CN109415486B - Epoxy resin and cured product thereof - Google Patents
Epoxy resin and cured product thereof Download PDFInfo
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- CN109415486B CN109415486B CN201780042058.4A CN201780042058A CN109415486B CN 109415486 B CN109415486 B CN 109415486B CN 201780042058 A CN201780042058 A CN 201780042058A CN 109415486 B CN109415486 B CN 109415486B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
Abstract
The invention provides an epoxy resin having extremely low dielectric constant and dielectric loss tangent, a curable resin composition containing the same, a cured product thereof, a printed circuit board, and a semiconductor sealing material. An epoxy resin characterized by comprising an ester (A) of a phenolic hydroxyl group-containing compound (a1) and an aromatic dicarboxylic acid or an acid halide thereof (a2), and a 2-functional epoxy compound (B) as essential reaction raw materials, a curable resin composition containing the epoxy resin, and a cured product thereof, a printed circuit board, and a semiconductor sealing material.
Description
Technical Field
The present invention relates to an epoxy resin having excellent heat resistance and a very low dielectric loss tangent, a curable resin composition containing the same, a cured product thereof, a printed circuit board, and a semiconductor sealing material.
Background
In the field of insulating materials for semiconductors, multilayer printed boards, and the like, development of new resin materials is being sought in accordance with the market trends as the operating temperature of various electronic components increases, and signals are becoming faster and higher in frequency. For example, with an increase in the operating temperature of electronic components, development of resin materials having high heat resistance is being advanced. In addition, in order to reduce energy loss such as heat generation associated with high-speed and high-frequency signals, development of resin materials having a low dielectric loss tangent has been advanced.
As a resin material having a low dielectric loss tangent, for example, a high molecular weight epoxy resin having a weight average molecular weight (Mw) of 5000 to 200000 obtained by reacting an epoxy resin such as biphenol diglycidyl ether with an ester compound such as bisacetoxybiphenyl is known (see patent document 1 below). The epoxy resin described in patent document 1 has a characteristic of low dielectric loss tangent as compared with a conventional resin material, but does not satisfy the recent market demand level and is a resin having low heat resistance.
Prior patent literature
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-89165
Disclosure of Invention
Problems to be solved by the invention
Accordingly, an object to be solved by the present invention is to provide an epoxy resin having excellent heat resistance and a very low dielectric loss tangent, a curable resin composition containing the same, a cured product thereof, a printed circuit board, and a semiconductor sealing material.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems and as a result, have found that an epoxy resin containing an esterified product of a phenolic hydroxyl group-containing compound and an aromatic dicarboxylic acid or an acid halide thereof, and a 2-functional epoxy compound as essential reaction raw materials is characterized by excellent heat resistance and an extremely low dielectric loss tangent, and have completed the present invention.
That is, the present invention relates to an epoxy resin characterized by using an ester (A) of a phenolic hydroxyl group-containing compound (a1) and an aromatic dicarboxylic acid or an acid halide thereof (a2), and a 2-functional epoxy compound (B) as essential reaction raw materials.
The present invention also relates to a curable resin composition containing the epoxy resin and a curing agent.
The present invention also relates to a cured product of the curable resin composition.
The present invention also relates to a printed wiring board using the curable resin composition.
The present invention also relates to a semiconductor sealing material using the curable resin composition.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, an epoxy resin having excellent heat resistance and a very low dielectric loss tangent, a curable resin composition containing the same, a cured product thereof, a printed circuit board, and a semiconductor sealing material can be provided.
Drawings
FIG. 1 is a GPC chart of epoxy resin (1) obtained in example 1.
FIG. 2 is a GPC chart of the epoxy resin (2) obtained in example 2.
FIG. 3 is a GPC chart of the epoxy resin (3) obtained in example 3.
FIG. 4 is a GPC chart of the epoxy resin (4) obtained in example 4.
FIG. 5 is a GPC chart of epoxy resin (5) obtained in example 5.
Detailed Description
The present invention will be described in detail below.
The epoxy resin of the present invention is characterized in that an ester (A) of a phenolic hydroxyl group-containing compound (a1) and an aromatic dicarboxylic acid or an acid halide thereof (a2), and a 2-functional epoxy compound (B) are used as essential reaction raw materials.
The phenolic hydroxyl group-containing compound (a1) may be any compound as long as it is an aromatic compound having a hydroxyl group on the aromatic ring, and the specific structure thereof is not particularly limited. In the present invention, the phenolic hydroxyl group-containing compound (a1) may be used singly or in combination of 2 or more. Specific examples of the phenolic hydroxyl group-containing compound (a1) include: phenols, naphthols, anthrals, compounds having one or more substituents on these aromatic nuclei. Examples of the substituent on the aromatic nucleus include: aliphatic hydrocarbon groups such as methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and nonyl; alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; halogen atoms such as fluorine atom, chlorine atom, and bromine atom; phenyl, naphthyl, anthryl, and aryl groups substituted with the above aliphatic hydrocarbon group, alkoxy group, halogen atom, etc. on the aromatic nucleus; and a phenylmethyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and an aralkyl group substituted with the above-mentioned aliphatic hydrocarbon group, alkoxy group, halogen atom, etc. on the aromatic nucleus.
