CN118103425A - Curable composition, cured product thereof, prepreg, circuit board, build-up film, semiconductor sealing material, and semiconductor device - Google Patents

Curable composition, cured product thereof, prepreg, circuit board, build-up film, semiconductor sealing material, and semiconductor device Download PDF

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CN118103425A
CN118103425A CN202280066410.9A CN202280066410A CN118103425A CN 118103425 A CN118103425 A CN 118103425A CN 202280066410 A CN202280066410 A CN 202280066410A CN 118103425 A CN118103425 A CN 118103425A
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curable composition
resin
group
mass
cured product
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金荣璨
林弘司
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DIC Corp
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DIC Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • 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
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • 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
    • 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
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention provides a curable composition, a cured product thereof, a prepreg, a circuit board, a build-up film, a semiconductor sealing material and a semiconductor device, wherein the curable composition has high compatibility even if the curable composition is prepared by blending a hydrocarbon resin (hydrocarbon plasticizer) with extremely low polarity, and the cured product of the curable composition has low dielectric loss tangent. A curable composition is used, which contains an active ester resin, a hydrocarbon resin and a hardener, wherein the active ester resin is a reaction product of a resin (A) having a phenolic hydroxyl group and an aromatic dicarboxylic acid or an acid halide (B) thereof, and the resin (A) having a phenolic hydroxyl group is a reaction product of a compound (a 1) having an alkyl group having 5 or more carbon atoms and a phenolic hydroxyl group and a divinyl compound (a 2).

Description

Curable composition, cured product thereof, prepreg, circuit board, build-up film, semiconductor sealing material, and semiconductor device
Technical Field
The present invention relates to a curable composition, a cured product thereof, a prepreg, a circuit board, a build-up film, a semiconductor sealing material, and a semiconductor device.
Background
Epoxy resin compositions containing an epoxy resin and a curing agent thereof as essential components are widely used in electronic components such as semiconductors and multilayer printed boards because cured products thereof exhibit excellent heat resistance and insulation properties. In the technical field of insulating materials represented by build-up films in such electronic component applications, in recent years, the speed and frequency of signals in various electronic devices have been increased. With the increase in the speed and frequency of the signals, a material having a lower dielectric constant and a lower dielectric loss tangent has been demanded. However, it is difficult to obtain a material that maintains a sufficiently low dielectric constant and has a low dielectric loss tangent.
Therefore, it has been reported that a hydrocarbon plasticizer is used in order to maintain a sufficiently low dielectric constant and dielectric loss tangent for signals subjected to high-speed and high-frequency operation and to improve reliability such as dimensional stability (for example, refer to patent documents 1 and 2). However, hydrocarbon plasticizers have extremely low polarity and therefore have extremely low compatibility with other resins, and it is difficult to prepare a uniform varnish. In addition, laminated boards, prepregs, and build-up films using varnishes adjusted in a state of low compatibility also have a problem of reliability failure, and the like.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2015-90954
Patent document 2: japanese patent laid-open publication No. 2013-135032
Disclosure of Invention
Problems to be solved by the invention
The object of the present invention is to provide a curable composition having high compatibility even when a hydrocarbon resin (hydrocarbon plasticizer) having extremely low polarity is blended, a cured product of the composition having low dielectric loss tangent, a prepreg, a circuit board, a build-up film, a semiconductor sealing material, and a semiconductor device.
Technical means for solving the problems
The present inventors have made an intensive study to solve the above-mentioned problems, and as a result, have found that a curable composition obtained by blending a hydrocarbon resin and a curing agent with a specific active ester has high compatibility and a cured product thereof has a low dielectric loss tangent, and have completed the present invention.
Specifically, the present invention relates to a curable composition containing an active ester resin, a hydrocarbon resin, and a hardener, wherein the active ester resin is a reaction product of a resin (A) having a phenolic hydroxyl group, which is a reaction product of a compound (a 1) having an alkyl group having 5 or more carbon atoms and a phenolic hydroxyl group, and a divinyl compound (a 2), and an aromatic dicarboxylic acid or an acid halide (B) thereof.
The present invention also relates to a cured product of the curable composition, a prepreg, a circuit board, a build-up film, a semiconductor sealing material, and a semiconductor device each using the curable composition.
ADVANTAGEOUS EFFECTS OF INVENTION
The curable composition of the present invention has high compatibility even when a hydrocarbon resin having extremely low polarity is blended, and the cured product thereof has a low dielectric loss tangent, and therefore, can be used for electronic components such as prepregs, circuit boards, build-up films, semiconductor sealing materials, and the like, and can be used for semiconductor devices using these electronic components.
Drawings
FIG. 1 is a GPC chart of an active ester resin (1) obtained in production example 1.
FIG. 2 is a GPC chart of the active ester resin (2) obtained in production example 2.
FIG. 3 is a GPC chart of an active ester resin (1') obtained in comparative production example 1.
Detailed Description
The present invention is described in detail below.
The active ester resin of the present invention is a reaction product of a resin (a) having a phenolic hydroxyl group, which is a reaction product of a compound (a 1) having an alkyl group having 5 or more carbon atoms and a phenolic hydroxyl group, and a divinyl compound (a 2), and an aromatic dicarboxylic acid or an acid halide (B) thereof.
The compound (a 1) is not particularly limited as long as it is a compound having an alkyl group having 5 or more carbon atoms and a phenolic hydroxyl group. The alkyl group of the compound (a 1) may be an alkyl group having 5 or more carbon atoms, and examples thereof include: pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like. The alkyl group may be a straight chain or branched, or may have an alicyclic structure. The alkyl group has 5 or more carbon atoms, but preferably 12 or less carbon atoms, more preferably 10 or less carbon atoms, and particularly preferably 8 or less carbon atoms.
Examples of the compound (a 1) include phenol and naphthol as a compound having a phenolic hydroxyl group. Specific examples of the compound (a 1) include: pentylphenol, hexylphenol, heptylphenol, octylphenol, nonylphenol, decylphenol, undecylphenol, dodecylphenol, pentylphenol, hexylnaphthol, heptylnaphthol, octylnaphthol, nonylnaphthol, decylnaphthol, undecylnaphthol, dodecylnaphthol, and the like. Further, the positions of substitution of the alkyl group and the phenolic hydroxyl group on the aromatic ring in the compound (a 1) are not particularly limited, and in the case where the compound (a 1) is phenol, it is preferable that the alkyl group and the phenolic hydroxyl group are substituted at the para position. In addition, the compound (a 1) may be used singly or in combination.
The divinyl compound (a 2) is not particularly limited as long as it is a compound that can react with the compound (a 1) to polymerize the compounds (a 1) with each other. Further, the divinyl compound (a 2) may be used singly or in combination. Among them, the active ester resin having an aromatic ring or alicyclic ring in the molecular structure is preferable for forming an active ester resin having excellent compatibility and excellent dielectric characteristics in a cured product. More preferable specific examples of the divinyl compound (a 2) include compounds represented by the following general formulae (1-1) to (1-4).
[ Chemical 1]
[ In the general formulae (1-1) to (1-4), R 1 is an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aralkyl group, Y is an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, a carbonyl group, i is 0 or an integer of 1 to 4, and j is an integer of 1 to 4 ]
R 1 in the general formulae (1-1) to (1-4) is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group, and specifically, examples thereof 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, anthracyl, and aryl groups having the aliphatic hydrocarbon group, alkoxy group, halogen atom, or the like substituted on the aromatic ring thereof; phenylmethyl, phenylethyl, naphthylmethyl, naphthylethyl, aralkyl groups in which the aliphatic hydrocarbon group, alkoxy group, halogen atom or the like is substituted on the aromatic ring thereof, and the like.
Among the compounds represented by the general formulae (1-1) to (1-4), the compounds represented by the general formula (1-1) are preferable in terms of formation of an active ester resin which is excellent in compatibility and dielectric characteristics in cured products.
When the compound represented by the general formulae (1-1) to (1-4) is used as the divinyl compound (a 2), the resin (a) having a phenolic hydroxyl group is obtained by bonding the compound (a 1) to a structural site represented by the following general formula (2).
[ Chemical 2]
[ In the general formula (2), X is represented by any one of the following general formulae (X-1) to (X-4) ]
[ Chemical 3]
[ In the general formulae (1-1) to (1-4), R 1 is an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aralkyl group, Y is an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, a carbonyl group, i is 0 or an integer of 1 to 4, and j is an integer of 1 to 4 ]
The resin (a) having a phenolic hydroxyl group may contain, as a reaction raw material, a compound other than the compound (a 1) and the divinyl compound (a 2). Examples of the other compounds include: various aldehyde compounds, etc., a compound (a 2') which is a compound other than the divinyl compound (a 2) and which can polymerize the compound (a 1), a substituent-introducing agent (a 3) for introducing an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aralkyl group as a substituent on an aromatic ring in the resin (a) having a phenolic hydroxyl group, etc.
When the compound (a 2 ') is used, the divinyl compound (a 2) is preferably 50 mass% or more, and more preferably 80 mass% or more, relative to the total of the divinyl compound (a 2) and the compound (a 2'), in terms of sufficiently exhibiting the effect of the present invention that the compatibility is good and the dielectric loss tangent in a cured product is low.
Examples of the substituent introducing agent (a 3) include: aralkyl introducers such as phenylmethanol compounds, phenylmethyl halide compounds, naphthylmethanol compounds, naphthylmethyl halide compounds, and styrene compounds.
The method for producing the resin (a) having phenolic hydroxyl groups is not particularly limited, but the ratio of the reaction raw materials is preferably adjusted so that the number of phenolic hydroxyl groups per molecule is 2 or more. For example, it can be manufactured by the following method: the compound (a 1) is used in a range of 2 to 10 mol based on 1 mol of the divinyl compound (a 2), and the mixture is heated and stirred at a temperature of about 80 to 180 ℃ under the condition of an acid catalyst. The reaction may be carried out in an organic solvent as required. After the completion of the reaction, the excess of the compound (a 1) may be distilled off as required.
