WO2006051820A1 - 熱硬化性樹脂組成物、熱硬化性フィルムおよびそれらの硬化物、ならびに電子部品 - Google Patents
熱硬化性樹脂組成物、熱硬化性フィルムおよびそれらの硬化物、ならびに電子部品 Download PDFInfo
- Publication number
- WO2006051820A1 WO2006051820A1 PCT/JP2005/020547 JP2005020547W WO2006051820A1 WO 2006051820 A1 WO2006051820 A1 WO 2006051820A1 JP 2005020547 W JP2005020547 W JP 2005020547W WO 2006051820 A1 WO2006051820 A1 WO 2006051820A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- parts
- thermosetting resin
- thermosetting
- copolymer
- Prior art date
Links
Classifications
-
- 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
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer
- H05K3/4676—Single layer compositions
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
-
- 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
- H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
- H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
- H05K3/4635—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials laminating flexible circuit boards using additional insulating adhesive materials between the boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L13/00—Compositions of rubbers containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- 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
- H05K1/0393—Flexible materials
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0133—Elastomeric or compliant polymer
Definitions
- thermosetting resin composition thermosetting film and cured products thereof, and electronic components
- the present invention relates to a thermosetting resin composition, a thermosetting film, a cured product thereof, and an electronic component. More specifically, a thermosetting resin composition capable of obtaining a cured product excellent in electrical characteristics such as electrical insulation such as low dielectric constant and low dielectric loss, a thermosetting film using the composition, and The present invention relates to a cured product thereof and an electronic component having an insulating layer formed using the composition.
- Such electronic components tend to be multilayered as the density, accuracy, and miniaturization increase, and an electronic component such as a multilayer circuit board requires an interlayer insulating film or a flat film. It has become.
- the resin material for such an interlayer insulating film or flat film is required to have excellent electrical insulation between conductors and also have excellent heat resistance to cope with high heat generation or high-temperature solder. It has been.
- thermosetting resins such as polyimide, phenol resin, and epoxy resin were mainly used.
- a method using a cross-linked acrylonitrile rubber with a small particle diameter is disclosed for an insulating material for the purpose of preventing the occurrence of cracks and achieving both (thermal) impact resistance, heat resistance, and electrical insulation.
- Patent Document 1 a method using a crosslinked acrylonitrile rubber having an average secondary particle diameter of 0.5 to 2 ⁇ m is disclosed (see Patent Document 2).
- Patent Document 2 a method using a crosslinked acrylonitrile rubber having an average secondary particle diameter of 0.5 to 2 ⁇ m is disclosed (see Patent Document 2).
- the technology disclosed here normally uses an elastic body containing 20% or more of acrylonitrile, which is excellent in compatibility with an epoxy resin or the like, but has electrical characteristics such as dielectric constant or dielectric loss tangent of the insulating resin, Alternatively, the insulation reliability tends to decrease, which is not preferable.
- thermosetting materials using polyimide, phenol resin, epoxy resin, etc. are generally hard and brittle toughness and have improved compatibility with resin to improve adhesion to metal conductors such as copper.
- An alicyclic linoleic butadiene copolymer or a carboxy-modified acrylonitrile butadiene copolymer having good solubility was added to the resin material (see Patent Documents 3 to 6).
- a thermosetting material having a lower dielectric constant and dielectric loss than a thermosetting material containing a copolymer containing acrylonitrile is required. It has been.
- styrene-butadiene copolymers are known to have excellent electrical characteristics due to their structure.
- a normal styrene-butadiene copolymer has poor compatibility with a thermosetting resin such as epoxy resin, and each component is separated during mixing or curing reaction, and it is difficult to obtain a uniform cured film. It was.
- Patent Documents 7 to 9 describe a heat containing hollow cross-linked resin particles obtained by polymerizing dibutylbenzene on polymer particles made of styrene-butadiene-itaconic acid copolymer from the viewpoint of improving low dielectric properties and low dielectric loss properties.
- a curable resin composition and a cured product thereof have been proposed.
- the cured product is composed of a styrene-butadiene-itaconic acid copolymer.
- a cured product containing spherical non-crosslinked resin particles obtained by polymerizing methyl methacrylate in polymer particles it is disclosed that it exhibits a low dielectric constant and a low dielectric loss and is excellent in insulation.
- this cured product has a lower dielectric constant and lower dielectric loss than the thermosetting material containing a copolymer containing acrylonitrile, but the insulation resistance value tends to decrease.
- the hollow crosslinked resin particles are copolymerized with dibutylbenzene using a styrene-butadiene-taconic acid copolymer as a seed polymer, the compatibility with epoxy resins and phenol resins is poor. Due to the high glass transition temperature, the cured product containing these hollow crosslinked resin particles tended to be inferior in thermal shock resistance (crack resistance).
- thermosetting resins from which such cured products can be obtained. There is a need for a composition.
- an epoxy resin having a polyfunctional epoxy resin as an essential component, a resin incompatible with the epoxy resin, a rubber elastic fine particle, and a phenolic novolak resin as a necessary curing agent are used as the composition for forming the insulating layer.
- a known epoxy resin composition Patent Document 10
- an epoxy resin as a main agent, a phenol novolak resin as a curing agent, and an imidazole silane as a coupling agent Patent Document 11
- the former is to reduce the thermal expansion of the insulating layer, and the latter is to improve the adhesion between the inner circuit and the insulating layer while maintaining high heat resistance.
- Patent Document 1 JP-A-8-139457
- Patent Document 2 JP 2003-113205 A
- Patent Document 3 JP 2002. — No. 20454
- Patent Literature 4 JP 2002. — No. 60467
- Patent Document 5 Japanese Patent Laid-Open No. 2003-246849
- Patent Document 6 Japanese Patent Laid-Open No. 2003-318499
- Patent Document 7 Japanese Patent Laid-Open No. 2000-311518
- Patent Document 8 JP 2000-313818
- Patent Document 9 JP 2000-315845 A Patent Document 10: Japanese Unexamined Patent Publication No. 2003-246849
- Patent Document 11 Japanese Unexamined Patent Publication No. 2003-318499
- the present invention is intended to solve the problems associated with the prior art as described above, and to obtain a cured product excellent in characteristics such as electrical insulation and electrical characteristics, and such a cured product.
- the first object is to provide a thermosetting resin composition that can be used. Furthermore, in addition to the first problem, a cured product having a high glass transition temperature with extremely small changes in physical properties during reliability testing and excellent properties such as thermal shock resistance and heat resistance, and such a cured product.
- the second problem is to provide a thermosetting resin composition capable of obtaining the above.
- Another object of the present invention is to provide a highly reliable electronic component that uses such a thermosetting resin composition and does not generate cracks or breaks due to thermal stress. It is.
- the present inventors have intensively studied to solve the above-mentioned problems, and are a heat comprising an epoxy resin, a bonded tali port, a genyl rubber having a nitrile amount of less than 10% by weight, a curing agent and / or a curing catalyst. It has been found that when a curable resin composition is used, a cured product excellent in electrical characteristics such as low dielectric constant and low dielectric loss and electrical insulation can be obtained, and the present invention has been completed. In addition, when a gen-based rubber or anti-aging agent having a specific functional group is used, a cured product excellent in mechanical properties, heat resistance, thermal shock resistance, and reliability, in which the change in physical properties during the reliability test is extremely small. As a result, the present invention was completed.