Among these, naphthol compounds are preferred, and 1-naphthol or 2-naphthol is particularly preferred, since epoxy resins having a lower dielectric loss tangent are obtained.
The specific structure of the aromatic dicarboxylic acid or its acid halide (a2) is not particularly limited as long as it is an aromatic compound that can react with the phenolic hydroxyl group of the phenolic hydroxyl group-containing compound (a1) to form the esterified compound (a), and any compound can be used. The aromatic dicarboxylic acid or its acid halide (a2) may be used alone or in combination of 2 or more. Specific examples of the aromatic dicarboxylic acid or the acid halide thereof (a2) include: benzene dicarboxylic acids such as isophthalic acid and terephthalic acid, benzene tricarboxylic acids such as trimellitic acid, naphthalene dicarboxylic acids such as naphthalene-1, 4-dicarboxylic acid, naphthalene-2, 3-dicarboxylic acid, naphthalene-2, 6-dicarboxylic acid, and naphthalene dicarboxylic acids such as naphthalene-2, 7-dicarboxylic acid, acid halides thereof, and compounds in which these aromatic nuclei are substituted with the above-mentioned aliphatic hydrocarbon group, alkoxy group, halogen atom, and the like. Examples of the acid halide include acid chloride, acid bromide, acid fluoride, and acid iodide. These may be used alone or in combination of 2 or more. Among them, from the viewpoint of being an epoxy resin having a lower dielectric loss tangent, a benzene dicarboxylic acid such as isophthalic acid or terephthalic acid, or an acid halide thereof is preferable.
The reaction of reacting the phenolic hydroxyl group-containing compound (a1) with the aromatic dicarboxylic acid or its acid halide (a2) to obtain the ester (a) can be carried out, for example, by heating and stirring in the presence of a basic catalyst at a temperature of about 40 to 65 ℃. The reaction may be carried out in an organic solvent as required. After the reaction is completed, the reaction product may be purified by washing with water, reprecipitation or the like as desired.
Examples of the basic catalyst include: sodium hydroxide, potassium hydroxide, triethylamine, pyridine, and the like. These may be used alone or in combination of 2 or more. In addition, the water-soluble polymer can be prepared into about 3.0-30% aqueous solution for use. Among them, sodium hydroxide or potassium hydroxide having high catalytic performance is preferable.
Examples of the organic solvent include: ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, carbitol solvents such as cellosolve and butyl carbitol, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide and N-methylpyrrolidone. These solvents may be used alone or as a mixture of 2 or more solvents.
The ratio of the reaction between the phenolic hydroxyl group-containing compound (a1) and the aromatic dicarboxylic acid or its acid halide (a2) is preferably 0.95 to 1.05 mol based on 1 mol of the total of the carboxyl groups or acid halide groups of the aromatic dicarboxylic acid or its acid halide (a2), and the phenolic hydroxyl group-containing compound (a1), from the viewpoint of obtaining the desired ester (a) in high yield.
The 2-functional epoxy compound (B) is not particularly limited in terms of other specific structures, presence or absence of a functional group, and the like, as long as it is a compound having 2 epoxy groups in its molecular structure, and may be any compound. The 2-functional epoxy compound (B) may be used alone or in combination of 2 or more.
The epoxy group of the 2-functional epoxy compound (B) has an oxirane structure represented by the following structural formula (1), and specific examples of the epoxy group include a glycidyl ether group, an epoxycyclohexyl group, and the like.
(wherein R represents a hydrogen atom, various hydrocarbon groups, etc., and R's may form a ring structure.)
Specific examples of the compound having a glycidyl ether group in the molecular structure among the 2-functional epoxy compounds (B) include diglycidyl etherates of various diol compounds.
Examples of the diol compound include diol compounds represented by any one of the following structural formulae (2-1) to (2-17), ring-opened polymers of these diol compounds and lactone compounds, and polyoxyalkylene-modified products.
[ formulae (2-1) to (2-17) wherein R1Is an aliphatic hydrocarbon group having 2 to 10 carbon atoms or a structural site having one or more alkoxy groups or halogen atoms on the carbon atom. R2、R3Each independently is any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. k is an integer of 1 to 4, l is 0 or an integer of 1 to 4, m is 0 or an integer of 1 to 6, p is 0 or an integer of 1 to 3, and q is 0 or an integer of 1 to 5. Ar (Ar)1Represents an optionally substituted aryl group, Ar2Represents a monohydroxyaryl group optionally having a substituent. In the formulae (2-13) and (2-14), x and y are bonded to carbon atoms adjacent to each other, each forming a xanthene structure or a dinaphthofuran structure. In the formula (2-17), Z is any one of a hydrocarbon group, an oxygen atom and a carbonyl group.]
