CN112074553B - Thermosetting resin composition, film comprising the same, and multilayer wiring board using the same - Google Patents

Thermosetting resin composition, film comprising the same, and multilayer wiring board using the same Download PDF

Info

Publication number
CN112074553B
CN112074553B CN201980029335.7A CN201980029335A CN112074553B CN 112074553 B CN112074553 B CN 112074553B CN 201980029335 A CN201980029335 A CN 201980029335A CN 112074553 B CN112074553 B CN 112074553B
Authority
CN
China
Prior art keywords
thermosetting resin
film
resin composition
component
silane coupling
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201980029335.7A
Other languages
Chinese (zh)
Other versions
CN112074553A (en
Inventor
黑川津与志
吉田真树
寺木慎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Namics Corp
Original Assignee
Namics Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Namics Corp filed Critical Namics Corp
Publication of CN112074553A publication Critical patent/CN112074553A/en
Application granted granted Critical
Publication of CN112074553B publication Critical patent/CN112074553B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • 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
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • 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
    • 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
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits

Abstract

The present invention provides the following films and thermosetting resin compositions for producing the same. The film has excellent adhesive strength to a metal foil and a substrate material which are wirings of a printed board. In addition, the film exhibits excellent electrical characteristics in a high frequency region. Specifically, the film exhibits a low dielectric constant (epsilon) and a low dielectric loss tangent (tan delta) in the frequency range of 1 to 100 GHz. In addition, the film can be cured at a lower temperature. A thermosetting resin composition for producing a film contains: (a) a thermosetting resin having a styryl group at the terminal; (B) a styrenic thermoplastic elastomer; (C) a sulfide-based silane coupling agent; and (D) a dialkyl peroxide-based radical polymerization initiator.