- thermosetting resin composition according to the present invention includes (A) an epoxy resin, (B) a gen-based crosslinked rubber having an amount of bonded phthalonitrile of less than 10% by weight, (D) a curing agent and / or (E) It contains a curing catalyst.
- the gen-based crosslinked rubber (B) is a copolymer having one or more glass transition temperatures, and at least one glass transition temperature thereof is 0 ° C. or lower, and at least a polymerizable unsaturated bond is present. It is a copolymer of two crosslinkable monomers and does not contain acrylonitrile, preferably at least selected from carboxyl group, hydroxyl group and epoxy group. Also preferred is a styrene-butadiene copolymer having one kind of functional group.
- the styrene-butadiene-based copolymer is selected from 5 to 40 parts by weight of styrene, 40 to 90 parts by weight of butadiene, and a carboxyl group, a hydroxyl group, and an epoxy group with respect to 100 parts by weight of a total of raw material monomers. It is preferable that the copolymer is obtained from 1 to 30 parts by weight of a monomer having at least one functional group, or 5 to 40 parts by weight of styrene with respect to 100 parts by weight of the total raw material monomers.
- butadiene 1 to 30 parts by weight of a monomer having at least one functional group selected from a carboxyl group, a hydroxyl group and an epoxy group, and at least two polymerizable unsaturated double bonds
- a copolymer obtained from 0.5 to 10 parts by weight of the monomer is preferred.
- the gen-based crosslinked rubber (B) is a crosslinked fine particle.
- the crosslinked fine particle preferably has a particle diameter in the range of 30 to 500 nm.
- thermosetting resin composition of the present invention the elastic modulus of a cured product obtained by thermosetting it is preferably 1.5 GPa or less.
- the cured product according to the present invention is obtained by thermosetting the thermosetting resin composition.
- thermosetting film according to the present invention is formed using the thermosetting resin composition, and the cured film according to the present invention thermally cures the thermosetting film. It is obtained by these.
- the electronic component according to the present invention has an insulating layer formed using the thermosetting resin composition.
- thermosetting resin composition according to the present invention By using the thermosetting resin composition according to the present invention, a thermosetting resin composition having excellent compatibility can be obtained, and excellent mechanical properties, insulating properties, electrical properties (low dielectric constant) A cured product having a low dielectric loss) can be obtained. Furthermore, it is possible to obtain a cured product having excellent heat resistance, thermal shock resistance, and reliability with very little change in physical properties during the reliability test.
- FIG. 1 is a cross-sectional view of a pattern substrate for thermal shock evaluation.
- FIG. 2 is a top view of a pattern substrate for thermal shock evaluation.
- thermosetting resin composition according to the present invention comprises an epoxy resin (A), a gen-based crosslinked rubber (B) having a bound acrylonitrile amount of less than 10% by weight, a curing agent (D) and / or a curing catalyst (E). contains.
- the thermosetting resin composition may contain an anti-aging agent (C), other polymers, organic solvents, inorganic fillers, adhesion assistants, surfactants, and other additive agents as necessary. You can also.
- the epoxy resin (A) used in the present invention is not particularly limited as long as it is an epoxy resin that can be used for an interlayer insulating film or a flattening film of a multilayer circuit board, a protective film or an electric insulating film of an electronic component, etc. ,In particular,
- Yore the present invention are diene-based crosslinked rubber (B) is bound acrylonitrile amount of less than 10 weight 0/0, preferably less than 8% by weight, particularly preferably 0 wt%.
- the gen-based crosslinked rubber (B) used in the present invention is a copolymer having one or more glass transition temperatures (Tg), and at least one glass transition temperature thereof is 0 ° C. or less, preferably 100 ° C. It is desirable to be in the range of ⁇ 0 ° C., more preferably in the range of 1-80 ° C. to 1-20 ° C.
- the cured product (cured film) of the thermosetting resin composition exhibits excellent flexibility (crack resistance).
- the Tg exceeds the upper limit, the cured product is inferior in crack resistance, in a temperature change is large environment is Rukoto force s to many cracks occurred on the surface of the substrate.
- Such a gen-based cross-linked rubber (B) includes, for example, a cross-linkable monomer having at least two polymerizable unsaturated bonds (hereinafter simply referred to as “cross-linkable monomer”) and other than the cross-linkable monomer.
- a copolymer with a monomer hereinafter referred to as “other monomer”
- the other monomer is selected so that the Tg of the copolymer is 0 ° C. or less.
- Copolymers that are other monomers are preferred.
- Further preferable other monomers include a functional group having no polymerizable unsaturated bond, such as a carboxyl group, an epoxy group, Examples thereof include monomers having a functional group such as amino group, isocyanate group, and hydroxyl group.
- crosslinkable monomer examples include diphenylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate.
- examples thereof include compounds having at least two polymerizable unsaturated bonds, such as rate, pentaerythritol tri (meth) acrylate, polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate. Of these, dibutylbenzene is preferably used.
- Butyl compounds such as butadiene, isoprene, dimethylbutadiene, and black-opened planes; 1,3-pentagen, (meth) acrylonitrile, chloro acrylonitrile nitrile, chloromethyl acrylonitrile, methoxy acrylonitrile, ethoxy acrylonitrile Unsaturated nitrile compounds such as nitrile crotonate, nitrile kainate, dinitrile itaconate, dinitrate maleate and dinitrile fumarate;
- Unsaturated amides such as N- (2-hydroxyethyl) (meth) acrylamide, N, N, —bis (2-hydroxyethyl) (meth) acrylamide, crotonic acid amide, key cinnamate amide;
- Aromatic butyl compounds such as styrene, monomethylol styrene, o-methoxystyrene, p-hydroxystyrene, p-isopropenylphenol;
- Epoxy (meth) acrylates obtained by reaction of diglycidyl ether of bisphenol or A or diglycidyl ether of glycol with (meth) acrylic acid or hydroxyalkyl (meth) acrylate.
- Epoxy group-containing unsaturated compounds such as glycidyl (meth) acrylate and (meth) aryl glycidyl ether;
- Unsaturated compounds containing amino groups such as dimethylamino (meth) acrylate and jetylamino (meth) acrylate;
- Amide group-containing unsaturated compounds such as (meth) acrylamide, dimethylenole (meth) acrylamide, etc.
- Hydroxyl-containing unsaturated compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate Can be mentioned.
- butadiene, isoprene, (meth) acrylonitrile, (meth) acrylic acid alkynole esters, styrene, ⁇ -hydroxystyrene, ⁇ -isopropenylphenol, glycidinole (meth) acrylate, (meth) Acrylic acid and hydroxyalkyl (meth) acrylates are preferred.
- Examples of the gen-based crosslinked rubber ( ⁇ ⁇ ) used in the present invention include a crosslinked rubber obtained from a bull compound, an aromatic vinyl compound, an unsaturated acid compound, and a crosslinkable monomer, a bull compound and an aromatic bull compound.