Examples of the acid catalyst include p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, oxalic acid, and the like, and hydrates of these may be used. One kind of these may be used, or two or more kinds may be used in combination. In addition, these acid catalysts may also be used in the form of aqueous solutions. The amount of the acid catalyst to be added is preferably in the range of 0.01 to 20% by mass based on the compound (a 1).
Examples of the organic solvents 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; a carbitol solvent such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide; dimethylacetamide; n-methylpyrrolidone, etc. One kind of these may be used, or two or more kinds may be used in combination.
Specific examples of the resin (a) having a phenolic hydroxyl group include, for example, a structure in which phenol is used as the compound (a 1) and divinylbenzene is used as the divinyl compound (a 2), and the following general formula (a-1) is exemplified. The following general formula (A-1) is merely an example of the resin (A) having a phenolic hydroxyl group, and other resins are not excluded.
[ Chemical 4]
[ In the general formula (A-1), R 1 is independently an alkyl group having 5 or more carbon atoms, R 2 is independently a hydrogen atom or a structural part represented by the following general formula (R-1), and n is an integer of 1 to 10 ]
[ Chemical 5]
[ In the general formula (R-1), R 1 is an alkyl group having 5 or more carbon atoms, and n is an integer of 1 to 10 ]
In addition, the divinylbenzene generally commercially available sometimes contains a part of ethylstyrene. In this case, R 2 in the general formula (B-1) may be partially introduced as a structure represented by the following formula (R-2).
[ Chemical 6]
The aromatic dicarboxylic acid or the acid halide (B) thereof is not particularly limited as long as it is an aromatic compound capable of reacting with the phenolic hydroxyl group of the resin (a) having a phenolic hydroxyl group to form an ester bond. Specific examples include: benzene dicarboxylic acids such as isophthalic acid and terephthalic acid; trimellitic acid such as trimellitic acid; naphthalene dicarboxylic acids such as naphthalene-1, 4-dicarboxylic acid, naphthalene-2, 3-dicarboxylic acid, naphthalene-2, 6-dicarboxylic acid, naphthalene-2, 7-dicarboxylic acid, and the like; acid halides of these compounds and compounds in which the aliphatic hydrocarbon group, the alkoxy group, the halogen atom and the like are substituted on the aromatic ring of these compounds. Examples of the acid halide include acid chloride, acid bromide, acid fluoride, and acid iodide. One kind of these may be used, or two or more kinds may be used in combination. Among them, benzene dicarboxylic acid such as isophthalic acid and terephthalic acid or acid halide thereof is preferable for forming an active ester resin having high reactivity and excellent hardenability.
The active ester resin of the present invention can be produced, for example, by the following method: the resin (A) having a phenolic hydroxyl group and the aromatic polycarboxylic acid or the acid halide (B) thereof are heated and stirred at a temperature of about 40 to 65 ℃ in the presence of a base catalyst. The reaction may be carried out in an organic solvent as required. The reaction product may be purified by washing with water or reprecipitation, if necessary, after completion of the reaction.
Examples of the base catalyst include sodium hydroxide, potassium hydroxide, triethylamine, pyridine, and the like. One kind of these may be used, or two or more kinds may be used in combination. The base catalyst may be used in the form of an aqueous solution having a mass% of about 3 to 30%. Among them, sodium hydroxide or potassium hydroxide having a high catalyst capacity is preferable.
Examples of the organic solvents 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; a carbitol solvent such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide; dimethylacetamide; n-methylpyrrolidone, etc. One kind of these may be used, or two or more kinds may be used in combination.
The curable composition of the present invention may further contain an ester compound obtained by reacting the compound (a 1) remaining in the resin (a) having a phenolic hydroxyl group with the aromatic polycarboxylic acid or the acid halide (B) thereof.
In the case where the cure shrinkage of the curable composition of the present invention is lower, the weight average molecular weight (Mw) of the active ester resin is preferably in the range of 600 to 50,000, more preferably in the range of 800 to 30,000. The weight average molecular weight (Mw) of the active ester resin is a value measured by gel permeation chromatography (gel permeation chromatography, GPC).
The softening point of the active ester resin of the present invention is preferably in the range of 80℃to 180℃and more preferably in the range of 85℃to 160℃as measured in accordance with Japanese Industrial Standard (Japanese Industrial Standards, JIS) K7234.
In the curable composition of the present invention, the functional group equivalent of the active ester resin is preferably in the range of 200 g/equivalent to 350 g/equivalent, more preferably in the range of 200 g/equivalent to 300 g/equivalent, because the compatibility is good and the curability is also excellent. In the present invention, the functional group in the active ester resin means an ester bond site and a phenolic hydroxyl group in the active ester resin. The functional group equivalent of the active ester resin is calculated from the amount of the raw material added.