Description

Thermosetting resin composition, film comprising the same, and multilayer wiring board using the same
Technical Field
The present invention relates to a thermosetting resin composition, a resin film containing the same, and a multilayer wiring board using the same.
Background
In recent years, printed wiring boards used in electric and electronic devices have been developed to reduce the size, weight, and performance of the devices. In particular, multilayer printed wiring boards are required to have higher layers, higher densities, thinner thicknesses, lighter weights, higher reliability, and molding processability.
In addition, with recent demands for higher speed of transmission signals of printed wiring boards, the increase in frequency of transmission signals has been significantly advanced. Thus, a material for a printed wiring board is required to be capable of reducing electric signal loss in a high frequency region, specifically, in a region having a frequency of 1GHz or more.
On the other hand, even for an interlayer adhesive used in a multilayer printed wiring board and an adhesive film used as a surface protective film (i.e., a cover film) of a printed wiring board, it is required to exhibit excellent electrical characteristics (low dielectric constant (epsilon) and low dielectric loss tangent (tan delta)) in a high frequency region.
The applicant of the present invention has proposed a resin film and a resin composition for producing the resin film in patent document 1. The resin film has excellent adhesive strength to a metal foil serving as a wiring of an FPC and a substrate material of the FPC such as a polyimide film. The resin film exhibits excellent electrical characteristics in a high frequency range of 1 to 10 GHz. Specifically, the resin film exhibits a low dielectric constant (epsilon) and a low dielectric loss tangent (tan delta) in the frequency range of 1 to 10 GHz.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2016-89137
Disclosure of Invention
Technical problem to be solved by the invention
In the resin composition described in patent document 1, a thermosetting resin having a styrene group at the terminal is used in order to obtain excellent electrical characteristics in a high frequency range.
On the other hand, from the viewpoint of low Coefficient of Thermal Expansion (CTE), it is known to blend glass cloth or filler into a thermosetting resin.
If glass cloth or filler is used, the adhesive strength of the thermosetting resin to the copper foil is lowered. In order to improve the adhesion to copper foil, patent document 1 proposes adding a sulfide-based silane coupling agent to a thermosetting resin.
However, the inventors of the present invention found the following problems. That is, the thermosetting resin having a styrene group at the end requires heating at a high temperature for curing. Further, if a sulfide-based silane coupling agent is added to the thermosetting resin, the radical polymerization reaction temperature is further shifted to the high temperature side.
In the examples described below, as the evaluation of the curing characteristics, a heat generation peak value obtained by differential scanning calorimeter measurement (differential scanning calorimetry: DSC) was used. In this regard, the inventors of the present invention found the following problems. That is, the heat generation peak of the thermosetting resin having a styrene group at the end obtained by DSC is as high as about 200 ℃. Further, if a sulfide-based silane coupling agent is added to a thermosetting resin having a styrene group at the end, the heat generation peak obtained by DSC is further increased by 30℃or more. From this phenomenon, it can be seen that: under the curing conditions (for example, 200 ℃ for 60 minutes) under which the sulfide-based silane coupling agent is not added, there is a possibility that the thermosetting resin is not sufficiently cured and the original characteristics cannot be obtained.
An object of the present invention is to provide a film as follows and a thermosetting resin composition for producing the film. The film has excellent adhesive strength to a metal foil and a substrate material which are wirings of a printed board. In addition, the film exhibits excellent electrical characteristics in a high frequency region. Specifically, the film exhibits a low dielectric constant (epsilon) and a low dielectric loss tangent (tan delta) in the frequency range of 1 to 100 GHz. In addition, the film has more excellent curability.
Technical proposal for solving the technical problems
In order to achieve the above object, according to one embodiment of the present invention, there is provided a thermosetting resin composition (the present thermosetting resin composition) comprising:
(A) A thermosetting resin having a styryl group at a terminal;
(B) A styrenic thermoplastic elastomer;
(C) Sulfide-based silane coupling agents; and
(D) Dialkyl peroxide-based radical polymerization initiators.
In the present thermosetting resin composition, it is preferable that the thermosetting resin of the component (a) is a thermosetting resin having a styryl group at the terminal and a phenylene ether skeleton.
In the present thermosetting resin composition, the thermosetting resin of the component (a) preferably has a number average molecular weight (Mn) of 1000 to 5000.
In the present thermosetting resin composition, it is preferable that the styrenic thermoplastic elastomer of the component (B) is hydrogenated.
In the present thermosetting resin composition, the (C) sulfide-based silane coupling agent is preferably a polysulfide-based silane coupling agent.
The present thermosetting resin composition preferably further contains (E) a silica filler.
In the present thermosetting resin composition, the silica filler of the component (E) is preferably surface-treated with a silane coupling agent.
In addition, as another embodiment of the present invention, a film (present film) comprising the present thermosetting resin composition is provided.
In addition, as another aspect of the present invention, a cured product of the present thermosetting resin composition and a cured product of the present film are provided.
In addition, as another aspect of the present invention, there are provided a multilayer wiring board comprising a cured product of the present thermosetting resin composition and a multilayer wiring board comprising a cured product of the present film.
Effects of the invention
The thermosetting resin composition can be sufficiently cured under the same conditions as those when the sulfide-based silane coupling agent is not used, even when the sulfide-based silane coupling agent is used.
The film has excellent adhesive strength to a metal foil and a substrate material which are wirings of a printed board. Further, the present film exhibits excellent electrical characteristics in a high frequency region. Specifically, the present film exhibits a low dielectric constant (ε) and a low dielectric loss tangent (tan. Delta.) in the frequency range of 1 to 100 GHz. Therefore, the film is suitable for use as an adhesive film for electric/electronic applications and a cover film for a printed wiring board. In addition, the film is suitable for interlayer adhesion between substrates of a semiconductor device. The film is particularly suitable for use as an adhesive film for millimeter wave substrates. In addition, the present film can be used as the FPC itself.
Detailed Description
Hereinafter, an embodiment of the thermosetting resin composition of the present invention will be described in detail.
The thermosetting resin composition of the present embodiment contains the following components (a) to (D).
(A) Thermosetting resin having styryl group at terminal
The thermosetting resin having a styrene group at the terminal of the component (a) (hereinafter, referred to as "thermosetting resin of the component (a)" in the present specification), preferably has a styrene group at the terminal and a phenylene ether skeleton.
The thermosetting resin having a styryl group at the terminal and a phenylene ether skeleton is preferably a compound represented by the following general formula (1).
[ chemical 1]
In the formula (1) - (O-X-O) -is represented by the following general formula (2) or (3).
[ chemical 2]
[ chemical 3]