- Cross-linked rubber obtained from a hydroxyl group-containing unsaturated acid compound and a cross-linkable monomer cross-linking obtained from a vinyl compound, an unsaturated nitrile compound, an unsaturated acid compound, a hydroxyl group-containing aromatic bur compound and a cross-linkable monomer Rubber is preferred.
- the crosslinkable monomer used for producing the gen-based crosslinked rubber is preferably:! To 20 wt%, more preferably 2 to 10 wt%, based on the total amount of monomers. Used in the amount of.
- the method for producing the gen-based crosslinked rubber ( ⁇ ) is not particularly limited, and for example, it is possible to use an emulsion polymerization method.
- a surfactant is used to emulsify monomers containing a crosslinkable monomer in water, and a radical polymerization initiator such as a peroxide catalyst or a redox catalyst is added as a polymerization initiator.
- a radical polymerization initiator such as a peroxide catalyst or a redox catalyst
- halogenated carbonization Add molecular weight regulators such as hydrogen.
- polymerization is carried out at 0 to 50 ° C., and after reaching a predetermined polymerization conversion rate, a polymerization terminator such as N, N-jetylhydroxylamine is added to stop the polymerization reaction. Thereafter, the gen-based crosslinked rubber (B) can be synthesized by removing the unreacted monomer in the polymerization system by steam distillation or the like.
- a polymerization terminator such as N, N-jetylhydroxylamine
- the surfactant is not particularly limited as long as it can produce the gen-based crosslinked rubber (B) by emulsion polymerization, and examples thereof include alkylnaphthalene sulfonate and alkylbenzene sulfonate.
- Nonionic surfactants such as sorbitan fatty acid esters and fatty acid monoglycerides; amphoteric surfactants; reactive emulsifiers. These surfactants can be used alone or in admixture of two or more.
- the latex containing the gen-based crosslinked rubber (B) obtained by the emulsion polymerization is coagulated by a method such as salting out, washed with water, and dried to obtain a solid gen-based crosslinked rubber (B).
- a method such as salting out
- the Gen-based crosslinked rubber (B) is heated to a cloud point higher than that of the nonionic surfactant when a nonionic surfactant is used as the surfactant. It can also be solidified.
- a nonionic surfactant is added after the polymerization, and the latex is heated to a cloud point or higher so that the gen-based crosslinked rubber (B) is heated. Can also solidify
- a method for producing the gen-based crosslinked rubber (B) without using a crosslinkable monomer a method of crosslinking a latex particle by adding a crosslinking agent such as a peroxide to the latex, or polymerization conversion Examples thereof include a method of gelling in latex particles by increasing the rate, and a method of crosslinking in latex particles by adding a crosslinking agent such as a metal salt using a functional group such as a carboxy group.
- the particle diameter of the gen-based crosslinked rubber (B) used in the present invention is usually 30 to 500 nm, preferably 40 to 200 nm.
- the particle size of the gen-based crosslinked rubber (B) is within the above range, the cured film has excellent mechanical properties and thermal shock resistance.
- the method for controlling the particle size of the gen-based crosslinked rubber (B) is not particularly limited. For example, when the crosslinked rubber particles are synthesized by emulsion polymerization, the number of micelles during emulsion polymerization is adjusted by adjusting the amount of emulsifier used. And the particle size can be controlled.
- the gen-based crosslinked rubber (B) is blended in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight with respect to 100 parts by weight of the epoxy resin (A). Is preferred. If the blending amount is less than the above lower limit, the thermal shock resistance of the cured film obtained by thermosetting the thermosetting resin composition is reduced, and if it exceeds the upper limit, the heat resistance of the cured film is reduced or the thermosetting property is decreased. The compatibility with other components in the resin composition may decrease.
- the styrene-butadiene copolymer (hereinafter also referred to as “SB copolymer”) used in the present invention is a styrene-butadiene-based copolymer having at least one functional group selected from a carboxyl group, a hydroxyl group and an epoxy group. It is a copolymer. By containing at least one functional group selected from a carboxyl group, a hydroxyl group and an epoxy group, the SB copolymer is excellent in compatibility with the epoxy resin (A).
- the glass transition temperature (Tg) of the SB copolymer is usually 0 ° C or lower, preferably -10 ° C or lower, more preferably -20 ° C or lower.
- Tg glass transition temperature
- the cured product (cured film) of the thermosetting resin composition exhibits excellent flexibility (crack resistance).
- Tg exceeds the above upper limit, the cured product is inferior in crack resistance, and in the environment where the temperature change is large, many cracks are generated on the substrate surface.
- the Tg of the SB copolymer in the present invention is obtained by solidifying and drying the SB copolymer dispersion, and then using a differential scanning calorimeter (SS C / 5200H) manufactured by Seiko Instruments Inc. -100 ° C ⁇ : It is a value measured at a heating rate of 10 ° CZmin in the range of 150 ° C (DSC method).
- the SB copolymer used in the present invention is a monomer having at least one functional group selected from styrene, butadiene, a carboxyl group, a hydroxyl group, and an epoxy group (hereinafter referred to as "specific functional group”). It is also referred to as “containing monomer”).
- styrene is usually 5 to 40 parts by weight, preferably 15 to 25 parts by weight
- butadiene is usually 40 to 90 parts by weight, preferably 50 parts per 100 parts by weight of the raw material monomers in total. It is desirable to copolymerize the specific functional group-containing monomer usually:! To 30 parts by weight, preferably 5 to 25 parts by weight.
- Copolymerization of the raw material monomers in the above proportions provides excellent compatibility with epoxy resins, excellent electrical properties such as low dielectric constant and low dielectric loss, and excellent electrical insulation and thermal shock resistance.
- a styrene monobutadiene copolymer capable of forming a product can be obtained.
- the SB copolymer is a crosslinked fine particle, styrene, butadiene, a specific functional group-containing monomer, and a monomer having at least two polymerizable unsaturated double bonds (hereinafter referred to as “the SB copolymer”).
- the SB copolymer also referred to as “crosslinkable monomer”.
- styrene is usually 5 to 40 parts by weight, preferably 15 to 25 parts by weight
- butadiene is usually 40 to 90 parts by weight, preferably 50 to 80 parts by weight, based on 100 parts by weight of the raw material monomers in total.
- the bridging monomer is usually 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight It is desirable to partially copolymerize. Copolymerization of raw material monomers in the above proportions provides excellent compatibility with epoxy resins, excellent electrical properties such as low dielectric constant and low dielectric loss, excellent electrical insulation, and excellent thermal shock resistance A styrene-butadiene copolymer capable of forming a product can be obtained.
- SB copolymers in addition to styrene, butadiene, a specific functional group-containing monomer and a crosslinkable monomer, other monomers (hereinafter also simply referred to as “other monomers”). ) May be copolymerized.
- the SB copolymer thus obtained is particularly excellent in compatibility with the epoxy resin (A).
- SB copolymers when a copolymer obtained by copolymerizing only styrene, butadiene and a specific functional group-containing monomer is used, a cured product having excellent insulation can be obtained.