The diglycidyl etherification of the diol compounds can be carried out, for example, by a method in which one or more of the diol compounds are reacted with an excess amount of epihalohydrin in the presence of a basic catalyst at a temperature of 20 to 120 ℃ for 0.5 to 10 hours. When the 2-functional epoxy compound (B) is obtained by this method, a by-product such as a reaction product of the produced diglycidyl etherate and the diol compound as a reaction raw material may be generated. In this case, the epoxy equivalent of the obtained 2-functional epoxy compound (B) is preferably within 2.0 times of the theoretical value.
Specific examples of the compound having an epoxycyclohexyl group in the molecular structure among the 2-functional epoxy compounds (B) include 3 ', 4' -epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate and the like.
The epoxy resin of the present invention may be prepared by using other compounds as reaction raw materials in addition to the ester (A) and the 2-functional epoxy compound (B). Other compounds are exemplified by: an epoxy compound (B') having 3 or more functions, a substituent-introducing agent (C) for introducing an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group or an aralkyl group as a substituent on the aromatic nucleus of the obtained epoxy resin, and the like. When the epoxy compound (B ') having 3 or more functions is used, it is preferable to use the epoxy compound (B') in a range where the average number of functional groups of the epoxy compound raw material is 2.5 or less in order to obtain a film-forming ability.
The reaction between the ester (A) and the 2-functional epoxy compound (B) can be carried out, for example, by heating and stirring in the presence of an appropriate reaction catalyst under a temperature condition of about 100 to 180 ℃. The reaction may be carried out in an organic solvent as required. After the reaction is completed, the reaction product may be purified by washing with water, reprecipitation or the like as desired.
Examples of the reaction catalyst include: phosphorus compounds, tertiary amines, imidazole compounds, pyridine compounds, organic acid metal salts, lewis acids, amine complex salts, and the like. Among them, triphenylphosphine is preferable as the phosphorus compound, 1, 8-diazabicyclo- [5.4.0] -undecene (DBU) is preferable as the tertiary amine, 2-ethyl-4-methylimidazole is preferable as the imidazole compound, and 4-dimethylaminopyridine is preferable as the pyridine compound, from the viewpoint of excellent catalytic performance.
Examples of the organic solvent include: ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, carbitol solvents such as cellosolve and butyl carbitol, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide and N-methylpyrrolidone. These solvents may be used alone or as a mixture of 2 or more solvents.
The ratio of the ester (A) to the 2-functional epoxy compound (B) is preferably in the range of 0.5 to 1 in terms of the number of moles of the ester-constituting site in the ester (A) per 1 mole of the epoxy group in the epoxy compound (B).
The epoxy group equivalent of the epoxy resin of the present invention is preferably in the range of 5000 to 100000 g/eq, more preferably in the range of 7500 to 50000 g/eq, from the viewpoint of providing an epoxy resin having a lower dielectric loss tangent.
The weight average molecular weight (Mw) of the epoxy resin of the present invention is preferably in the range of 5000 to 100000, more preferably in the range of 7500 to 60000, and particularly preferably in the range of 8000 to 50000, from the viewpoint of obtaining an epoxy resin having a low film-forming ability and a low dielectric loss tangent. The molecular weight distribution (Mw/Mn) is preferably in the range of 1.5 to 20, more preferably in the range of 2 to 12.
The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the epoxy resin of the present invention are values measured by GPC measured under the following conditions.
A measuring device: HLC-8320GPC, manufactured by Tosoh corporation,
Column: "HXL-L" protective column manufactured by Tosoh corporation "
+ manufactured by Tosoh corporation of "TSK-GEL G4000 HXL"
+ TSK-GEL G3000HXL manufactured by Tosoh corporation "
+ TSK-GEL G2000HXL manufactured by Tosoh corporation "
+ TSK-GEL G2000HXL manufactured by Tosoh corporation "
A detector: RI (differential refractometer)
Data processing: "EcoSEC-WorkStation" of Tosoh corporation "
The measurement conditions were as follows: column temperature 40 deg.C
Tetrahydrofuran as developing solvent
Flow rate 1.0 ml/min
The standard is as follows: the following monodisperse polystyrene having a known molecular weight was used according to the manual of measurement of "GPC-8320" described above.