In the formula (2), R 1 、R 2 、R 3 、R 7 R is as follows 8 Alkyl groups having 6 or less carbon atoms or phenyl groups may be the same or different from each other. R is R 4 、R 5 R is as follows 6 Is a hydrogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group, and may be the same or different from each other.
In the formula (3), R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 R is as follows 16 Is a hydrogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group, and may be the same or different from each other. -A-is a linear, branched or cyclic 2-valent hydrocarbon group having 20 or less carbon atoms.
In the formula (1) - (Y-O) -is represented by the general formula (4). In- (Y-O) -one structure or two or more structures are arranged randomly.
[ chemical 4]
In the formula (4), R 17 R is as follows 18 Alkyl groups having 6 or less carbon atoms or phenyl groups may be the same or different from each other. R is R 19 R is as follows 20 Is a hydrogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group, and may be the same or different from each other.
In the formula (1), a and b are integers of 0 to 100. at least one of a and b is not 0.
Examples of the "A" in the formula (3) include 2-valent organic groups such as methylene, ethylene, 1-methylethylene, 1-propylene, 1, 4-phenylenedi (1-methylethylene), 1, 3-phenylenedi (1-methylethylene), cyclohexylene, phenylmethylene, naphthylmethylene, and 1-phenylenedi. However, the-A-in the formula (3) is not limited to these groups.
As the compound represented by the formula (1), R is preferable 1 、R 2 、R 3 、R 7 、R 8 、R 17 R is as follows 18 Is an alkyl group having 3 or less carbon atoms and R 4 、R 5 、R 6 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 19 R is as follows 20 Is a compound having a hydrogen atom or an alkyl group having 3 or less carbon atoms. Particularly more preferably- (O-X-O) -represented by the general formula (2) or the general formula (3) is a compound represented by the general formula (5), the general formula (6) or the general formula (7), and- (Y-O) -represented by the general formula (4) is a compound represented by the formula (8) or the formula (9) or- (Y-O) -represented by the general formula (4) is a structure in which a compound represented by the formula (8) and a compound represented by the formula (9) are randomly arranged.
[ chemical 5]
[ chemical 6]
[ chemical 7]
[ chemical 8]
[ chemical 9]
The method for producing the compound represented by the formula (1) is not particularly limited. For example, the compound represented by the formula (1) can be produced by subjecting the terminal phenolic hydroxyl group of a 2-functional phenylene ether oligomer obtained by oxidative coupling of a 2-functional phenol compound and a 1-functional phenol compound to vinylbenzyl ether.
The number average molecular weight of the thermosetting resin of the component (a) is preferably in the range of 1000 to 5000, more preferably in the range of 1000 to 3000, and even more preferably in the range of 1000 to 2500 in terms of polystyrene by GPC. When the number average molecular weight is 1000 or more, tackiness is less likely to occur when the resin composition of the present embodiment is formed into a film. In addition, if the number average molecular weight is 5000 or less, the resin composition of the present embodiment can be inhibited from decreasing in solubility in solvents. Further, by using the thermosetting resin having the component (a) with a number average molecular weight in the above range, the electric characteristics and curability of the resin composition of the present embodiment at high frequencies can be improved.
(B) Styrene thermoplastic elastomer
The styrenic thermoplastic elastomer of component (B) refers to a thermoplastic elastomer containing styrene, a homolog thereof or an analog thereof.
The presence of unsaturated bonds in the molecule leads to an increase in the dielectric loss tangent (tan delta). Therefore, as the styrene-based thermoplastic elastomer of the component (B), a hydrogenated styrene-based thermoplastic elastomer is preferably used. By using the hydrogenated styrenic thermoplastic elastomer, a low dielectric loss tangent (tan delta) can be further obtained as compared with using an unhydrogenated styrenic thermoplastic elastomer.
Examples of the component (B) include styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block copolymer (SBBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene block copolymer (SEP), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-propylene-styrene block copolymer (SEEPS), and hydrogenated products of these copolymers. The compounds exemplified herein may be used alone or in combination of two or more.
The mass ratio of the component (a) to the component (B) is preferably the component (a): component (B) =10: 90-90: 10, more preferably 20: 80-80: 20, further preferably 20: 80-50: 50.
if the component (B) is increased, the component (a) is relatively decreased, so that the thermosetting resin composition of the present embodiment is poor in curability, and it becomes difficult to obtain properties such as peel strength. Conversely, if the component (a) is increased, the component (B) is relatively decreased, so that the film comprising the thermosetting resin composition of the present embodiment and the cured product thereof become hard and brittle, and the film properties are impaired. Therefore, there is a possibility that cracks, peel strength, and the like may occur as physical properties of the cured product are reduced.
(C) Sulfide-based silane coupling agent
The thermosetting resin composition of the present embodiment can maintain the electrical characteristics of a film containing the thermosetting resin composition at high frequencies and can improve the adhesive strength with a copper foil widely used as a wiring of a printed board by containing a sulfide-based silane coupling agent as the component (C). As a result, the risk of the thermosetting resin composition being peeled off after bonding can be reduced.
The sulfide-based silane coupling agent is preferably a polysulfide-based silane coupling agent having 2 or more sulfur bonds.
Examples of polysulfide-based silane coupling agents include bis (trimethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) tetrasulfide, bis (tributoxysilylpropyl) tetrasulfide, bis (dimethoxymethylsilylpropyl) tetrasulfide, bis (diethoxymethylsilylpropyl) tetrasulfide, bis (dibutoxysilanelpropyl) tetrasulfide, bis (trimethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) disulfide, bis (tributoxysilylpropyl) disulfide, bis (dimethoxymethylsilylpropyl) disulfide, bis (diethoxymethylsilylpropyl) disulfide, and bis (dibutoxysilanelpropyl) disulfide.
The number of sulfur bonds in the polysulfide-based silane coupling agent is preferably 2, 3 or 4, and particularly preferably 4, from the viewpoint of adhesion.
For polysulfide-based silane coupling agents, from the viewpoint of stability, alkoxy groups bonded to Si are preferably methoxy or ethoxy, and more preferably ethoxy.
The sulfide-based silane coupling agent of the component (C) is preferably contained in an amount of 0.1 to 5.0 parts by mass, more preferably 0.1 to 3.0 parts by mass, and even more preferably 0.1 to 2.0 parts by mass, based on 100 parts by mass of the total of the component (a) and the component (B).
(D) Dialkyl peroxide radical polymerization initiator
By adding a dialkyl peroxide-based radical polymerization initiator as component (D) to the thermosetting resin composition of the present embodiment, the radical polymerization temperature can be suppressed from moving to the high temperature side even when the thermosetting resin having a styryl group at the terminal is contained as component (a) and the sulfide-based silane coupling agent is contained as component (C). As the radical polymerization initiator, diacyl peroxide, hydroperoxide, ketone peroxide, and the like are also available. However, these radical polymerization initiators hardly inhibit the shift of the radical polymerization reaction temperature to the high temperature side.
The dialkyl peroxide-based radical polymerization initiator as the component (D) is preferably a polymerization initiator that is solid at ordinary temperature. The polymerization initiator which is solid at ordinary temperature is excellent in handling property because it is difficult to volatilize.