- Examples of the specific functional group-containing monomer include a carboxyl group-containing monomer, a hydroxyl group-containing monomer, and an epoxy group-containing monomer. These monomers may be used alone or in combination of two or more.
- carboxyl group-containing monomer acrylic acid, methacrylic acid, itaconic acid, 2_ (meth) Ataliloyloxetyl succinic acid, 2— (Meth) Atalyloxyxetyl maleic acid, 2- (Meth) Atalyloxyxetyl phthalic acid, 2 -— (Meth) Atalyloxyxetyl hexyl Examples thereof include sahydrophthalic acid, acrylic acid dimer, ⁇ -carboxy-polypolyprolatathone monoatrate.
- hydroxyethyl (meth) acrylate hydroxypropinole (meth) acrylate, hydroxy butyl (meth) acrylate, 2-hydroxy 1 _phenoxypropyl (meth) acrylate, 2-hydroxy-1-3-phenoxypropyl (meth) acrylate.
- epoxy group-containing monomer examples include glycidyl (meth) acrylate and allyl glycidyl ether.
- the structural unit derived from these specific functional group-containing monomers is usually 0.1 mol% with respect to 100 mol% of all monomer structural units constituting the SB copolymer. It is desirable that it is contained at a ratio of ⁇ 30 mol%, preferably 0.5 mol% to 20 mol%.
- crosslinkable monomer examples include divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) And compounds having at least two polymerizable unsaturated groups, such as acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate.
- Examples of other monomers include isoprene, dimethylbutadiene, black mouth
- Gen-based monomers such as 1,3-pentagen; (meth) acrylamide, N, ⁇ '-methylenebis (meth) acrylamide, ⁇ , N'-ethylenebis (meth) acrylamide, ⁇ , N'-hexamethy
- Unsaturated amides such as amides, crotonic acid amides, and cinnamate amides; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylyl (Meth) acrylates such as acid hexyl, (meth) acrylate lauryl, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate; bis-methylstyrene, ⁇ -methoxystyrene, ⁇ -hydroxystyrene , ⁇ -Isopropureurfe Aromatic vinyl compounds such as diols; Epoxy (meth) obtained by reaction of bisphenol A diglycidyl ether, glycol diglycidyl ether, etc.
- the method for producing the styrene-butadiene copolymer is not particularly limited, and for example, an emulsion polymerization method or a suspension polymerization method can be used.
- a radical polymerization initiator such as a peroxide catalyst or a redox catalyst is used as a polymerization initiator.
- Polymerization is carried out at 0 to 50 ° C with addition of a molecular weight regulator such as a mercabtan compound or a halogenated hydrocarbon.
- a polymerization stopper is added to stop the polymerization reaction, such as N, N-jetylhydroxynoramine.
- a copolymer emulsion can be synthesized by removing unreacted monomers in the polymerization system by steam distillation or the like. By adding this copolymer emulsion into an aqueous electrolyte solution having a predetermined concentration and drying the precipitated copolymer, it is possible to isolate the copolymer.
- Crosslinking fine particles can be obtained by adding a crosslinkable monomer and copolymerizing during the polymerization.
- a method of producing crosslinked fine particles without using a crosslinking monomer a method of crosslinking a latex particle by adding a crosslinking agent such as a peroxide to the latex, and increasing the polymerization conversion rate in the latex particle
- a crosslinking agent such as a peroxide
- the cloud point of the nonionic surfactant is used.
- the copolymer can be solidified by heating as described above.
- a surfactant other than the nonionic surfactant is used, a nonionic surfactant is added after the polymerization so that it exceeds the cloud point.
- the copolymer can be solidified by heating.
- the surfactant used in the production of the SB copolymer by emulsion polymerization is not particularly limited.
- an anionic surfactant such as an alkylbenzene sulfonate; alkyl naphthalene sulfonate; Cationic surfactants such as alkyltrimethylammonium salts and dialkyldimethylammonium salts; polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, etc.
- Nonionic surfactants and amphoteric surfactants; and reactive emulsifiers can be used. These surfactants can be used alone or in admixture of two or more.
- the size of the fine particle is usually 30 to 500 nm, preferably 40 to 20 Onm, more preferably. 45 ⁇ :! OOnm.
- the average particle size of the particulate copolymer is determined by diluting the dispersion of the particulate copolymer according to a conventional method using a light scattering flow distribution measuring device (LPA-3000) manufactured by Otsuka Electronics. It is a measured value.
- the method for controlling the particle size of the particulate copolymer is not particularly limited.
- the particulate copolymer is synthesized by emulsion polymerization, the number of micelles during emulsion polymerization is determined depending on the amount of the emulsifier used.
- the particle size can be controlled by controlling.
- the SB copolymer is blended in an amount of usually:! To 150 parts by weight, preferably 5 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin (A).
- the blending amount is more than the above lower limit, the toughness of the obtained cured film is improved, and cracks are generated in the cured film during long-term use. Further, when the blending amount is not more than the above upper limit, the compatibility between the SB copolymer and other components is improved, and the heat resistance of the obtained cured product is improved.
- anti-aging agent used in the present invention examples include phenol-based anti-aging agents, thio-based anti-aging agents, amine-based anti-aging agents, and the like, and phenol-based anti-aging agents are particularly preferred.
- an anti-aging agent it is possible to extend the product life of electronic components where the change in physical properties during the reliability test is extremely small.
- phenolic antioxidants include 2,6-di_t_butyl_4_methyl. Phenols, 2, 6 Di-tert-butyl ether, 2, 4, 6 Tri-tert-butyl phenol, Butylhydroxyanisole, 1-Hydroxy-3-methyl-4-isopropylbenzene, Mono-tert-butyl-p-cresol, Mono-tert-butyl-m-cresol 2, 4—Dimethyl mono 6 _t_butyl phenol, triethylene glycol mono bis [3— (3_t_butyl _ 5 _methyl _4-hydroxyphenyl) propionate], 1, 6 _Hexanediol mono bis [3— (3,5-di-t_butyl_4-hydroxyphenyl) probione], 2,4_bis_ (n-octylthio) one 6 _ (4-hydroxy_3,5_di-t-butylenolanino) 1,1,3,5
- amine-based antioxidants include bis (2, 2, 6, 6-tetramethyl _4-piperidyl) sebacate, tetrakis (1, 2, 2, 6, 6 _pentamethyl _4— Piperidyl) 1, 2, 3, 4_butanetetracarboxylate, tetrakis (2, 2, 6, 6-tetramethyl _4-piperidinole) 1, 2, 3, 4_butanetetra force noroxylate, 1, 2, 2 , 6, 6 _ pentamethinore 4-h.
- the io antioxidant include dilauryl thiopropionate. These antioxidants can be used alone or in combination of two or more.
- the blending amount of the anti-aging agent is preferably from 0.5 to 20 parts by weight, particularly preferably from 0.5 to 10 parts by weight per 100 parts by weight of the component (ii).
- the curing agent (D) used in the present invention is not particularly limited as long as it causes a curing reaction with the epoxy group in the resin, but is aliphatic or aromatic amines, phenols, acid anhydrides, polyamide resins. , Phenolic resins, polysulfide resins, polybutanol And the like.