(polystyrene used)
"A-500" made by Tosoh corporation "
"A-1000" made by Tosoh corporation "
"A-2500" made by Tosoh corporation "
"A-5000" manufactured by Tosoh corporation "
"F-1" made by Tosoh corporation "
"F-2" made by Tosoh corporation "
"F-4" made by Tosoh corporation "
"F-10" made by Tosoh corporation "
"F-20" made by Tosoh corporation "
"F-40" made by Tosoh corporation "
"F-80" made by Tosoh corporation "
"F-128" made by Tosoh corporation "
Sample preparation: a tetrahydrofuran solution (1.0 mass% in terms of solid content of resin) was filtered through a microfilter (50. mu.l)
Examples of specific structures of the epoxy resin of the present invention include theoretical structures in the case of using naphthol as the phenolic hydroxyl group-containing compound (a1), using isophthaloyl dichloride as the aromatic dicarboxylic acid or its acid halide (a2), and using diglycidyl ether of bisphenol a as the 2-functional epoxy compound (B), and are shown in the following structural formula (3). The following structural formula (3) is only an example of a specific structure of the epoxy resin of the present invention, and does not exclude other resin structures that can be produced by reacting the ester (a) of the phenolic hydroxyl group-containing compound (a1) and the aromatic dicarboxylic acid or its acid halide (a2) with the 2-functional epoxy compound (B).
The epoxy resin of the present invention can be used as a curable resin composition by blending with a curing agent and a curing accelerator. The curing agent is not particularly limited as long as it is a compound capable of reacting with the epoxy resin of the present invention, and various compounds can be used. Examples of the curing agent include: diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3Amine compounds such as amine complexes and guanidine derivatives; amide compounds such as polyamide resins synthesized from dimers of dicyandiamide and linolenic acid and ethylenediamine; anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride; phenol resins such as phenol novolac resins, cresol novolac resins, naphthol novolac resins, bisphenol novolac resins, biphenol novolac resins, dicyclopentadiene-phenol addition type resins, phenol aralkyl resins, naphthol aralkyl resins, trisphenol methane type resins, tetraphenol ethane type resins, and aminotriazine modified phenol resins; an active ester resin; cyanate ester resin; bismaleimide resin; a benzoxazine resin; styrene-maleic anhydride resin; allyl group-containing resins represented by diallyl bisphenol and triallyl isocyanurate, polyphosphate esters, phosphate-carbonate copolymers, and the like. These may be used alone or in combination of 2 or more.
The curable resin composition of the present invention may be used in combination with other epoxy resins other than the aforementioned epoxy resins. Examples of other epoxy resins include: phenol novolac type epoxy resins, cresol novolac type epoxy resins, naphthol novolac type epoxy resins, bisphenol novolac type epoxy resins, biphenol novolac type epoxy resins, bisphenol type epoxy resins, biphenyl type epoxy resins, triphenol methane type epoxy resins, tetraphenol ethane type epoxy resins, dicyclopentadiene-phenol addition reaction type epoxy resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, and the like.
The mixing ratio of the epoxy resin of the present invention, the curing agent, and the other epoxy resin is not particularly limited, and may be appropriately adjusted according to the desired properties of the cured product and the like. As an example of the compounding, the ratio of 0.7 to 1.5 moles to 1 mole of the total of epoxy groups in the curable resin composition and the total of functional groups in the curing agent is preferable.
The curable resin composition of the present invention may contain various additives such as a curing accelerator, a flame retardant, an inorganic filler, a silane coupling agent, a release agent, a pigment, and an emulsifier, if necessary.
Examples of the curing accelerator include: phosphorus compounds, tertiary amines, imidazole compounds, pyridine compounds, organic acid metal salts, lewis acids, amine complex salts, and the like. Among these, triphenylphosphine is preferable as the phosphorus compound and 1, 8-diazabicyclo- [5.4.0] -undecene (DBU) is preferable as the tertiary amine, 2-ethyl-4-methylimidazole is preferable as the imidazole compound, and 4-dimethylaminopyridine is preferable as the pyridine compound, from the viewpoint of excellent curability, heat resistance, electrical characteristics, moisture resistance reliability, and the like.
Examples of the flame retardant include: inorganic phosphorus compounds such as ammonium phosphates and phosphoric acid amides, including red phosphorus, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate and ammonium polyphosphate; organic phosphorus compounds such as phosphate compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, cyclic organic phosphorus compounds such as 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives obtained by reacting these compounds with compounds such as epoxy resins and phenol resins; nitrogen flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine, and the like; silicone-based flame retardants such as silicone oil, silicone rubber, and silicone resin; inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. When these flame retardants are used, they are preferably contained in the curable resin composition in an amount of 0.1 to 20% by mass.
For example, when the curable resin composition of the present invention is used for semiconductor sealing materials or the like, the inorganic filler is added. Examples of the inorganic filler include: fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, and the like. Among these, the fused silica is preferable because the inorganic filler can be blended in a larger amount. The fused silica may be in a crushed form or a spherical form, and in order to increase the amount of the fused silica to be blended and to suppress an increase in melt viscosity of the curable composition, it is preferable to mainly use spherical fused silica. Further, in order to increase the amount of the spherical silica to be blended, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling ratio is preferably in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable resin composition.