The dialkyl peroxide-based radical polymerization initiator of the component (D) is preferably dicumyl peroxide (manufactured by Nikko Co., ltd., product name: PERCUMYLD) from the viewpoint of storage stability.
The dialkyl peroxide-based radical polymerization initiator of the component (D) is preferably contained in an amount of 0.1 to 5.0 parts by mass, more preferably 0.1 to 3.0 parts by mass, and even more preferably 0.1 to 2.0 parts by mass, based on 100 parts by mass of the total of the component (a) and the component (B).
The thermosetting resin composition of the present invention may contain the following components as needed in addition to the above components (a) to (D).
(E) Silica filler
In the case of containing a silica filler as the component (E), the Coefficient of Thermal Expansion (CTE) of the film comprising the thermosetting resin composition of the present invention can be reduced.
The surface treatment of the silica filler of component (E) with a silane coupling agent is preferable because the moisture resistance reliability can be improved (the rate of change in dielectric constant and dielectric loss tangent is small).
The silane coupling agent used for the surface treatment is preferably a silane coupling agent represented by the following general formula (10).
[ chemical 10]
In the above formula, R 1 ～R 3 Are each independently an alkyl group having 1 to 3 carbon atoms, R 4 Is a functional group having an unsaturated double bond at least at the terminal, and n is 3 to 9. R of the formula (10) from the viewpoint of improving peel strength 4 Any one of vinyl, (meth) acryl and (meth) acryloyloxy is preferable. In the general formula (10), if n is 5 to 9, the stress against external force of the cured product of the thermosetting resin composition can be relaxed, so that excellent solder heat resistance can be obtained. In particular, if R 4 The vinyl group can provide extremely excellent solder heat resistance.
R of the formula (10) from the viewpoint of improving peel strength 4 Vinyl groups are preferred. In general formula (10), n is preferably 3 or 4 from the viewpoint of low thermal expansion.
The silane coupling agent represented by the general formula (10) includes octenyl trialkoxysilane and (meth) acryloxyalkyl trialkoxysilane. Examples of octenyl trialkoxysilane include octenyl trimethoxysilane and octenyl triethoxysilane. Examples of the (meth) acryloyloxy alkyl trialkoxysilane include (meth) acryloyloxy octyl trimethoxysilane and (meth) acryloyloxy octyl triethoxysilane. From the viewpoint of improving the peel strength, octenyl trimethoxysilane is more preferably used. As the commercially available silane coupling agent represented by the general formula (10), there may be mentioned octenyl trimethoxysilane (trade name: KBM-1083) produced by Xin Yue chemical and methacryloxy octyl trimethoxysilane (trade name: KBM-5803) produced by Xin Yue chemical.
Further, as a silane coupling agent other than the above, 3-methacryloxypropyl trimethoxysilane and the like are mentioned. As a commercially available product of the silane coupling agent, 3-methacryloxypropyl trimethoxysilane (trade name: KBM-503) produced by the more chemical system is mentioned.
The silane coupling agent used in the surface treatment may be used alone or in combination of two or more.
The silica filler of the component (E) includes, but is not particularly limited to, fused silica, ordinary silica, spherical silica, crushed silica, crystalline silica, amorphous silica, and the like. The silica filler is preferably spherical fused silica from the viewpoints of dispersibility of the silica filler, flowability of the thermosetting resin composition, surface smoothness of the cured product, dielectric characteristics, low thermal expansion, and adhesion. The average particle diameter (average maximum diameter in the case of not spherical) of the silica filler is not particularly limited. However, if the specific surface area is small, the average particle diameter of the silica filler is preferably 0.05 to 20. Mu.m, more preferably 0.1 to 15. Mu.m, still more preferably 0.5 to 10. Mu.m, when the improvement of moisture resistance after curing is considered. The average particle diameter of the silica filler means a volume-based median particle diameter measured by a laser scattering diffraction particle size distribution measuring apparatus. The silica filler used as the component (E) may be used alone or in combination of two or more.
The method of surface-treating the silica filler with the silane coupling agent is not particularly limited, and examples thereof include a dry method and a wet method.
In the dry method, a silica filler and a silane coupling agent in an appropriate amount relative to the surface area of the silica filler are placed in a stirring device, and stirred under appropriate conditions. Alternatively, the silica filler may be previously placed in a stirring device, and a silane coupling agent or the like in an appropriate amount with respect to the surface area of the silica filler may be added by dropping or spraying the silica filler in a stock solution or a solution while stirring the silica filler under appropriate conditions. The silane coupling agent can be uniformly attached to the surface of the silica filler by stirring, and the surface treatment can be performed (by hydrolyzing it). Examples of the stirring device include a henschel mixer and the like capable of stirring and mixing by rotating at a high speed. However, the stirring device is not particularly limited.
In the wet method, a surface treatment solution is prepared by dissolving a silane coupling agent in an amount sufficient to surface area of a silica filler subjected to surface treatment in water or an organic solvent. The silica filler is added to the surface treatment solution and stirred so as to be in a slurry form, whereby the silane coupling agent and the silica filler are sufficiently reacted. Thereafter, the silica filler is separated from the surface treatment solution by filtration, centrifugal separation, or the like, and is heat-dried, thereby performing surface treatment.
When the silica filler is contained as the component (E), it is preferably contained in an amount of 50 to 600 parts by mass, more preferably 100 to 500 parts by mass, and even more preferably 200 to 400 parts by mass, based on 100 parts by mass of the total of the component (a) and the component (B). In the case of surface treatment of the silica filler, these ranges are mass ranges containing a surface treatment agent (e.g., a silane coupling agent).
The thermosetting resin composition of the present embodiment may further contain components other than the above components (a) to (E), as needed. Specific examples of such components include epoxy resins, curing agents for epoxy resins, other thermosetting resins, curing agents for other thermosetting resins, thermoplastic resins, antioxidants, defoamers, leveling agents, thixotropic agents, flame retardants, antifrosters, anti-blocking agents, and dispersants. The types and amounts of the components (compounding agents) are as described in the conventional methods.
(preparation of thermosetting resin composition)
The thermosetting resin composition of the present embodiment can be produced by a conventional method.
For example, the above components (a) to (D) (and when the thermosetting resin composition contains the above component (E) and/or any other component (s)), are dissolved and mixed by a heating and stirring mixer in the presence of a solvent. Alternatively, the following means may be employed: the above components (a) to (D) are dissolved in a predetermined solvent so that the components are contained in a desired ratio, and these components (when the thermosetting resin composition contains the above component (E) and/or other optional components, these optional components are also added to a mixer at a predetermined amount, and mixed and stirred. When the filler such as component (E) is contained, a dispersing device is preferably used.
The thermosetting resin composition of the present embodiment has the following suitable characteristics.
The thermosetting resin composition of the present embodiment has excellent electrical characteristics at high frequencies. Specifically, the thermosetting resin composition preferably has a dielectric constant (. Epsilon.) of 3.5 or less, more preferably 3.3 or less in the frequency range of 1 to 100 GHz. The dielectric loss tangent (tan delta) in the frequency range of 1 to 100GHz is preferably 0.004 or less, more preferably 0.003 or less.