- Examples of amines include jetylamine, diethylenetriamine, triethylenetetramine, jetylaminopropylamine, aminoethylpiperazine, mensendiamine, metaxylylenediamine, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, Examples include cherenandaniline and metaphenidamine.
- the phenols are not particularly limited as long as they have a phenolic hydroxyl group, but biphenol, bisphenol A, bisphenol F, phenol novolak, crezo novolac, bisphenol novolac, xylene monovolak, melamine novolac. , P-hydroxystyrene (co) polymers, their halides, alkyl group-substituted products, and the like.
- Acid anhydrides include hexahydrophthalic anhydride (HPA), tetrahydrophthalic anhydride (T HPA), pyromellitic anhydride (PMDA), chlorendic anhydride (HET), nadic anhydride (NA), There are methyl nadic anhydride (MNA), dodecynyl succinic anhydride (DDSA), phthalic anhydride (PA), methylhexahydrophthalic anhydride (MeHPA), maleic anhydride, etc.
- HPA hexahydrophthalic anhydride
- T HPA tetrahydrophthalic anhydride
- PMDA pyromellitic anhydride
- HET chlorendic anhydride
- NA nadic anhydride
- MNA dodecynyl succinic anhydride
- PA phthalic anhydride
- MeHPA methylhexahydrophthalic anhydride
- maleic anhydride etc.
- the hardener (D) is preferably added in an amount of:! To 100 parts by weight, preferably 10 to 70 parts by weight, with respect to 100 parts by weight of the epoxy resin (A).
- the curing catalyst (E) used in the present invention is not particularly limited.
- amines, strong rubonic acids, acid anhydrides, dicyandiamide, dibasic acid dihydrazide, imidazoles, organic boron, organic phosphine, guanidines and These salts can be used, and these can be used singly or in combination of two or more.
- the curing catalyst (E) is added in an amount of 0.:! To 20 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin (A). Is preferred. Moreover, a curing accelerator can be used in combination with a curing catalyst) for the purpose of accelerating the curing reaction, if necessary.
- a “curing agent” forms a crosslinked structure by itself, and a “curing catalyst” does not form a crosslinked structure by itself, but promotes a crosslinking reaction. Is cured It increases the catalytic action of the catalyst.
- an organic solvent can be used as necessary in order to improve the handleability of the thermosetting resin composition and to adjust the viscosity and storage stability.
- the organic solvent (F) used in the present invention is not particularly limited.
- Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethino ethenore acetate, ethylene glycol monomethino create and teracetate; propylene glycol monomethino ethenore, propylene glycol monomethino ethenore, propylene Propylene glycol monoalkyl ethers such as glyconomonopropinoreethenole, propyleneglycolenobutinoleate;
- Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol jetyl ether, propylene glycolenoresin propinoatenore, propyleneglycolonebutyinoatenore;
- Propylene glycol monoalkyl etherate acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl etherate acetate, propylene glycol monomono propinoate etherate acetate, propylene glycol monobutyl ether acetate;
- Cellosolves such as cetylceol solve and butylcexol sorb;
- Carbitols such as butyl carbitol
- Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate;
- Aliphatic carboxylic acid esters such as ethyl acetate, n- propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate and isobutyl propionate ;
- esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate;
- Aromatic hydrocarbons such as toluene and xylene; Ketones such as 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, methyl amyl ketone, cyclohexanone;
- Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methinorepyrrolidone;
- organic solvents may be used alone or in combination of two or more.
- thermosetting resin composition according to the present invention can contain other resins other than the epoxy resin as necessary, for example, resins having a phenolic hydroxyl group, polyimides, acrylic polymers, polystyrenes. Resins, phenoxy resins, polyolefin elastomers, styrene butadiene elastomers, silicon elastomers, diisocyanate compounds such as tolylene diisocyanate or blocked products thereof, high density polyethylene, medium density polyethylene , Polypropylene, Polycarbonate, Polyarylate, Polyamide, Polyimide, Polysulfone, Polyethersulfone, Polyetherketone, Polyphenylenesulfide, (Modified) Polycarposimide, Polyetherimide, Polyesterimide, Modified Polyolefin Okishido may contain a thermoplastic or thermosetting tree butter, and the like such as a resin having a Okisetan group. These resins can be used in amounts that do not impair the effects of the present invention
- thermosetting resin composition comprises, as necessary, an adhesion aid, a leveling agent, an inorganic filler, a polymer additive, a reactive diluent, a wettability improver, a surfactant, It can also contain plasticizers, antistatic agents, antifungal agents, humidity control agents, flame retardants and other additives, and these additives can be used in amounts that do not impair the effects of the present invention. it can.
- a resin other than the epoxy resin (A) hereinafter also referred to as “other resin” may be added.
- thermosetting resin composition Preparation of thermosetting resin composition
- thermosetting resin composition of the present invention includes, for example, each component of the epoxy resin (A), the gen-based crosslinking rubber (B), the curing agent (D) and / or the curing catalyst (E), and if necessary. Solvent and It can manufacture by mixing with other components, such as anti-aging agent (c).
- Solvent and It can manufacture by mixing with other components, such as anti-aging agent (c).
- As a method for producing the thermosetting resin composition conventionally known methods can be used as appropriate, and each component may be added at once or in any order and stirred and mixed.
- the epoxy resin (A) is dissolved in the organic solvent (F) to prepare a varnish, and the varnish is mixed with a gen-based crosslinked rubber (B) and a curing agent (D) and / or a curing catalyst (E ).
- thermosetting resin composition includes at least an epoxy resin (A), a gen-based crosslinked rubber (B), a curing agent (D), and a curing catalyst (E), and each component has good compatibility. Show.
- thermosetting this thermosetting resin composition a cured product excellent in electrical characteristics such as low dielectric constant and low dielectric loss, and insulation can be obtained.
- a thermosetting resin composition further containing an anti-aging agent (C) and a thermosetting resin composition in which the gen-based crosslinked rubber (B) is a styrene-butadiene copolymer having a specific functional group are thermally cured.
- a cured product excellent in mechanical properties, thermal shock resistance, and heat resistance, in which the change in physical properties before and after the reliability test is extremely small can be obtained.
- thermosetting resin composition according to the present invention particularly includes an interlayer insulating film or a planarizing film of a multilayer circuit board, a protective film or an electric insulating film for various electric devices and electronic components, and various electronic materials. It can be used extremely favorably for adhesives, condenser films and the like. Further, it can be suitably used as a semiconductor sealing material, an underfill material, or a liquid crystal sealing material.
- thermosetting resin composition according to the present invention can be prepared in the form of powder, pellets, etc. and used as a thermosetting molding material.
- thermosetting resin composition according to the present invention can be impregnated into a glass cloth or the like to prepare a prepreg, and can be used as a laminate material such as a copper-clad laminate.
- the prepreg can be prepared by impregnating the thermosetting resin composition of the present invention as it is into a glass cloth or the like, and the thermosetting resin composition of the present invention is mixed with a solvent to prepare a solution. It can also be prepared by impregnating this solution into glass cloth or the like.