When the curable resin composition of the present invention is used for an electrically conductive paste or the like, an electrically conductive filler such as silver powder or copper powder can be used.
As described in detail above, the epoxy resin of the present invention has excellent heat resistance and an extremely low dielectric loss tangent. In addition, general performance requirements for resin materials, such as solubility in general-purpose organic solvents and curability with various curing agents, are sufficiently high, and they are widely used in applications such as paints, adhesives, and molded articles, in addition to electronic materials, such as printed circuit boards, semiconductor sealing materials, and resist materials.
When the curable resin composition of the present invention is used for printed circuit boards and laminated adhesive films, it is generally preferable to dilute the composition with an organic solvent. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. The type and amount of the organic solvent can be suitably adjusted depending on the use environment of the curable resin composition, and for example, in the case of printed wiring board use, a polar solvent having a boiling point of 160 ℃ or lower such as methyl ethyl ketone, acetone, dimethylformamide, cyclohexanone is preferable, and the organic solvent is preferably used in a proportion such that the nonvolatile component is 25 to 80 mass%. For the use of the build-up adhesive film, it is preferable to use a ketone solvent such as acetone, methyl ethyl ketone, cyclohexanone, etc., an acetate solvent such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc., a carbitol solvent such as cellosolve, butyl carbitol, etc., an aromatic hydrocarbon solvent such as toluene, xylene, etc., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and it is preferable to use them in a proportion such that the nonvolatile content is 25 to 60 mass%.
In addition, a method for producing a printed circuit board using the curable resin composition of the present invention includes, for example, a method in which a prepreg is obtained by impregnating a reinforcing base material with the curable resin composition and curing the impregnated reinforcing base material, and the prepreg is stacked on a copper foil and then thermally pressed. The reinforcing base material includes: paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass felt, glass roving cloth and the like. The amount of the curable resin composition to be impregnated is not particularly limited, and is preferably adjusted to 20 to 60% by mass of the resin component in the prepreg.
When the curable resin composition of the present invention is used for a semiconductor sealing material, it is generally preferable to add an inorganic filler. The semiconductor sealing material can be prepared by mixing the compounds using, for example, an extruder, a kneader, a roller, or the like. The semiconductor package can be molded using the obtained semiconductor sealing material by molding the semiconductor sealing material using a cast molding machine, a transfer molding machine, an injection molding machine, or the like, and further heating the molded material at a temperature of 50 to 200 ℃ for 2 to 10 hours, whereby a semiconductor device as a molded product can be obtained.
Examples
The present invention will be described more specifically with reference to examples and comparative examples. The descriptions of "parts" and "%" in the examples are based on mass unless otherwise specified. The measurement conditions of GPC in the present example are as follows.
Measurement conditions of GPC
A measuring device: HLC-8320GPC, manufactured by Tosoh corporation,
Column: "HXL-L" protective column manufactured by Tosoh corporation "
+ manufactured by Tosoh corporation of "TSK-GEL G4000 HXL"
+ TSK-GEL G3000HXL manufactured by Tosoh corporation "
+ TSK-GEL G2000HXL manufactured by Tosoh corporation "
+ TSK-GEL G2000HXL manufactured by Tosoh corporation "
A detector: RI (differential refractometer)
Data processing: "EcoSEC-WorkStation" of Tosoh corporation "
The measurement conditions were as follows: column temperature 40 deg.C
Tetrahydrofuran as developing solvent
Flow rate 1.0 ml/min
The standard is as follows: the following monodisperse polystyrene having a known molecular weight was used according to the manual of measurement of "GPC-8320" described above.
(polystyrene used)
"A-500" made by Tosoh corporation "
"A-1000" made by Tosoh corporation "
"A-2500" made by Tosoh corporation "
"A-5000" manufactured by Tosoh corporation "
"F-1" made by Tosoh corporation "
"F-2" made by Tosoh corporation "
"F-4" made by Tosoh corporation "
"F-10" made by Tosoh corporation "
"F-20" made by Tosoh corporation "
"F-40" made by Tosoh corporation "
"F-80" made by Tosoh corporation "
"F-128" made by Tosoh corporation "
Sample preparation: a tetrahydrofuran solution (1.0 mass% in terms of solid content of resin) was filtered through a microfilter (50. mu.l)
EXAMPLE 1 preparation of epoxy resin (1) solution
A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer was charged with 202 parts by mass of isophthaloyl dichloride and 1250 parts by mass of toluene, and the system was dissolved by nitrogen substitution under reduced pressure. Then, 288 parts by mass of 1-naphthol was added thereto, and the system was dissolved by nitrogen substitution under reduced pressure. Subsequently, 0.6 part by mass of tetrabutylammonium bromide was added, and while purging with nitrogen gas, 400 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while controlling the temperature in the system to 60 ℃ or lower. After the completion of the dropwise addition, the reaction mixture was stirred for 1 hour. After the reaction, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. After the remaining organic layer was stirred and mixed with water for about 15 minutes, the mixture was allowed to stand for liquid separation, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer was 7, followed by drying under reduced pressure with heating to obtain 395 parts by mass of an esterified product (A-1) represented by the following structural formula (a).