By setting the dielectric constant (epsilon) and the dielectric loss tangent (tan delta) in the frequency range of 1 to 100GHz to the above-described ranges, the electric signal loss in the high-frequency range can be reduced.
In addition, the thermosetting resin composition of the present embodiment is excellent in moisture resistance reliability of electrical characteristics at high frequencies. Specifically, by the procedure described in the examples described later, the rate of change of the dielectric constant (. Epsilon.) in the frequency range of 1 to 100GHz after 1000 hours of standing at 85 ℃ C./85% RH is preferably 5% or less, more preferably 3% or less. The change rate (tan δ) of the dielectric loss tangent in the frequency range of 1 to 100GHz is preferably 120% or less, more preferably 80% or less, and still more preferably 60% or less.
The thermosetting resin composition of the present embodiment has sufficient adhesive strength as a thermosetting product. Specifically, the peel strength (180 degree peel) of the thermosetting resin composition to a copper foil (glossy surface and roughened surface) measured in accordance with JIS K6854-2 is preferably 4N/cm or more, more preferably 6N/cm or more.
The heat generation peak value of the thermosetting resin composition of the present embodiment is 190 ℃ or lower when measured by a Differential Scanning Calorimeter (DSC), and is lower than 200 ℃ when the component (a) alone. Therefore, the thermosetting resin composition of the present embodiment can be sufficiently cured under the same predetermined curing conditions of 200 ℃.
A film containing the thermosetting resin composition of the present embodiment (hereinafter referred to as "film of the present embodiment" in the present specification) can be obtained by a well-known method. For example, the thermosetting resin composition of the present embodiment is diluted with a solvent to an appropriate viscosity to obtain a coating liquid. The coating liquid is applied to at least one surface of the support and dried. Thus, the film according to the present embodiment can be provided as a film with a support or a film peeled from a support.
Examples of the solvent that can be used for the coating liquid include ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; high boiling point solvents such as cyclohexanone, dimethylformamide and 1-methyl-2-pyrrolidone. The amount of the solvent to be used is not particularly limited as long as the coating liquid can be adjusted to have an optimal viscosity. The amount of the solvent to be used is preferably 20 to 70% by mass based on the solid content.
The support may be appropriately selected according to the method of producing the film and the use thereof, and is not particularly limited. Examples of the support include metal foils such as copper and aluminum, substrates made of resins such as polyimide, liquid crystal polymer and PTFE, and carrier films made of resins such as polyester and polyethylene.
The method of applying the coating liquid is not particularly limited. Examples of the coating method include a slit die method, a gravure method, and a doctor blade method. The coating method may be appropriately selected according to the desired film thickness or the like.
The thickness of the film of the present embodiment is appropriately designed based on the characteristics required for the application, such as the substrate thickness, the component thickness, and the mechanical strength. The thickness of the film of this embodiment is usually 10 to 200. Mu.m.
The drying conditions are appropriately designed according to the type and amount of the solvent used for the coating liquid, the thickness of the coating liquid applied, the drying apparatus, and the like, and are not particularly limited. For example, the drying may be carried out at a temperature of 60 to 150℃under atmospheric pressure.
In the case where the film of the present embodiment is used as an adhesive film for electric/electronic use, the procedure for use thereof is as follows.
The film according to the present embodiment is placed on the surface to be bonded of one of the objects to be bonded using the film according to the present embodiment. Thereafter, the other object is placed so that the surface to be bonded contacts the exposed surface of the film. Here, when a film with a support is used, the film is placed so that the exposed surface of the film contacts the surface to be bonded of one object. The film is then temporarily pressed against the surface to be bonded. Here, the temperature at the time of temporary press-bonding may be set to 130 ℃, for example. At the time of temporary press bonding, the support is peeled off to expose the film.
Next, the other object is placed on the exposed surface of the film (insulating film) so that the surface to be bonded is in contact with the exposed surface of the film. After these steps, thermocompression bonding is performed at a predetermined temperature for a predetermined time, and then thermal curing is performed.
The temperature at the time of thermocompression bonding is preferably 100 to 160 ℃. The time for thermocompression bonding is preferably 0.5 to 3 minutes.
The temperature of the heat curing is preferably 160 to 240 ℃, more preferably 180 to 220 ℃. The time for heat curing is preferably 30 to 120 minutes.
In addition, the temporary pressure bonding step and the thermocompression bonding step may be omitted.
In addition, the following steps may be performed instead of using a material that has been previously formed. That is, the thermosetting resin composition of the present embodiment diluted with a solvent to an appropriate viscosity is applied to the surface to be bonded of one of the objects to be bonded, and dried. Then, one of the objects is placed on the dried thermosetting resin composition.
In the case where the film of the present embodiment is used as a cover film, the steps for use thereof are as follows.
The film according to the present embodiment is disposed at a predetermined position of the resin substrate with wiring having wiring patterns formed on the main surface, that is, at a position covered with a cover film on the side where the wiring patterns are formed. Thereafter, temporary press bonding, thermocompression bonding, and heat curing are performed at a predetermined temperature and for a predetermined time. In addition, the temporary pressure bonding step and the thermocompression bonding step may be omitted.
The temperature and time for temporary press-bonding, thermocompression bonding, and heat curing are the same as in the case of using as the adhesive film for electric/electronic use described above.
The thermosetting resin composition of the present embodiment and the cured product of the film of the present embodiment can be used as a flexible wiring board including a wiring resin substrate having a wiring pattern formed on a main surface thereof, because of their excellent electrical characteristics at high frequencies.
The wired resin substrate includes a resin substrate such as a polyimide film and a liquid crystal polymer film, and a wiring pattern formed on a main surface of the resin substrate. The flexible wiring board is obtained by bonding the film of the present embodiment to the wiring pattern side of the wiring resin substrate and curing the film through the steps described above.
The flexible wiring board according to the present embodiment may be formed as follows. The thermosetting resin composition of the present embodiment diluted with a solvent so as to have an appropriate viscosity is applied to the wiring pattern side of the above-described wiring-carrying resin substrate. Thereafter, a layer formed of a cured product of the resin composition is formed on the wiring pattern.
The film of the present embodiment can be used for interlayer adhesion between substrates of a semiconductor device. In this case, the object to be bonded is a plurality of substrates stacked on each other, which constitute the semiconductor device. In addition, the thermosetting resin composition of the present embodiment diluted with a solvent so as to have an appropriate viscosity may be used instead of the film formed in advance for interlayer adhesion between substrates of a semiconductor device.