- thermosetting resin composition according to the present invention is applied to a copper foil to form a thermosetting thin film. Therefore, it can be used as an insulating adhesive layer for flexible printed wiring boards. ⁇ Thermosetting film>
- thermosetting film according to the present invention is formed by applying the thermosetting resin composition to a suitable support that has been surface-released in advance to form a thermosetting thin film, and does not thermoset the thin film. It can be obtained by peeling from the support.
- the obtained thermosetting film can be used as a low-stress adhesive film or an (insulating) adhesive film for electronic parts such as printed wiring boards and electrical devices.
- the support is not particularly limited, and examples thereof include metals such as iron, nickel, stainless steel, titanium, aluminum, copper, and various alloys; silicon nitride, silicon carbide, sialon, aluminum nitride, and nitride. Ceramics such as boron, boron carbide, zirconium oxide, titanium oxide, alumina, silica, and mixtures thereof; semiconductors such as Si, Ge, SiC, SiGe, and GaAs; ceramic materials such as glass and ceramics; polyamide, polyamideimide, Examples thereof include heat-resistant resins such as polyimide, PBT (polybutylene terephthalate), PET (polyethylene terephthalate), and wholly aromatic polyesters.
- metals such as iron, nickel, stainless steel, titanium, aluminum, copper, and various alloys
- Ceramics such as boron, boron carbide, zirconium
- the support may be subjected to a mold release treatment in advance.
- thermosetting resin composition As a method of applying the thermosetting resin composition to a support, a known application method can be used. For example, a coating method such as a datebing method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, or an ink jet method can be used.
- the coating thickness can be appropriately controlled by adjusting the solid content concentration and viscosity of the coating means and the composition solution.
- thermosetting resin cured product according to the present invention can be produced, for example, by the following method using the thermosetting resin composition, and is excellent in electrical characteristics and electrical insulation.
- an anti-aging agent (C) or a styrene-butadiene copolymer having a specific functional group is used, the thermal shock resistance and heat resistance are small, with little change in physical properties before and after the reliability test.
- the thermosetting resin composition is applied to a suitable surface-treated support in advance to form a thermosetting thin film, and the thin film is transferred to a substrate together with the support using a laminator and then cured.
- the support used at this time can be the same as the support used in the production of the thermosetting film described above.
- a cured film of a thermosetting resin composition which is one of the cured products, can be produced by thermosetting the thermosetting film.
- the cured film is formed by applying the thermosetting resin composition to an appropriate support that has been subjected to a release treatment in advance to form a thermosetting film layer, and the thermosetting film layer is heated to be cured. Then, a cured film can be produced by peeling the obtained cured film layer from the support.
- the support used at this time can be the same as the support used in the production of the thermosetting film described above.
- thermosetting resin composition are not particularly limited, but depending on the use of the obtained cured product and the type of curing agent and / or curing catalyst, for example, 50-200 ° C.
- the composition can be cured by heating at a temperature in the range of C for about 10 minutes to 48 hours.
- heating is performed in two stages to allow the curing to proceed sufficiently and to prevent the formation of bubbles.
- heating is performed in the first stage, at a temperature of 50 to: 100 ° C. for about 10 minutes to 10 hours, and in the second stage, heating is performed at a temperature of 80 to 200 ° C. for about 30 minutes to 12 hours to cure. I'll do it with you.
- a general oven, an infrared furnace, or the like can be used as a heating facility.
- thermosetting resin cured product according to the present invention is excellent in electrical characteristics and electrical insulation properties, it can be applied to electronic components such as semiconductor elements, semiconductor packages, and printed wiring boards, and a cured film of a thermosetting resin composition. By forming the film, it can act as an insulating layer.
- thermosetting resin cured products using an anti-aging agent (C) and a styrene-butadiene copolymer having a specific functional group conform to JIS K7113 (plastic tensile test method).
- the tensile modulus of elasticity (hereinafter also referred to simply as “elastic modulus”) is usually 1.5 GPa or less, preferably 1. OGPa or less, and cracks are unlikely to occur even in environments with large temperature changes. This is preferable because the change in physical properties before and after the reliability test is extremely small and the thermal shock resistance and heat resistance are excellent.
- Examples 1_1 to 1_7 and Comparative Example 1_1 will be described.
- the raw materials used in these examples and the physical property evaluation methods of the obtained cured products are shown below.
- A1-1 Phenolic-piphenylene glycol condensation type epoxy resin
- Talylate Z dibulebenzene 78Z5Z5ZlO / 2 (weight ratio)
- D1— 2 Phenolic novolak resin (made by Showa Polymer Co., Ltd., trade name: CRG—951)
- D1— 3 Dicyandiamide
- Gen-based rubber latex was purified by precipitation with methanol, vacuum-dried, and then subjected to elemental analysis and determined from the nitrogen content. [0073] (2) Glass transition temperature
- the resin composition was applied to a PET film and heated in a convection oven at 80 ° C. for 30 minutes. After further heating at 170 ° C for 2 hours, the PET film was peeled off to produce a cured film with a thickness of 50 ⁇ m.
- the resin composition was applied to a PET film and heated in a convection oven at 80 ° C. for 30 minutes. After further heating at 170 ° C for 2 hours, the PET film was peeled off to produce a cured film with a thickness of 50 ⁇ m.
- the resin composition was applied to a SUS substrate and heated in a convection oven at 80 ° C. for 30 minutes to produce a uniform resin film having a thickness of 50 ⁇ m.
- the film was further heated at 170 ° C for 2 hours to obtain a cured film.
- the cured film was subjected to a resistance test for 500 hours under the conditions of a temperature of 85 ° C and a humidity of 85% using a constant temperature and constant chamber test device (manufactured by Tabai Espec).
- the volume resistivity between the cured film layers was measured before and after the test in accordance with JIS C6481.
- the resin composition was applied to the release-treated PET film, and heated in a convection oven at 80 ° C for 30 minutes to prepare a uniform resin film having a thickness of 50 / m. Furthermore, it was heated at 170 ° C for 2 hours to obtain a cured film. This cured film was applied to a thermal shock tester (Tanoku Yecspec TSA-40L
- thermosetting resin composition was applied to a mirror-finished plate-like SUS and heated in a convection oven at 80 ° C. for 30 minutes. Furthermore, it was heated at 170 ° CX for 2 hours to produce a 10 ⁇ m thick cured film on the plate-like SUS. An aluminum electrode was formed on the cured film, and the dielectric constant and dielectric loss were measured under a condition of a frequency of 1 MHz using a dielectric constant Z dielectric loss measuring device (manufactured by Hewlett Packard: LCR meter HP4248). [0078] [Example 1]
- A2-2 phenol-naphthol Z formaldehyde condensation type epoxy resin (Nippon Kayaku Co., Ltd., trade name: NC_7000L, softening point 83-93 ° C)
- A2-3 o-Talesol Z formaldehyde condensation novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EOCN_104S, softening point 90-94 ° C)
- SB copolymer styrene-butadiene copolymer
- NB copolymer acrylonitrile-butadiene copolymer
- the SB copolymer (B2-2) was prepared in the same manner as in Synthesis Example 1 except that 60 parts of butadiene, 20 parts of styrene, 18 parts of 2-hydroxybutyl methacrylate and 2 parts of dibutenebenzene were used as raw material monomers. Synthesized and isolated. When the glass transition temperature (Tg) of the SB copolymer (B2-2) was measured by DSC method, it was -45. C.
