture was stirred at 120°C for 1 hour, and then at 200°C for 4 hours to obtain a reaction solution. Then, the reaction solution was poured into 3 L of water to collect white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 5 hours.

Example 1 10 g of TEPIC-VL (trade name, manufactured by Nissan Chemical Co., Ltd.) as component (A), 0.6 g of CPI-310FG (trade name, manufactured by SANAPRO Co., Ltd.) as component (B), 0.1 g of UVS-1331 (trade name, manufactured by Kawasaki Chemical Industry Co., Ltd.) as component (C), 10 g of 1007 (trade name, manufactured by Mitsubishi Chemical Co., Ltd.) as BisA-type epoxy resin, and 10 g of silane compound KBM-403 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.8 g was dissolved in GBL. Additives other than the solvent were defined as solid content, and the added amount of the solvent was adjusted so that the solid content concentration became 60% by mass. Then, pressure filtration was performed using a filter retaining a particle diameter of 1 μm to obtain a resin composition varnish.

The obtained resin composition varnish was coated on a PET film with a thickness of 50 μm using a notched roller coater, and dried at 120° C. for 8 minutes. Then, a PP film with a thickness of 30 μm was laminated as a protective film. Thus, a resin composition film is obtained. The film thickness of the resin composition film was adjusted to 20 μm. Using the obtained resin composition film, transmittance and pattern processability were evaluated as described above.

Furthermore, 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 resin, and 0.8 g of KBM-403 as silane compound were used, together with the above A resin composition film was produced in the same manner, and the transmittance of the resin composition film after removing component (C) was evaluated. The results are shown in Table 1.

Example 2 to Example 11 A resin composition film was produced in the same manner as in Example 1, except that components (A) to (C) and other components were changed to compounds with the following structures and their mixing ratios were changed as described in Table 1. The transmittance and pattern processability were evaluated. The results are shown in Table 1.

Comparative Example 1 ~ Comparative Example 2 A resin composition film was produced in the same manner as in Example 1, except that components (A) to (C) and other components were changed to compounds with the following structures and their mixing ratios were changed as described in Table 1. The transmittance and pattern processability were evaluated. The results are shown in Table 1.

[Table 1-1] [Table 1-1] Resin composition (parts by mass) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 (A) Ingredients TEPIC-VL 100 100 PETG 50 50 50 50 50 50 BATG 50 50 50 50 50 50 (B) Ingredients CPI-210S 6 CPI-310FG 6 6 6 6 6 6 6 (C) Ingredients UVS-1331 1 1 1 0.5 1 0.2 0.3 0.5 (D) Ingredients Polyimide (D-1) 100 100 100 100 100 100 Polyamide imide (D-2) 100 Phenoxy resin 1007 100 Silane compound KBM-403 8 8 8 8 8 8 8 8 (C) Total content of ingredients (mass %) 0.5 0.5 0.5 0.2 0.5 0.09 0.1 0.2 Transmittance (%) 45 45 45 30 30 70 65 60 Pattern processability developer PGMEA TMAH TMAH TMAH TMAH TMAH TMAH TMAH eluent IPA water water water water water water water Through hole resolution (μm) 10 20 20 20 10 30 20 20 Line/space resolution (μm) 20/10 20/10 20/10 40/20 20/10 60/30 40/20 40/20 Transmittance (%) when component (C) is removed 75 75 75 50 98 75 75 75

[Table 1-2] [Table 1-2] Resin composition (parts by mass) Example 9 Example 10 Example 11 Comparative example 1 Comparative example 2 (A) Ingredients TEPIC-VL PETG 50 50 50 50 50 BATG 50 50 50 50 50 (B) Ingredients CPI-210S CPI-310FG 6 6 6 6 12 (C) Ingredients UVS-1331 2 3 4 (D) Ingredients Polyimide (D-1) 100 100 100 100 100 Polyamide imide (D-2) Phenoxy resin 1007 Silane compound KBM-403 8 8 8 8 8 (C) Total content of ingredients (mass %) 1.0 1.4 1.4 - - Transmittance (%) 30 15 10 75 60 Pattern processability developer TMAH TMAH TMAH TMAH TMAH eluent water water water water water Through hole resolution (μm) 10 20 30 0 0 Line/space resolution (μm) 20/10 40/20 60/30 0 0 Transmittance (%) when component (C) is removed 75 75 75 75 60

In the table, "transmittance (%)" refers to the transmittance of a resin composition film with a thickness of 20 μm formed from the resin composition of Examples or Comparative Examples.

In the table, "transmittance when component (C) is removed" refers to the transmission of a resin composition C film with a thickness of 20 μm formed using resin composition C obtained by removing component (C) from the resin composition of Examples or Comparative Examples. Rate. In addition, the structure of the compound used in each synthesis example, Example, and Comparative Example is as follows.

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

[Chemical 6]

(B) Photocationic polymerization initiator CPI-210S (onium salt photoacid generator, manufactured by SANAPRO (Co., Ltd.)) CPI-310FG (onium salt photoacid generator, manufactured by SANAPRO Co., Ltd.).

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

[Chemical 7]

(D) Polymer compounds D-1: Polyimide with carboxylic acid residue at the end of the molecular chain D-2: Polyamide imine with a carboxylic acid residue at the end of the molecular chain.

Polymer compounds other than (D) 1007 (BisA type phenoxy resin, manufactured by Mitsubishi Chemical Co., Ltd.) Silane compound KBM-303 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.).

without

without

Claims (15)

A resin composition contains: (A) a cationic polymerizable compound, and (B) a photocationic polymerization initiator, and the resin composition is characterized by further containing (C) a sensitizer. The resin composition according to claim 1, wherein the total amount of the (C) sensitizer is 0.1 mass % or more and 5.0 mass % or less when the entire resin composition is 100 mass %. The resin composition according to Claim 1 or Claim 2, wherein a resin composition film with a thickness of 20 μm formed from the resin composition has a transmittance of 20% or more and 65% or less, The transmittance of a 20 μm-thick resin composition C film formed using the resin composition C from which the sensitizer (C) is removed is 70% or more and 100% or less. The resin composition according to any one of claims 1 to 3, further containing (D) a polymer compound, wherein the (D) polymer compound is selected from the group consisting of polyamide, polyimide, and polyamide. At least one compound in the group consisting of amine imine and polybenzoxazole. The resin composition according to claim 4, wherein the molecular chain end of the (D) polymer compound is a structure derived from a carboxylic acid residue. The resin composition according to claim 4 or claim 5, wherein the (A) cationic polymerizable compound is 30 parts by mass or more when the (D) polymer compound is 100 parts by mass and Less than 200 parts by mass. The resin composition according to any one of claims 1 to 6, wherein the (C) sensitizer is an anthracene compound. The resin composition according to any one of claims 4 to 7, wherein the (D) polymer compound is selected from the group consisting of polyamide, polyimide, and polyamideimine. At least one compound in the group, and further having a structure derived from an alicyclic tetracarboxylic dianhydride. The resin composition according to any one of claims 1 to 8, which is a negative photosensitive resin composition. 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. A resin composition film formed from the resin composition according to any one of claims 1 to 10. The resin composition film according to claim 11, wherein the transmittance is 20% or more and 65% or less. A resin composition film having the resin composition film according to claim 11 or claim 12, and a support. A cured film obtained by curing the resin composition according to any one of claims 1 to 10, or the resin composition film according to claim 11 or 12. An electronic component including the cured film according to claim 14.