[ solution 5]
176 parts by mass of bisphenol A epoxy resin ("EXA-850 CRP" manufactured by DIC corporation, epoxy equivalent 173 g/equivalent), 209 parts by mass of the ester (A-1) obtained above and 165 parts by mass of cyclohexanone were charged into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, and the mixture was dissolved by nitrogen substitution under reduced pressure. Then, 0.15 part by mass of dimethylaminopyridine was added thereto, and the temperature in the system was raised to 150 ℃ while purging with nitrogen. After allowing the mixture to react at 150 ℃ for 24 hours, 285 parts by mass of cyclohexanone and 450 parts by mass of methyl ethyl ketone were added to dilute the mixture, thereby obtaining 1220 parts by mass of an epoxy resin (1) solution. The epoxy equivalent of the epoxy resin (1) was 19450 g/equivalent, the weight average molecular weight (Mw) was 37180, and the molecular weight distribution (Mw/Mn) was 9.3. The GPC chart of the obtained epoxy resin (1) is shown in FIG. 1.
EXAMPLE 2 preparation of epoxy resin (2) solution
A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer was charged with 72 parts by mass of a dihydroxynaphthalene type epoxy resin ("HP-4032D" manufactured by DIC corporation, epoxy equivalent 141 g/equivalent), 105 parts by mass of the ester (A-1) obtained above and 76 parts by mass of cyclohexanone, and the inside of the system was dissolved by nitrogen substitution under reduced pressure. Then, 0.07 part by mass of dimethylaminopyridine was added thereto, and the temperature in the system was raised to 150 ℃ while purging with nitrogen. After allowing the mixture to react at 150 ℃ for 12 hours, 130 parts by mass of cyclohexanone and 206 parts by mass of methyl ethyl ketone were added to dilute the mixture, thereby obtaining 549 parts by mass of an epoxy resin (1) solution. The epoxy equivalent of the epoxy resin (2) was 34860 g/equivalent, the weight average molecular weight (Mw) was 23940, and the molecular weight distribution (Mw/Mn) was 6.8. The GPC chart of the obtained epoxy resin (2) is shown in FIG. 2.
EXAMPLE 3 preparation of epoxy resin (3) solution
66 parts by mass of an alicyclic epoxy resin ("CEL 2021P" manufactured by Daicel Chemical Industries, ltd., epoxy equivalent 130 g/equivalent), 105 parts by mass of the ester (a-1) obtained above, and 73 parts by mass of cyclohexanone were charged into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, and the system was dissolved by nitrogen substitution under reduced pressure. Then, 0.07 part by mass of dimethylaminopyridine was added thereto, and the temperature in the system was raised to 150 ℃ while purging with nitrogen. After allowing the mixture to react at 150 ℃ for 12 hours, 126 parts by mass of cyclohexanone and 199 parts by mass of methyl ethyl ketone were added to dilute the mixture, thereby obtaining 532 parts by mass of an epoxy resin (3) solution. The epoxy resin (3) had an epoxy group equivalent of 8210 g/equivalent, a weight average molecular weight (Mw) of 10000 and a molecular weight distribution (Mw/Mn) of 5.7. The GPC chart of the obtained epoxy resin (3) is shown in FIG. 3.
EXAMPLE 4 preparation of epoxy resin (4) solution
In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, 136 parts by mass of an epoxy resin (epoxy equivalent: 265 g/equivalent) containing a xanthene-type epoxy compound represented by the following structural formula (b) as a main component, 105 parts by mass of the ester (A-1) obtained in the previous step and 103 parts by mass of cyclohexanone were charged, and the system was dissolved by nitrogen substitution under reduced pressure. Then, 0.10 part by mass of dimethylaminopyridine was added thereto, and the temperature in the system was raised to 150 ℃ while purging with nitrogen gas. After allowing the mixture to react at 150 ℃ for 12 hours, 178 parts by mass of cyclohexanone and 281 parts by mass of methyl ethyl ketone were added to dilute the mixture, thereby obtaining 750 parts by mass of an epoxy resin (4) solution. The epoxy resin (4) had an epoxy group equivalent of 8520 g/equivalent, a weight average molecular weight (Mw) of 23530, and a molecular weight distribution (Mw/Mn) of 8.3. The GPC chart of the obtained epoxy resin (4) is shown in FIG. 4.