- B copolymer (B2-4) was synthesized and isolated. With respect to the SB copolymer (B2-4), the glass transition temperature (Tg) was measured by DSC method, which was -57 ° C.
- the SB copolymer was prepared in the same manner as in Synthesis Example 1, except that 20 parts of butadiene, 68 parts of styrene, 5 parts of 2-hydroxybutyl methacrylate, 5 parts of methacrylic acid and 2 parts of dibutenebenzene were used as raw material monomers. (B2-5) was synthesized and isolated. About SB copolymer (B2-5)
- the glass transition temperature (Tg) measured by DSC method was 12 ° C.
- NB copolymer (b-6) was synthesized in the same manner as in Synthesis Example 1, except that 70 parts of butadiene, 20 parts of acrylonitrile, 5 parts of 2-hydroxybutyl methacrylate and 5 parts of methacrylic acid were used as raw material monomers. Isolated. With respect to the NB copolymer (b-6), the glass transition temperature (Tg) was measured by DSC method, and was found to be _55 ° C.
- a NB copolymer (b_7) was synthesized in the same manner as in Synthesis Example 1 except that 60 parts of butadiene, 20 parts of acrylonitrile, 18 parts of 2-hydroxybutyl methacrylate and 2 parts of dibutylbenzene were used as raw material monomers. Isolated. With respect to the NB copolymer (b_7), the glass transition point (Tg) was measured by DSC method, and was found to be _42 ° C.
- thermosetting resin composition was applied to a mirror-finished plate-like SUS, and heated in a convection oven at 80 ° C. for 30 minutes. Furthermore, it was heated at 150 ° C for 4 hours to produce a 10 / im thick cured film on the plate-like SUS. An aluminum electrode was formed on this cured film, and the dielectric constant and dielectric loss were measured with a dielectric constant / dielectric loss measuring device (Hewlett Packard, LCR meter HP4248) under the condition of a frequency of 1 MHz.
- a dielectric constant / dielectric loss measuring device Hewlett Packard, LCR meter HP4248
- thermosetting resin composition was applied to a PET film and heated in a convection oven at 80 ° C for 30 minutes. After further heating at 150 ° C for 4 hours, the PET film was peeled off to produce a 50 ⁇ ⁇ ⁇ thick cured film. This cured film is punched and formed with a dumbbell to produce a 3 mm wide test piece, and glass transition using the thermomechanical analyzer (TMA / SS6100) manufactured by Seiko Instruments Inc. by the TMA viscoelastic method. The temperature (Tg) was determined.
- thermosetting resin composition was applied to a mirror-finished plate-like SUS and heated in a convection oven at 80 ° C. for 30 minutes to prepare a uniform resin film having a thickness of 50 ⁇ m. The film was further heated at 150 ° C. for 4 hours to obtain a cured film. The temperature of the cured film is 85 ° C and the humidity is 85 using a constant temperature and humidity test device (manufactured by Tabai Espec Co., Ltd.). /. Under these conditions, a 500 hour resistance test was conducted. Cured film body before and after resistance test according to JIS C6481 The product resistivity was measured.
- a 50 ⁇ m thick cured film was produced in the same manner as in the above (2) glass transition temperature measurement method, and then the cured film was punched and formed with a dumbbell to prepare a test piece having a width of 5 mm.
- the test piece was measured according to JIS K7113 (plastic tensile test method), and the tensile modulus was described as the elastic modulus.
- JIS K7113 plastic tensile test method
- the tensile modulus is defined as the ratio of the tensile stress within the tensile proportional limit (the initial linear part of the stress-strain curve) and the corresponding strain.
- thermosetting resin composition was applied to the pattern substrate shown in FIG. 1 and heated in a convection oven at 80 ° C. for 30 minutes to prepare a uniform resin film having a thickness of 50 zm.
- the substrate was further heated at 150 ° C for 4 hours to obtain a substrate with a cured film.
- a thermal shock test was conducted on a substrate with this cured film using a thermal shock tester (TSA-40L, manufactured by Tabai Espec Co., Ltd.) with one cycle from 65 ° C / 30 minutes to 150 ° C / 30 minutes. .
- TSA-40L thermal shock tester
- the number of cycles in which defects such as cracks occurred in the cured resin was confirmed up to 1000 cycles every 100 cycles, and the number of cycles in which cracks occurred was evaluated. If no crack occurred after 1000 cycles, it was evaluated as “no crack”.
- thermosetting resin composition was prepared by dissolving the epoxy resin (A2), styrene-butadiene copolymer (B2) and curing agent (D2) shown in Table 3 in the solvent (F2).
- a cured film was prepared from the thermosetting resin composition according to the method described in the above evaluation method, and each physical property was measured. The results are shown in Table 3.
- thermosetting resin composition comprising the components shown in Table 3 was prepared in the same manner as in Example 2-1, and the cured film was obtained. Each physical property was measured in the same manner as in Example 2-1. The results are shown in Table 3.