The curable composition of the present invention contains a hydrocarbon resin and a curing agent in addition to the active ester resin. The hydrocarbon resin is not particularly limited as long as it is a resin containing carbon atoms and hydrogen atoms, and examples thereof include thermoplastic elastomers. The hydrocarbon resin may be used singly or in combination. Examples of the thermoplastic elastomer include: polystyrene-based thermoplastic elastomers such as styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), and the like; olefinic thermoplastic elastomers, polybutadiene, and the like.
Among the thermoplastic elastomers, a polystyrene-based thermoplastic elastomer is preferable, and further, among them, a styrene-ethylene-butylene-styrene block copolymer (SEBS) is more preferable. Examples of commercial products of the SEBS include: "Tafutai (Tuftec)", manufactured by Santsubishi chemical corporation, "lablab (Rabalon)", manufactured by Mitsubishi chemical corporation, "Ai Kuda ma (Actymer)", manufactured by Nippon chemical corporation, manufactured by Aron chemical corporation, an "Elastomer (Elastomer) AR", manufactured by Nippon Polymer (Kraton Polymer Japan), a "Kosun (Kraton) G", manufactured by Nippon Kogyo Co, and "B series", "BI series", and the like.
The proportion of the hydrocarbon resin in the curable composition of the present invention (excluding the organic solvent) is preferably in the range of 5 to 40 mass%, more preferably in the range of 10 to 35 mass%, in terms of good compatibility and lower dielectric loss tangent in the cured product.
The hardener is not particularly limited as long as it is a compound that can react with the active ester resin, and examples of the hardener include epoxy resins.
Examples of the epoxy resin include: phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, bisphenol type epoxy resin, biphenyl type epoxy resin, triphenol methane type epoxy resin, tetraphenol ethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, and the like. One kind of these may be used, or two or more kinds may be used in combination.
In the case of using an epoxy resin as the hardener, other hardeners for epoxy resins may be used in combination in addition to the active ester resin. Examples of the other epoxy resin curing agent include: amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF 3 -amine complex, guanidine derivative, and the like; amide compounds such as dicyandiamide, and polyamide resins synthesized from a dimer of linoleic 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, biphenyl novolac resins, dicyclopentadiene-phenol addition resins, phenol aralkyl resins, naphthol aralkyl resins, triphenol methane resins, tetraphenol ethane resins, aminotriazine modified phenol resins, and the like. One kind of these may be used, or two or more kinds may be used in combination.
When an epoxy resin is used as a hardener in the curable composition of the present invention and other epoxy resin hardeners are used in combination, the blending ratio of these is preferably a ratio of 0.7 to 1.5 mol in terms of the total of the active ester resin and the functional groups in the other epoxy resin hardeners, relative to 1 mol in terms of the total of the epoxy groups in the epoxy resin.
The curable composition of the present invention may contain a cyanate resin as another resin; bismaleimide resin; benzoxazine resins; styrene-maleic anhydride resin; allyl-containing resins such as diallyl bisphenol and triallyl isocyanurate; polyphosphates; phosphate-carbonate copolymers, and the like. One kind of these may be used, or two or more kinds may be used in combination.
The curable composition of the present invention may optionally contain various additives such as a curing accelerator, a flame retardant, an inorganic filler, a silane coupling agent, a mold release agent, a pigment, and an emulsifier.
Examples of the hardening accelerator 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 (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 in view of excellent curability, heat resistance, electrical characteristics, moisture resistance and reliability.
Examples of the flame retardant include: inorganic phosphorus compounds such as ammonium phosphates (e.g., red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate); organic phosphorus compounds such as phosphate compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphane (phosphorane) compounds, organic nitrogen-containing phosphorus compounds, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and cyclic organic phosphorus compounds such as 10- (2, 7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazines; silicone flame retardants such as silicone oils, silicone rubbers, and silicone resins; 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, the amount of the flame retardant is preferably in the range of 0.1 to 20% by mass in the curable composition.
The inorganic filler is formulated, for example, when the curable composition of the present invention is used for a semiconductor sealing material. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Among them, the fused silica is preferable in that the inorganic filler can be more blended. The fused silica may be used in the form of a crushed or spherical particle, and it is preferable to mainly use spherical silica in order to increase the amount of the fused silica to be blended and to suppress the increase in melt viscosity of the curable composition. 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 mass% in the curable composition.
In addition, when the curable composition of the present invention is used for applications such as conductive paste, a conductive filler such as silver powder or copper powder can be used.
As described in detail above, the curable composition of the present invention has excellent properties of low cure shrinkage and low dielectric loss tangent in cured products. In addition, even if a hydrocarbon resin having extremely low polarity is blended, the compatibility is excellent, and therefore a uniform curable composition is formed, and a uniform cured product is obtained, and therefore, even if used for electronic component applications, adverse effects on electrical characteristics can be reduced. Accordingly, the curable composition of the present invention can be preferably used for prepregs, circuit boards, semiconductor sealing materials, semiconductor devices including cured products of semiconductor sealing materials, and the like used for electronic components. Further, the present invention can be widely used for applications other than electronic component applications, such as coating materials, adhesives, and molded articles.
When the curable composition of the present invention is used for prepregs, circuit boards, build-up films, and the like, it is generally preferable to use the curable composition after diluting the curable composition with an organic solvent. The organic solvents may be exemplified by: methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diethylene glycol acetate, propylene glycol monomethyl ether acetate, and the like. The type and amount of the organic solvent to be blended may be appropriately adjusted depending on the environment in which the curable composition is used, and for example, in the case of prepreg (circuit board) applications, a polar solvent having a boiling point of 160 ℃ or less such as methyl ethyl ketone, acetone, dimethylformamide and the like is preferably used in a proportion of 40 to 80 mass% of the nonvolatile component. In the use of the build-up film, a ketone solvent such as acetone, methyl ethyl ketone, or cyclohexanone is preferably used; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; a carbitol solvent such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like are preferably used in a proportion of 30 to 60% by mass of nonvolatile components.
The cured product of the present invention can be obtained by curing the curable composition of the present invention. The hardening method is not particularly limited, and a conventional method can be used. The cured product may be a laminate, a cast product, an adhesive layer, a coating film, a film, or the like.
The prepreg of the present invention may have a reinforcing base material and a semi-cured product of the curable composition of the present invention impregnated in the reinforcing base material. The method for obtaining a prepreg using the curable composition of the present invention is not particularly limited, and the following methods may be mentioned: the curable composition prepared by preparing the organic solvent and varnishing is impregnated into a reinforcing substrate (for example, paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass felt, glass gauze, etc.), and then heated at a heating temperature (preferably 50 to 170 ℃) corresponding to the type of solvent used, thereby semi-curing (or not curing) the curable composition.
The mass ratio of the curable composition to the reinforcing base material to be used is not particularly limited, but is preferably 20 to 60 mass% based on the resin component in the prepreg.
The semi-cured product of the curable composition can be obtained by adjusting the heating temperature and heating time and stopping the curing reaction in the middle of the curing reaction. The hardening degree of the half hardened material may be, for example, 85% or less and 5% or more. Here, the cured product may have a higher degree of cure than the half cured product. The hardening heat value of the semi-hardened material and the hardening heat value of the semi-hardened material can be measured by a differential scanning calorimeter (DIFFERENTIAL SCANNING calorimeter, DSC) and calculated by the following formula.
Hardening degree (%) = [1- (hardening heat generation amount of semi-hardened substance/hardening heat generation amount of hardening composition) ]×100
The circuit board of the present invention comprises a laminate comprising the prepreg of the present invention and a copper foil. The method for obtaining the circuit board is not particularly limited, and examples thereof include the following methods: the prepreg of the present invention is laminated as needed, and the copper foil is laminated, and is heat-pressed at 170 to 300 ℃ for 10 minutes to 3 hours under a pressure of 1 to 10 MPa.
The build-up film of the present invention contains the curable composition of the present invention. The method for producing the multilayer film is not particularly limited, and examples thereof include the following methods: the curable composition of the present disclosure is applied to a support film to form a curable composition layer, thereby producing an adhesive film for a multilayer printed wiring board.
The build-up film is required to soften under the temperature conditions (usually 70 to 140 ℃) at which the build-up film is laminated in a vacuum lamination method, and to exhibit fluidity (resin flow) that enables resin filling in via holes or through holes existing in a circuit board, the curable composition is preferably formulated with the components such as the inorganic filler and the organic solvent in order to exhibit such characteristics.
Here, the diameter of the through hole of the circuit board is usually 0.1mm to 0.5mm, and the depth is usually 0.1mm to 1.2mm, and it is generally preferable that the resin filling is possible in the above-mentioned range. In the case of laminating both sides of the circuit board, it is desirable to fill about 1/2 of the through hole.
In the method of manufacturing the adhesive film described above, specifically, it can be manufactured by: after preparing the curable composition in the form of a varnish, the composition in the form of a varnish is applied to the surface of the support film (Y), and then the organic solvent is dried by heating or blowing hot air or the like to form a composition layer (X) containing the curable composition.
The thickness of the composition layer (X) formed is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 μm to 70 μm, the thickness of the resin composition layer is preferably 10 μm to 100 μm. The composition layer (X) may be protected by a protective film described later. By protecting with the protective film, adhesion or damage of dust or the like on the surface of the resin composition layer can be prevented.
The support film (Y) and the protective film described above may be: examples of the polyester include polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes referred to as "PET (Polyethylene terephthalate)"), polyester such as polyethylene naphthalate, polycarbonate and polyimide, and metal foil such as release paper, copper foil and aluminum foil. The support film and the protective film may be subjected to a mold release treatment in addition to the matting treatment and the corona treatment. The thickness of the support film is not particularly limited, and is usually 10 μm to 150. Mu.m, preferably 25 μm to 50. Mu.m. The thickness of the protective film is preferably 1 μm to 40 μm.
The support film (Y) is laminated on the circuit board or is thermally cured to form an insulating layer, and then peeled off. When the support film (Y) is peeled off after the adhesive film is heat-cured, adhesion of dust or the like during the curing step can be prevented. When peeling is performed after hardening, the support film is usually subjected to a mold release treatment in advance.