The multilayer wiring board of the present embodiment includes a cured product of the thermosetting resin composition of the present embodiment or a cured product of the film of the present embodiment. The multilayer wiring board of the present embodiment is produced by curing the thermosetting resin composition of the present embodiment or the film of the present embodiment. The multilayer wiring board is excellent in heat resistance, moisture resistance reliability, and moisture absorption reflow resistance because it includes a cured product of the thermosetting resin composition of the present embodiment or a cured product of the film of the present embodiment. Examples of the multilayer wiring board include substrates for microwave and millimeter wave communication, and particularly printed wiring boards for high frequency applications such as vehicle-mounted millimeter wave radar substrates. The method for manufacturing the multilayer wiring board is not particularly limited. As a method for manufacturing a multilayer wiring board, the same method as that in the case of manufacturing a printed wiring board using a general prepreg can be used.
Examples
Hereinafter, the present embodiment will be described in detail with reference to examples. However, the present embodiment is not limited thereto.
Examples 1 to 9 and comparative examples 1 to 4
Sample preparation and measurement method
The components were measured so as to be the blending ratios (parts by mass) shown in the following table. Thereafter, the component (A) and the component (B) were placed in a heating stirrer into which toluene was previously charged in a predetermined amount. While heating to 70 ℃, the stirring blade was rotated at 35rpm, and dissolution mixing was performed at normal pressure for 2 hours. After cooling to room temperature, the other components were put into a heating stirrer, and stirring and mixing were performed for 1 hour by rotating a stirring blade at a rotation speed of 60 rpm. Thereafter, a predetermined amount of toluene was further added and stirred so as to have a viscosity suitable for application, and the resin composition was diluted. Thereafter, the resin composition was dispersed by a wet-type micronizer (NANOMIZER MN2-2000AR, manufactured by Jitian Chengsu Co., ltd.).
The coating liquid containing the resin composition thus obtained was applied to one surface of a support (a PET film after release treatment), and dried at 100 ℃. Thus, a film (thickness: 100 μm) with a support was obtained.
The shorthand symbols in the tables indicate the following.
Component (A)
(A1) The method comprises the following steps OPE-2St 2200 (product name, mitsubishi gas chemical Co., ltd.), the phenylene ether oligomer (modified polyphenylene ether represented by the above general formula (1) (in the formula (1) - (O-X-O) -is represented by the general formula (5)), the- (Y-O) -in the formula (1) is the formula (8)) (mn=2200)
Component (B)
(B1) The method comprises the following steps Styrene-ethylene-butene-styrene Block copolymer (SEBS), G1652 (product name, manufactured by Korea Polymer Japanese Co., ltd.)
Component (C)
(C1) The method comprises the following steps Bis (triethoxysilylpropyl) tetrasulfide, KBE846 (product name, from Xinyue chemical Co., ltd.)
Component (D)
(D1) The method comprises the following steps Dicumyl peroxide (PERCUMYL D) (manufactured by Nipple Co., ltd.)
(D' 1): tert-butyl peroxybenzoate, PERBUTYL Z (manufactured by Nipple Co., ltd.)
Component (E)
(E1) The method comprises the following steps Untreated spherical silica, FB-3SDX (manufactured by Kagaku Co., ltd.), had an average particle diameter of 3.4. Mu.m
(E2) The method comprises the following steps FB-3SDX surface-treated with 7-octenyl trimethoxysilane (trade name: KBM-1083, silane coupling agent manufactured by Xinyue chemical Co., ltd.)
(E3) The method comprises the following steps FB-3SDX surface-treated with 8-methacryloxyoctyl trimethoxysilane (trade name: KBM-5803, silane coupling agent manufactured by Xinyue chemical Co., ltd.)
(E4) The method comprises the following steps FB-3SDX surface-treated with 3-methacryloxypropyl trimethoxysilane (trade name: KBM-503, silane coupling agent manufactured by Xinyue chemical Co., ltd.)
The surface treatments (E2) to (E4) were performed by the dry method described above. At this time, regarding the amount of the silane coupling agent to be added, the minimum coverage area (m 2 Per g) and specific surface area (m) of the silica filler 2 /g), the amount of silica filler surface covered with a layer is calculated and determined.
Addition amount (g) of silane coupling agent= (mass (g) of silica filler x specific surface area (m) 2 (g))/minimum coverage area (m) of silane coupling agent 2 /g)
DSC peak temperature: the test piece was mounted on a measuring instrument using a differential scanning calorimeter (DSC, NETZSCH DSC 204F 1 Phoenix). The heat generation peak was read from a DSC curve obtained by a predetermined temperature program (temperature rise from 25 ℃ to 300 ℃ at 5 ℃ C./min). The temperature of the peak top was set to be the DSC peak temperature.
Dielectric constant (ε), dielectric loss tangent (tan δ): the film was cured by heating at 200℃for 60 minutes and peeled from the support. Thereafter, a test piece (50.+ -. 1 mm. Times.70.+ -. 2 mm) was cut out from the film, the thickness of the test piece was measured, and the dielectric constant (. Epsilon.) and the dielectric loss tangent (tan. Delta.) of the test piece were measured by the dielectric resonator method (SPDR method) (10 GHz).
Moisture resistance reliability: the test pieces described above were left to stand at 85℃under 85% RH for 1000 hours. Thereafter, the dielectric constant (. Epsilon.) and the dielectric loss tangent (. Tan. Delta.) of the test piece were measured by the same procedure as described above.
Peel strength: copper foil (CF-T9 FZSV, manufactured by Fufield Metal foil powder Co., ltd., thickness: 18 μm) was adhered to both sides of the film, and press-cured (200 ℃ C., 60 minutes, 10 kgf) was carried out by a press. The test piece was cut to a width of 10mm and peeled off by a universal tester. The peel strength (180-degree peel) of the test piece was measured in accordance with JIS K6854-2. The peel strength was measured for the peel strength when the glossy surface of the copper foil was adhered to the inner side and the peel strength when the roughened surface was adhered.
TABLE 1
TABLE 2
/>
Examples 1 to 9 are excellent in all aspects of dielectric characteristics (dielectric constant (. Epsilon.), dielectric loss tangent (tan. Delta.)) (initial value) and peel strength with respect to copper foil. The DSC peak temperature is 190 ℃ or lower. In addition, the moisture resistance reliability of example 1 and examples 7 to 9 was also excellent.
In example 2, the blending ratio of the components (A1) and (B1) was changed from that of example 1. Examples 3 to 5 are examples in which the blending ratio of the component (C1) was changed from example 2. Example 6 is an example in which the blending ratio of the components (A1), (B1) and (D1) was changed from that of example 1. Examples 7 to 9 are examples in which component (E2) was changed to component (E3), (E4) or (E1) respectively, with respect to example 1. Examples 1, 7, and 8 using the silica fillers (E2), (E3), and (E4) surface-treated with the silane coupling agent further improved moisture resistance reliability as compared with example 9 using the untreated silica filler (E1).
In comparative examples 1 and 2, the component (D' 1) of the alkyl peroxide-based radical polymerization initiator was used instead of the component (D1) of the dialkyl peroxide-based radical polymerization initiator. In comparative examples 1 and 2, the DSC peak temperature was 230℃or higher.
In comparative example 3 in which the component (C1) was not used, the DSC peak temperature was 190℃or lower. However, the peel strength to the copper foil tends to be low, and the peel strength to the glossy surface is particularly low, 4N/cm or less.
In comparative example 4 in which component (C1) was not used and (D1) (dicumyl peroxide) was used, the DSC peak temperature was 190℃or lower. However, the peel strength to the copper foil tends to be low, and the peel strength to the glossy surface is particularly low, 4N/cm or less.