- thermosetting resin composition and the cured product thereof according to the present invention for example, a multilayer circuit When an interlayer insulating film or the like of the substrate is formed, a circuit substrate having excellent electrical characteristics can be manufactured.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/719,024 US20080039585A1 (en) | 2004-11-10 | 2005-11-09 | Thermosetting Resin Composition, Thermosetting Film, Cured Product of Those, and Electronic Component |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004326288A JP2006137791A (ja) | 2004-11-10 | 2004-11-10 | 熱硬化性樹脂組成物およびその硬化物 |
JP2004-326288 | 2004-11-10 | ||
JP2004-346198 | 2004-11-30 | ||
JP2004346198A JP2006152148A (ja) | 2004-11-30 | 2004-11-30 | 熱硬化性樹脂組成物、熱硬化性フィルムおよびそれらの硬化物、ならびに電子部品 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006051820A1 true WO2006051820A1 (ja) | 2006-05-18 |
Family
ID=36336497
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2005/020547 WO2006051820A1 (ja) | 2004-11-10 | 2005-11-09 | 熱硬化性樹脂組成物、熱硬化性フィルムおよびそれらの硬化物、ならびに電子部品 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20080039585A1 (ja) |
KR (1) | KR20070085911A (ja) |
TW (1) | TW200624503A (ja) |
WO (1) | WO2006051820A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007099803A (ja) * | 2005-09-30 | 2007-04-19 | Jsr Corp | 樹脂組成物およびその硬化物 |
JP2009108144A (ja) * | 2007-10-26 | 2009-05-21 | Panasonic Electric Works Co Ltd | フレキシブルハロゲンフリーエポキシ樹脂組成物、樹脂付き金属箔、カバーレイフィルム、プリプレグ、プリント配線板用積層板、金属張フレキシブル積層板 |
CN109644568A (zh) * | 2016-09-06 | 2019-04-16 | 松下知识产权经营株式会社 | 印刷布线板、印刷电路板、半固化片 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009058295A2 (en) * | 2007-10-30 | 2009-05-07 | Henkel Ag & Co. Kgaa | Epoxy paste adhesives resistant to wash-off |
KR100975964B1 (ko) * | 2008-03-27 | 2010-08-13 | 엘지이노텍 주식회사 | 향상된 경화율이 구현된 언더필 및 이를 이용한 패키지반도체 및 반도체 패키징 방법 |
JP5287390B2 (ja) * | 2009-03-16 | 2013-09-11 | ソニー株式会社 | 半導体装置、伝送システム、半導体装置の製造方法及び伝送システムの製造方法 |
WO2015125928A1 (ja) * | 2014-02-21 | 2015-08-27 | 三井金属鉱業株式会社 | 内蔵キャパシタ層形成用銅張積層板、多層プリント配線板及び多層プリント配線板の製造方法 |
DE102015100914A1 (de) * | 2015-01-22 | 2016-07-28 | Grass Gmbh & Co. Kg | Verfahren zur Herstellung eines Sensors zu einem Möbelteil |
JP6557155B2 (ja) * | 2015-02-02 | 2019-08-07 | 株式会社日本触媒 | 硬化性樹脂およびその製造方法 |
CN116614940A (zh) * | 2016-11-15 | 2023-08-18 | 株式会社力森诺科 | 导体基板、布线基板及布线基板的制造方法 |
JP7090428B2 (ja) * | 2018-02-05 | 2022-06-24 | デクセリアルズ株式会社 | 接着剤組成物、熱硬化性接着シート及びプリント配線板 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS624744A (ja) * | 1985-06-29 | 1987-01-10 | Japan Synthetic Rubber Co Ltd | エポキシ樹脂用フレキシビライザ |
JPH02117948A (ja) * | 1988-08-30 | 1990-05-02 | Japan Synthetic Rubber Co Ltd | 変性エポキシ組成物 |
JPH04202351A (ja) * | 1990-11-30 | 1992-07-23 | Japan Synthetic Rubber Co Ltd | 変性エポキシ組成物 |
JP2000311518A (ja) * | 1999-04-28 | 2000-11-07 | Jsr Corp | 有機絶縁材用組成物、有機絶縁材、封止材および回路基板 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6146749A (en) * | 1999-05-03 | 2000-11-14 | Jsr Corporation | Low dielectric composition, insulating material, sealing material, and circuit board |
JP3943883B2 (ja) * | 2001-10-02 | 2007-07-11 | 新日鐵化学株式会社 | 絶縁用樹脂組成物及びこれを用いた積層体 |
-
2005
- 2005-11-09 KR KR1020077012925A patent/KR20070085911A/ko not_active Application Discontinuation
- 2005-11-09 US US11/719,024 patent/US20080039585A1/en not_active Abandoned
- 2005-11-09 WO PCT/JP2005/020547 patent/WO2006051820A1/ja active Application Filing
- 2005-11-10 TW TW094139468A patent/TW200624503A/zh unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS624744A (ja) * | 1985-06-29 | 1987-01-10 | Japan Synthetic Rubber Co Ltd | エポキシ樹脂用フレキシビライザ |
JPH02117948A (ja) * | 1988-08-30 | 1990-05-02 | Japan Synthetic Rubber Co Ltd | 変性エポキシ組成物 |
JPH04202351A (ja) * | 1990-11-30 | 1992-07-23 | Japan Synthetic Rubber Co Ltd | 変性エポキシ組成物 |
JP2000311518A (ja) * | 1999-04-28 | 2000-11-07 | Jsr Corp | 有機絶縁材用組成物、有機絶縁材、封止材および回路基板 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007099803A (ja) * | 2005-09-30 | 2007-04-19 | Jsr Corp | 樹脂組成物およびその硬化物 |
JP2009108144A (ja) * | 2007-10-26 | 2009-05-21 | Panasonic Electric Works Co Ltd | フレキシブルハロゲンフリーエポキシ樹脂組成物、樹脂付き金属箔、カバーレイフィルム、プリプレグ、プリント配線板用積層板、金属張フレキシブル積層板 |
CN109644568A (zh) * | 2016-09-06 | 2019-04-16 | 松下知识产权经营株式会社 | 印刷布线板、印刷电路板、半固化片 |
Also Published As
Publication number | Publication date |
---|---|
TW200624503A (en) | 2006-07-16 |
US20080039585A1 (en) | 2008-02-14 |
KR20070085911A (ko) | 2007-08-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2006051820A1 (ja) | 熱硬化性樹脂組成物、熱硬化性フィルムおよびそれらの硬化物、ならびに電子部品 | |
KR101685775B1 (ko) | 중합체 분체, 경화성 수지 조성물 및 그의 경화물 | |
JP5816752B2 (ja) | フレキシブルなビスマレイミド、ベンズオキサジン、エポキシ−無水物付加生成物複合接着剤 | |
US20060079609A1 (en) | Heat curable resin composition having a low elastic modulus, heat curable film using same, and cured products | |
EP3127933A1 (en) | Heat-curable epoxy resin composition | |
JP2011162615A (ja) | プリプレグおよび金属張り積層板 | |
TWI784366B (zh) | 黏接劑組成物 | |
JP2010209140A (ja) | プリプレグ、金属張り積層板及びプリント配線板 | |
JP2020128501A (ja) | 樹脂組成物 | |
TW202216888A (zh) | 樹脂組成物、預浸體、附有樹脂之金屬箔、積層板、印刷線路板、及樹脂組成物的製造方法 | |
JP2020015859A (ja) | 樹脂組成物 | |
JP2017188667A (ja) | 絶縁材料及び電子部品 | |
KR20110131271A (ko) | (메트)아크릴레이트계 중합체, 수지 조성물 및 성형체 | |
JP2001192539A (ja) | 熱硬化性樹脂組成物、その硬化物およびその硬化物を含む回路基板 | |
TW202317702A (zh) | 熱硬化性樹脂組成物、樹脂片、附樹脂之金屬箔、覆金屬積層板及印刷配線板 | |
JP2020015860A (ja) | 樹脂組成物 | |
JP2007269922A (ja) | ポリシロキサン複合架橋粒子および該複合架橋粒子を含む樹脂組成物 | |
JP2006137791A (ja) | 熱硬化性樹脂組成物およびその硬化物 | |
TWI761501B (zh) | 密封用薄膜、密封結構體、及密封結構體的製造方法 | |
JP4529247B2 (ja) | 熱硬化性樹脂組成物、その硬化物およびその硬化物を含む回路基板 | |
JP2007099803A (ja) | 樹脂組成物およびその硬化物 | |
JP2020059820A (ja) | 樹脂材料及び多層プリント配線板 | |
JP7501583B2 (ja) | 樹脂組成物 | |
JP2002060467A (ja) | 熱硬化性樹脂組成物およびその硬化物 | |
TWI843792B (zh) | 樹脂組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KM KN KP KR KZ LC LK LR LS LT LU LV LY MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 11719024 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020077012925 Country of ref document: KR |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 05806197 Country of ref document: EP Kind code of ref document: A1 |
|
WWP | Wipo information: published in national office |
Ref document number: 11719024 Country of ref document: US |