The semiconductor sealing material of the present invention contains the curable composition of the present invention. The curable composition of the present invention has excellent properties of low cure shrinkage and low dielectric loss tangent in cured products. In addition, even if a hydrocarbon resin having extremely low polarity is blended, it has excellent compatibility, and thus a uniform curable composition is formed, and thus a uniform cured product is obtained, and thus it is also preferable for use in semiconductor sealing materials.
As described above, the semiconductor sealing material of the present invention preferably contains an inorganic filler in the curable composition of the present invention. In the semiconductor sealing material of the present invention, various additives may be blended, and examples of the additive include additives described in relation to the curable composition.
The method for producing the semiconductor sealing material of the present invention is not particularly limited, and the semiconductor sealing material can be obtained by mixing the curable composition of the present invention and, if necessary, various additives, and examples thereof include a method in which the curable composition is sufficiently melt-mixed until it becomes uniform by using an extruder, a kneader, a roll, or the like.
The semiconductor device of the present disclosure includes the cured product of the semiconductor sealing material of the present invention described above. The semiconductor device of the present invention can be obtained by heat-curing the semiconductor sealing material of the present invention, and examples thereof include the following methods: casting or molding is performed using a transfer molding machine, an injection molding machine, or the like, and further heat curing is performed at a temperature range of room temperature (20 ℃) to 250 ℃.
The cured product obtained from the curable composition of the present invention has high uniformity and low dielectric loss tangent, and thus can be preferably used for electronic components. Particularly, the resin composition is preferably used for prepregs, circuit boards, build-up films, build-up boards, semiconductor sealing materials, semiconductor devices, conductive pastes, and the like. The electronic component thus obtained can be preferably used for various purposes, and examples thereof include: industrial machine parts, general machine parts, parts such as automobiles, railways, vehicles, etc., aerospace related parts, electronic/electric parts, construction materials, containers/packaging members, living goods, sports/leisure goods, frame members for wind power generation, etc., but are not limited thereto.
Examples
The present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these examples. Further, the measurement conditions of GPC in this example are as follows.
[ Measurement conditions of GPC ]
Measurement device: "HLC-8320GPC", manufactured by Tosoh Co., ltd,
And (3) pipe column: protective column "HXL-L" manufactured by Tosoh Co., ltd "
"TSK-GEL G4000HXL" manufactured by +Tosoh Co., ltd "
"TSK-GEL G3000HXL" manufactured by +Tosoh Co., ltd "
"TSK-GEL G2000HXL" manufactured by +Tosoh Co., ltd "
"TSK-GEL G2000HXL" manufactured by +Tosoh Co., ltd "
A detector: RI (differential refractometer)
And (3) data processing: "GPC workstation (GPC WorkStation) EcoSEC-workstation (WorkStation)" manufactured by Tosoh Co., ltd "
Measurement conditions: the temperature of the pipe column is 40 DEG C
Developing solvent tetrahydrofuran
Flow rate 1.0 ml/min
Standard: according to the measurement guidelines of the "GPC-8320", the following monodisperse polystyrene having a known molecular weight is used.
(Polystyrene used)
"A-500" manufactured by Tosoh Co., ltd "
"A-1000" manufactured by Tosoh Co., ltd "
"A-2500" manufactured by Tosoh Co., ltd "
"A-5000" manufactured by Tosoh Co., ltd "
"F-1" manufactured by Tosoh Co., ltd "
"F-2" manufactured by Tosoh Co., ltd "
"F-4" manufactured by Tosoh Co., ltd "
"F-10" manufactured by Tosoh Co., ltd "
"F-20" manufactured by Tosoh Co., ltd "
"F-40" manufactured by Tosoh Co., ltd "
"F-80" manufactured by Tosoh Co., ltd "
"F-128" manufactured by Tosoh Co., ltd "
Sample: a tetrahydrofuran solution (50. Mu.l) having a mass% of 1.0% as calculated by resin solid matter conversion was filtered by a microfilter
Production example 1 production of active ester resin (1)
To a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer were added 1135.4 parts by mass of p-tert-amylphenol, 461.5 parts by mass of toluene, and 2.3 parts by mass of p-toluenesulfonic acid monohydrate. The content of the flask was heated to 120℃while stirring, 300.0 parts by mass of divinylbenzene (purity of "DVB-810" divinylbenzene manufactured by Nitrofechemical & materials Co., ltd., 81% by mass) was added dropwise at 120℃while paying attention to heat, and after the completion of the addition, the mixture was stirred at the same temperature for 1 hour to react. After the completion of the reaction, the reaction mixture was cooled to 80℃and 1.0 part by mass of a 49% by mass aqueous sodium hydroxide solution was added thereto to neutralize the reaction mixture, followed by cooling to 25 ℃.
Then, 699.2 parts by mass of isophthaloyl chloride, 3302.3 parts by mass of toluene and 2.8 parts by mass of tetrabutylammonium bromide were added, the temperature in the reaction system was controlled to 60℃or lower, and 1426.2 parts by mass of a 20% by mass aqueous sodium hydroxide solution was dropwise added over 3 hours. After the completion of the dropwise addition, stirring was continued for 1 hour directly to allow the reaction. After the completion of the reaction, the reaction mixture was allowed to stand to separate the liquid, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was left to stand to separate the liquid, and the water layer was removed. The above operation was repeated until the pH of the aqueous layer became 7, and toluene and the like were distilled off under heating and reduced pressure to obtain an active ester resin (1). If the functional group equivalent of the active ester resin (1) is calculated based on the ratio added, it is 272 g/equivalent. The GPC chart of the obtained active ester resin (1) is shown in FIG. 1.
Production example 2 production of active ester resin (2)
To a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 333.3 parts by mass of p-tert-octylphenol, 107.8 parts by mass of toluene, and 0.54 parts by mass of p-toluenesulfonic acid monohydrate were added. The content of the flask was heated to 120℃while stirring, 70.0 parts by mass of divinylbenzene (purity of "DVB-810" divinylbenzene manufactured by Nitrofechemical & materials Co., ltd., 81% by mass) was added dropwise at 120℃while paying attention to heat, and after the completion of the addition, the mixture was stirred at the same temperature for 1 hour to react. After the completion of the reaction, the reaction mixture was cooled to 80℃and 0.23 part by mass of a 49% by mass aqueous sodium hydroxide solution was added thereto to neutralize the reaction mixture, followed by cooling to 25 ℃.
Then, 163.2 parts by mass of isophthaloyl chloride, 907.2 parts by mass of toluene and 0.8 parts by mass of tetrabutylammonium bromide were added, the temperature in the reaction system was controlled to 60℃or lower, and 332.8 parts by mass of a 20% by mass aqueous sodium hydroxide solution was dropwise added over 3 hours. After the completion of the dropwise addition, stirring was continued for 1 hour directly to allow the reaction. After the completion of the reaction, the reaction mixture was allowed to stand to separate the liquid, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was left to stand to separate the liquid, and the water layer was removed. The above operation was repeated until the pH of the aqueous layer became 7, and toluene and the like were distilled off under heating and reduced pressure to obtain an active ester resin (2). If the functional group equivalent of the active ester resin (2) is calculated based on the ratio added, it is 314 g/equivalent. The GPC diagram of the obtained active ester resin (2) is shown in fig. 2.
Comparative production example 1 production of active ester resin (1')
To a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer were added 131.7 parts by mass of p-tert-butylphenol, 58.5 parts by mass of toluene, and 0.3 parts by mass of p-toluenesulfonic acid monohydrate. The content of the flask was heated to 120℃while stirring, 38.0 parts by mass of divinylbenzene (purity of "DVB-810" divinylbenzene manufactured by Nitrofechemical & materials Co., ltd., 81% by mass) was added dropwise at 120℃while paying attention to heat, and after the completion of the addition, the mixture was stirred at the same temperature for 1 hour to react. After the completion of the reaction, the reaction mixture was cooled to 80℃and 0.1 part by mass of a 49% by mass aqueous sodium hydroxide solution was added thereto to neutralize the reaction mixture, followed by cooling to 25 ℃.
Then, 88.6 parts by mass of isophthaloyl chloride, 394.1 parts by mass of toluene and 0.3 part by mass of tetrabutylammonium bromide were added, the temperature in the reaction system was controlled to 60℃or lower, and 180.7 parts by mass of a 20% by mass aqueous sodium hydroxide solution was dropwise added over 3 hours. After the completion of the dropwise addition, stirring was continued for 1 hour directly to allow the reaction. After the completion of the reaction, the reaction mixture was allowed to stand to separate the liquid, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was left to stand to separate the liquid, and the water layer was removed. The above operation was repeated until the pH of the aqueous layer became 7, and toluene and the like were distilled off under heating and reduced pressure to obtain an active ester resin (1'). If the functional group equivalent of the active ester resin (1') is calculated based on the ratio added, it is 258 g/equivalent. GPC chart of the obtained active ester resin (1') is shown in FIG. 3.
EXAMPLE 1 preparation of curable composition (1)
70 Mass% toluene solution obtained by dissolving 44 parts by mass of the active ester resin (1) obtained in production example 1 in toluene, and a hardener (Ai Bike long (EPICLON) 850-S) manufactured by Dielsen (DIC) Co., ltd.); bisphenol a type epoxy resin) 31 parts by mass, a hydrocarbon resin (taffy (Tuftec) H1221 manufactured by the asahi chemical company, inc; SESB) 25 parts by mass of a 20% by mass toluene solution obtained by dissolving in toluene and 1.5 parts by mass of a hardener for epoxy resins (ku-lei (Curezol) 1B2 MZ) manufactured by Kunzea chemical industry Co., ltd.) were uniformly mixed to obtain a curable composition (1).
EXAMPLE 2 preparation of curable composition (2)
A 70 mass% toluene solution obtained by dissolving 47 parts by mass of the active ester resin (2) obtained in production example 2 in toluene, and a hardener (Ai Bike long (EPICLON) 850-S) manufactured by Dieisen (DIC) corporation); bisphenol a type epoxy resin) 28 parts by mass, a hydrocarbon resin (taffy (Tuftec) H1221 manufactured by the asahi chemical company, inc.; SESB) 25 parts by mass of a 20% by mass toluene solution obtained by dissolving in toluene and 1.5 parts by mass of a hardener for epoxy resins (ku-lei (Curezol) 1B2 MZ) manufactured by Kunzea chemical industry Co., ltd.) were uniformly mixed to obtain a curable composition (2).
Comparative example 1 preparation of curable composition (1')
70 Mass% toluene solution obtained by dissolving 43 parts by mass of the active ester resin (1') obtained in comparative production example 1 in toluene, and a hardener (Ai Bike long (EPICLON) 850-S) (manufactured by Dielsen (DIC) Co., ltd.); bisphenol a type epoxy resin) 32 parts by mass, a hydrocarbon resin (taffy (Tuftec) H1221 manufactured by the asahi chemical company, inc.; SESB) 25 parts by mass of a 20% by mass toluene solution obtained by dissolving in toluene and 1.5 parts by mass of a hardener for epoxy resins (Kunzel (Curezol) 1B2MZ manufactured by Kukuku-koku Co., ltd.), A curable composition (1') was obtained.
The curable compositions (1), (2) and (1') obtained in example 1, example 2 and comparative example 1 were used for the following evaluation.
[ Evaluation of compatibility of varnish ]
For each curable composition, a varnish was prepared by diluting with toluene so that the total nonvolatile content became 30 mass%. The appearance of the varnish prepared was visually observed, and the compatibility of the varnish was evaluated according to the following criteria.
O: is a solution with satisfactory uniformity and transparency.
X: is a solution that does not satisfy at least one of uniformity and transparency.
[ Measurement of dielectric loss tangent ]
Toluene was distilled off from each curable composition by vacuum distillation at 100℃for 5 minutes by a rotary evaporator. The curable composition after toluene was distilled off was pressed at 180℃for 30 minutes, cured, and molded, and then heated at 200℃for 3 hours to obtain a test piece. For the obtained test piece, dielectric loss tangent at 10GHz of the test piece was measured in accordance with JIS-C-6481 by means of an impedance Material Analyzer (IMPEDANCE MATERIAL analyzer) "HP4291B" manufactured by Agilent technologies (Agilent Technologies) Co., ltd.
The compositions and evaluation results of the curable compositions (1), curable compositions (2) and curable compositions (1') obtained in example 1, example 2 and comparative example 1 are shown in table 1. The composition shown in Table 1 is the blending amount in terms of 100% by mass of the nonvolatile components.
TABLE 1
It was confirmed that the curable compositions of the present invention of example 1 and example 2 were excellent in compatibility and also suppressed in dielectric loss tangent.
On the other hand, the curable composition of comparative example 1 is an example of a curable composition in which the carbon number of the alkyl group of the compound having an alkyl group and a phenolic hydroxyl group is less than 5, which is a raw material of the active ester resin used in the curable composition. The curable composition of comparative example 1 was found to have poor compatibility and a slightly higher dielectric loss tangent than the curable composition of the present invention.

Claims (8)

1. A curable composition comprising an active ester resin, a hydrocarbon resin and a hardener, wherein the active ester resin is a reaction product of a resin (A) having a phenolic hydroxyl group, which is a reaction product of a compound (a 1) having an alkyl group having 5 or more carbon atoms and a phenolic hydroxyl group, and a divinyl compound (a 2), and an aromatic dicarboxylic acid or an acid halide (B) thereof.
2. The curable composition according to claim 1, wherein the resin (A) having a phenolic hydroxyl group has a structure represented by the following general formula (2).
[ Chemical 1]
In the general formula (2), X is represented by any one of the following general formulae (X-1) to (X-4). ]
[ Chemical 2]
[ In the general formulae (X-1) to (X-4), R 1 is an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group, Y is an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group, i is 0 or an integer of 1 to 4, and j is an integer of 1 to 4. ]
3. A cured product of the curable composition according to claim 1 or 2.
4. A prepreg comprising a reinforcing substrate and a semi-cured product of the curable composition according to claim 1 or 2 impregnated in the reinforcing substrate.
5. A circuit board comprising the prepreg according to claim 4 and a copper foil.
6. A build-up film comprising the curable composition according to claim 1 or 2.
7. A semiconductor sealing material comprising the curable composition according to claim 1 or 2.
8. A semiconductor device comprising the cured product of the semiconductor sealing material according to claim 7.
CN202280066410.9A 2021-11-18 2022-10-13 Curable composition, cured product thereof, prepreg, circuit board, build-up film, semiconductor sealing material, and semiconductor device Pending CN118103425A (en)

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JP2528784B2 (en) * 1993-09-03 1996-08-28 三洋化成工業株式会社 Oxyalkylene ether, antistatic agent and resin composition
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