Claims (11)

1. A thermosetting resin composition comprising:
(A) A thermosetting resin having a styryl group at a terminal;
(B) A styrenic thermoplastic elastomer;
(C) Sulfide-based silane coupling agents;
(D) Dialkyl peroxide radical polymerization initiators; the method comprises the steps of,
(E) A silica filler,
the dialkyl peroxide-based radical polymerization initiator as the component (D) is contained in an amount of 0.1 to 5.0 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B).
2. The thermosetting resin composition according to claim 1, wherein,
the thermosetting resin of the component (a) is a thermosetting resin having a styryl group at the terminal and a phenylene ether skeleton.
3. The thermosetting resin composition according to claim 1 or 2, wherein,
the thermosetting resin of the component (A) has a number average molecular weight Mn of 1000 to 5000.
4. The thermosetting resin composition according to claim 1 or 2, wherein,
the styrenic thermoplastic elastomer of the component (B) is hydrogenated.
5. The thermosetting resin composition according to claim 1 or 2, wherein,
the sulfide-based silane coupling agent (C) is a polysulfide-based silane coupling agent.
6. The thermosetting resin composition according to claim 1 or 2, wherein,
the silica filler of the component (E) is surface-treated with a silane coupling agent.
7. A film comprising the thermosetting resin composition of any one of claims 1 to 6.
8. A cured product of the thermosetting resin composition according to any one of claims 1 to 6.
9. A cured product of the film of claim 7.
10. A multilayer wiring board comprising a cured product of the thermosetting resin composition according to claim 8.
11. A multilayer wiring board comprising the cured product of the film of claim 9.
CN201980029335.7A 2018-05-29 2019-05-22 Thermosetting resin composition, film comprising the same, and multilayer wiring board using the same Active CN112074553B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2018102458 2018-05-29
JP2018-102458 2018-05-29
PCT/JP2019/020331 WO2019230531A1 (en) 2018-05-29 2019-05-22 Thermosetting resin composition, film containing same, and multilayer wiring board using same