[ solution 6]
EXAMPLE 5 preparation of epoxy resin (5) solution
127 parts by mass of an epoxy resin (epoxy equivalent: 246 g/equivalent) containing a fluorene type epoxy resin represented by the following structural formula (c) as a main component, 105 parts by mass of the ester (A-1) obtained above, and 99 parts by mass of cyclohexanone were charged into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, and the mixture was dissolved by nitrogen substitution under reduced pressure. Then, 0.09 part by mass of dimethylaminopyridine was added thereto, and the temperature in the system was raised to 150 ℃ while purging with nitrogen gas. After allowing the mixture to react at 150 ℃ for 12 hours, 171 parts by mass of cyclohexanone and 270 parts by mass of methyl ethyl ketone were added to dilute the mixture, thereby obtaining 738 parts by mass of an epoxy resin (5) solution. The epoxy resin (5) had an epoxy group equivalent of 13270 g/equivalent, a weight average molecular weight (Mw) of 21000, and a molecular weight distribution (Mw/Mn) of 5.8. The GPC chart of the obtained epoxy resin (5) is shown in FIG. 5.
[ solution 7]
Comparative production example 1 production of epoxy resin (1') solution
97 parts by mass of bisphenol A epoxy resin ("EPICLON 850-S" manufactured by DIC corporation, epoxy equivalent 188 g/equivalent), 109 parts by mass of bisphenol A dibenzoate, and 88 parts by mass of cyclohexanone were charged into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, and the inside of the system was replaced with nitrogen under reduced pressure to dissolve the bisphenol A dibenzoate. Then, 0.08 part by mass of dimethylaminopyridine was added thereto, and the temperature in the system was raised to 150 ℃ while purging with nitrogen gas. After allowing the reaction to proceed at 150 ℃ for 36 hours, 152 parts by mass of cyclohexanone and 240 parts by mass of methyl ethyl ketone were added to dilute the mixture, thereby obtaining 650 parts by mass of an epoxy resin (1') solution. The epoxy resin (1') had an epoxy group equivalent of 6650 g/equivalent, a weight average molecular weight (Mw) of 7380, and a molecular weight distribution (Mw/Mn) of 2.3.
Examples 6 to 10 and comparative example 1
Production and evaluation of film
The epoxy resin solutions obtained in examples 1 to 5 and comparative production example 1 were applied to a separator (silicone-treated polyethylene terephthalate film) with an applicator, and dried at 80 ℃ for 10 minutes and further at 150 ℃ for 1 hour to prepare an epoxy resin film having a thickness of 70 μm. The shape that can hold the film is judged as A, and the shape that cannot hold the film is judged as B.
Measurement of Heat resistance (DSC-Tg)
The DSC822e manufactured by METTLER TOLEDO corporation was used to measure the DSC-Tg of the epoxy resin film obtained above at 10 ℃/min.
Determination of dielectric loss tangent
The obtained epoxy resin film was dried under vacuum and heated, and then stored in a room at 23 ℃ and a humidity of 50% for 24 hours. Thereafter, the dielectric loss tangent at 1GHz of the epoxy resin film was measured according to JIS-C-6481 using an impedance material analyzer "HP 4291B" manufactured by Agilent Technologies Japan, Ltd.
[ Table 1]
TABLE 1
| Example 6 | Example 7 | Example 8 | Example 9 | Example 10 | Comparative example 1 | |
| Epoxy resin | (1) | (2) | (3) | (4) | (5) | (1′) |
| Shape of film | A | A | A | A | A | B |
| Heat resistance [ deg.C] | 94 | 105 | 125 | 139 | 123 | 72 |
| Dielectric loss tangent (1GHz) | 0.0085 | 0.0065 | 0.0090 | 0.0082 | 0.0062 | 0.0145 |
Claims (11)
1. An epoxy resin solution containing an epoxy resin and an organic solvent, wherein the epoxy resin is obtained by using an ester (A) of a phenolic hydroxyl group-containing compound (a1) and an aromatic dicarboxylic acid or an acid halide thereof (a2) as essential raw materials, and a 2-functional epoxy compound (B), the epoxy resin has an average functional group number of 2.5 or less, an epoxy equivalent of 5000 to 100000 g/equivalent, and a weight average molecular weight Mw of 5000 to 100000.
2. The epoxy resin solution of claim 1, wherein the epoxy resin has a molecular structure represented by the following structural formula,
wherein X is a structural site derived from a phenolic hydroxyl group-containing compound (a1), Y is a structural site derived from an aromatic dicarboxylic acid or an acid halide thereof (a2), Z is a structural site derived from a 2-functional epoxy compound (B), and n is an integer representing the number of repeating units.
3. The epoxy resin solution according to claim 1, wherein the reaction ratio of the phenolic hydroxyl group-containing compound (a1) to the aromatic dicarboxylic acid or its acid halide (a2) is 0.95 to 1.05 mol based on 1 mol of the total of the carboxyl groups or acid halide groups of the aromatic dicarboxylic acid or its acid halide (a2), and the phenolic hydroxyl group-containing compound (a 1).
4. The epoxy resin solution according to claim 1, wherein the phenolic hydroxyl group-containing compound (a1) is 1-naphthol or 2-naphthol.
5. The epoxy resin solution according to claim 1, wherein the organic solvent is an organic solvent having a boiling point of 160 ℃ or less.
6. The epoxy resin solution according to any one of claims 1 to 5, wherein the nonvolatile content is 25 to 80% by mass.
7. The epoxy solution of claim 6, wherein the organic solvent is methyl ethyl ketone, acetone, dimethylformamide, or cyclohexanone.
8. A process for producing an epoxy resin solution, characterized by reacting an ester (A) of a phenolic hydroxyl group-containing compound (a1) and an aromatic dicarboxylic acid or its acid halide (a2), wherein the epoxy compound (A) contains a 2-functional epoxy compound (B), and the average number of functional groups of the epoxy compound in the raw material is 2.5 or less, with an epoxy compound at a temperature of 100 to 180 ℃, and diluting the reaction product with an organic solvent.
9. The method for producing an epoxy resin solution according to claim 8, wherein the phenolic hydroxyl group-containing compound (a1) and the aromatic dicarboxylic acid or its acid halide (a2) are used in a proportion of 0.95 to 1.05 mol based on 1 mol of the total of the carboxyl groups or acid halide groups of the aromatic dicarboxylic acid or its acid halide (a2), and the phenolic hydroxyl group-containing compound (a 1).
10. The method for producing an epoxy resin solution according to claim 8, wherein the epoxy resin in the epoxy resin solution has an epoxy group equivalent of 5000 to 100000 g/eq and a weight average molecular weight Mw of 5000 to 100000.
11. A method for producing an epoxy resin film, comprising the steps of:
a step of reacting an epoxy compound having an average functional group number of 2.5 or less and containing a 2-functional epoxy compound (B) with an ester (A) of a phenolic hydroxyl group-containing compound (a1) and an aromatic dicarboxylic acid or an acid halide thereof (a2) to obtain an epoxy resin solution in which an epoxy resin having an epoxy group equivalent of 5000 to 100000 g/equivalent and a weight average molecular weight Mw of 5000 to 100000 is dissolved in an organic solvent,
and a step of applying the epoxy resin solution obtained above to a separator and drying the resultant coating by heating.
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| JP7007999B2 (en) * | 2018-08-29 | 2022-01-25 | 上野製薬株式会社 | Diester compound and its manufacturing method |
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| JP2003261650A (en) * | 2002-03-07 | 2003-09-19 | Dainippon Ink & Chem Inc | Epoxy resin composition, its pre-cured product and cured product |
| CN101152772A (en) * | 2002-12-27 | 2008-04-02 | Tdk株式会社 | Resin composition, cured resin, sheet-like cured resin, laminated body, prepreg, electronic parts and multilayer boards |
| JP2014101449A (en) * | 2012-11-20 | 2014-06-05 | Dic Corp | Phenoxy resin, curable resin composition, cured product thereof, prepreg, circuit board and buildup film |
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| JP2002012650A (en) * | 2000-06-30 | 2002-01-15 | Dainippon Ink & Chem Inc | Epoxy resin composition for low-dielectric material |
| JP4632077B2 (en) * | 2002-10-15 | 2011-02-16 | Ｄｉｃ株式会社 | Epoxy resin composition, method for producing epoxy resin, novel epoxy resin, and novel phenol resin |
| JP4241005B2 (en) * | 2002-11-08 | 2009-03-18 | Ｄｉｃ株式会社 | Epoxy resin composition and cured product thereof |
| JP2006059999A (en) * | 2004-08-19 | 2006-03-02 | Tdk Corp | Printed-wiring board and electronic component |
| TWI646142B (en) * | 2012-12-21 | 2019-01-01 | 台光電子材料股份有限公司 | Resin composition and copper foil substrate and printed circuit board using same |
| JP6672699B2 (en) | 2014-10-29 | 2020-03-25 | 三菱ケミカル株式会社 | Epoxy resin, epoxy resin composition, cured product, laminate for electric / electronic circuit, and method for producing epoxy resin |
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| JP2003082063A (en) * | 2001-09-12 | 2003-03-19 | Dainippon Ink & Chem Inc | Epoxy resin composition for electronic material and electronic material having low permittivity |
| JP2003261650A (en) * | 2002-03-07 | 2003-09-19 | Dainippon Ink & Chem Inc | Epoxy resin composition, its pre-cured product and cured product |
| CN101152772A (en) * | 2002-12-27 | 2008-04-02 | Tdk株式会社 | Resin composition, cured resin, sheet-like cured resin, laminated body, prepreg, electronic parts and multilayer boards |
| JP2014101449A (en) * | 2012-11-20 | 2014-06-05 | Dic Corp | Phenoxy resin, curable resin composition, cured product thereof, prepreg, circuit board and buildup film |
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