Publications (2)

Publication Number Publication Date
CN112074553A CN112074553A (en) 2020-12-11
CN112074553B true CN112074553B (en) 2023-10-20

Family

ID=68698831

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201980029335.7A Active CN112074553B (en) 2018-05-29 2019-05-22 Thermosetting resin composition, film comprising the same, and multilayer wiring board using the same

Country Status (5)

Country Link
JP (1) JP7233740B2 (en)
KR (1) KR20210015760A (en)
CN (1) CN112074553B (en)
TW (1) TWI818994B (en)
WO (1) WO2019230531A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022161530A (en) * 2021-04-09 2022-10-21 エルジー・ケム・リミテッド Thermosetting resin composition, and cured product thereof and prepreg, laminate including cured product of composition or cured product of prepreg, metal-foil-clad laminate, and printed wiring board
WO2024048055A1 (en) * 2022-08-31 2024-03-07 ナミックス株式会社 Resin composition, adhesive film, bonding sheet for interlayer adhesion, and resin composition for semiconductor package with antenna

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200813124A (en) * 2006-08-08 2008-03-16 Namics Corp Thermosetting resin composition and a un-cured film constituted by such thermosetting resin composition
CN101314630A (en) * 2007-05-31 2008-12-03 三菱瓦斯化学株式会社 Curable resin composition, curable film and their cured products
JP2010111758A (en) * 2008-11-06 2010-05-20 Hitachi Chem Co Ltd Resin composition, prepreg, laminate and printed board
CN102807658A (en) * 2012-08-09 2012-12-05 广东生益科技股份有限公司 Polyphenyl ether resin composite and prepreg and copper clad laminate made of polyphenyl ether resin composite
CN104508040A (en) * 2012-08-10 2015-04-08 纳美仕有限公司 Resin composition, and adhesive film and coverlay film each of which is formed of same
CN105051111A (en) * 2013-03-22 2015-11-11 纳美仕有限公司 Resin composition and adhesive film, coverlay film, and interlayer adhesive using resin composition
CN106398173A (en) * 2015-07-30 2017-02-15 松下知识产权经营株式会社 Thermosetting resin composition, and resin varnish, metal foil with resin, resin film, metal-clad laminate, and printed wiring board using the same
CN107075222A (en) * 2014-11-11 2017-08-18 纳美仕有限公司 Resin combination, the dielectric film and semiconductor device for having used the resin combination

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007262191A (en) 2006-03-28 2007-10-11 Nippon Steel Chem Co Ltd Flame-retardant curable resin composition
JP2008248141A (en) 2007-03-30 2008-10-16 Nippon Steel Chem Co Ltd Flame retardant curable resin composition
JP2009040934A (en) 2007-08-10 2009-02-26 Nippon Steel Chem Co Ltd Curable resin composition
JP2009179730A (en) * 2008-01-31 2009-08-13 Mitsubishi Gas Chem Co Inc Curable resin composition, prepreg and copper-clad laminate
WO2015089807A1 (en) * 2013-12-19 2015-06-25 Dow Global Technologies Llc Vinyl-capped poly(phenylene) ether and styrene-butadiene copolymer blends for curable compositions

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200813124A (en) * 2006-08-08 2008-03-16 Namics Corp Thermosetting resin composition and a un-cured film constituted by such thermosetting resin composition
CN101314630A (en) * 2007-05-31 2008-12-03 三菱瓦斯化学株式会社 Curable resin composition, curable film and their cured products
JP2010111758A (en) * 2008-11-06 2010-05-20 Hitachi Chem Co Ltd Resin composition, prepreg, laminate and printed board
CN102807658A (en) * 2012-08-09 2012-12-05 广东生益科技股份有限公司 Polyphenyl ether resin composite and prepreg and copper clad laminate made of polyphenyl ether resin composite
CN104508040A (en) * 2012-08-10 2015-04-08 纳美仕有限公司 Resin composition, and adhesive film and coverlay film each of which is formed of same
CN105051111A (en) * 2013-03-22 2015-11-11 纳美仕有限公司 Resin composition and adhesive film, coverlay film, and interlayer adhesive using resin composition
CN107075222A (en) * 2014-11-11 2017-08-18 纳美仕有限公司 Resin combination, the dielectric film and semiconductor device for having used the resin combination
CN106398173A (en) * 2015-07-30 2017-02-15 松下知识产权经营株式会社 Thermosetting resin composition, and resin varnish, metal foil with resin, resin film, metal-clad laminate, and printed wiring board using the same

Also Published As

Publication number Publication date
KR20210015760A (en) 2021-02-10
TWI818994B (en) 2023-10-21
JPWO2019230531A1 (en) 2021-07-08
WO2019230531A1 (en) 2019-12-05
CN112074553A (en) 2020-12-11
TW202003690A (en) 2020-01-16
JP7233740B2 (en) 2023-03-07

Similar Documents

Publication Publication Date Title
JP7202691B2 (en) Resin compositions, films, laminates and semiconductor devices
TW202003691A (en) Resin composition, prepreg, metal foil-clad laminate, resin sheet and printed wiring board
EP3715393B1 (en) Resin composition, prepreg, resin-including film, resin-including metal foil, metal-clad laminate, and wiring board
JP6906170B2 (en) Thermosetting resin composition, and resin varnish, prepreg, metal foil with resin, resin film, metal-clad laminate and printed wiring board using it.
US20240084133A1 (en) Polyphenylene ether resin composition, prepreg using same, film with resin, metal foil with resin, metal-clad laminate and wiring board
JP2017031276A (en) Thermosetting resin composition, resin varnish, metal foil with resin, resin film, metal clad laminated board and printed wiring board using the same
CN112074553B (en) Thermosetting resin composition, film comprising the same, and multilayer wiring board using the same
TW202108679A (en) Resin composition, prepreg, resin-attached film, resin-attached metal foil, metal-cladded laminate sheet, and wiring board
JP2019044090A (en) Thermosetting resin composition, and prepreg, metal foil with resin, resin film, metal-clad laminated plate and wiring board using the same
WO2017094489A1 (en) Thermally curable resin composition, thermally curable resin film, printed wiring board, and semiconductor device
JP7264485B2 (en) Thermosetting resin composition, insulating film, interlayer insulating film, multilayer wiring board, and semiconductor device
WO2020203320A1 (en) Resin composition, prepreg obtained using same, resin-coated film, resin-coated metal foil, metal-clad laminate, and wiring board
WO2023042578A1 (en) Resin composition, and printed wiring board, cured product, prepreg, and electronic component for high frequency in which same is used
WO2022054861A1 (en) Resin composition, prepreg, resin-coated film, resin-coated metal foil, metal-clad laminate, and wiring board
JP7204214B2 (en) Thermosetting resin composition, insulating film, interlayer insulating film, multilayer wiring board, and semiconductor device
JP6994660B2 (en) Metal-clad laminate and printed wiring board
TW202411282A (en) Resin compositions, and cured products, prepregs, printed circuit boards and high-frequency electronic components using the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant