WO2014059653A1 - Cyanate ester resin composition, and prepreg, laminate, and metal-clad laminate that are fabricated by using the same - Google Patents
Cyanate ester resin composition, and prepreg, laminate, and metal-clad laminate that are fabricated by using the same Download PDFInfo
- Publication number
- WO2014059653A1 WO2014059653A1 PCT/CN2012/083184 CN2012083184W WO2014059653A1 WO 2014059653 A1 WO2014059653 A1 WO 2014059653A1 CN 2012083184 W CN2012083184 W CN 2012083184W WO 2014059653 A1 WO2014059653 A1 WO 2014059653A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cyanate resin
- resin composition
- prepreg
- weight
- epoxy resin
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/012—Flame-retardant; Preventing of inflammation
-
- 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
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
Definitions
- the present invention relates to a resin composition, and more particularly to a cyanate resin composition and a prepreg, a laminate and a metal foil-clad laminate produced using the same. Background technique
- Cyanate resin has excellent dielectric properties, heat resistance, mechanical properties and processability, and is a commonly used matrix resin in the production of metal foil laminates for high-end printed wiring boards.
- prepregs and laminates using a resin containing a bisphenol A type cyanate resin and a maleimide compound have been widely used in semiconductor packaging. Used in high performance printed circuit board materials.
- the bisphenol A type cyanate resin composition has excellent heat resistance, chemical resistance, adhesion, etc., but the cured product thereof has a problem of high water absorption rate, insufficient heat and humidity resistance, and mechanical properties such as elastic modulus. Performance does not meet the performance requirements of high-end substrates.
- DCPD type cyanate resin composition has excellent dielectric properties, heat resistance, heat and humidity resistance and good mechanical properties. It is widely used in high frequency circuit boards, high performance composite materials, etc., and can be used to make up for bisphenol A type. The problem that the cyanate resin is insufficient in moist heat resistance. However, its flame retardancy is poor and it cannot meet the performance requirements of high-end substrates.
- the resin composition for producing a metal foil-clad laminate is generally required to have flame retardancy, and therefore it is generally required to simultaneously use a bromine-containing flame retardant to achieve flame retardancy.
- a compound-containing compound due to the increased attention to environmental issues in recent years, it is necessary to use a compound-containing compound to achieve flame retardancy.
- phosphorus compounds are frequently used as flame retardants, but various intermediates and production processes of the tablet compounds have certain toxicity. Phosphorus compounds may generate toxic gases (such as methylphosphine) and toxic substances (such as triphenyl) during combustion. Phosphine, etc.), its waste may pose a potential hazard to the aquatic environment.
- U.S. Patent (US7655871) uses a phenolic cyanate resin, a biphenyl epoxy resin, a phenolic resin as a matrix resin, a large amount of silicon micropowder as a filler, a glass fiber cloth as a reinforcing material, and a heat resistance. Excellent, achieved no! 3 ⁇ 4 flame retardant.
- the phenolic cyanate resin is cured under the general process conditions, the cured product has a large water absorption rate and poor heat and humidity resistance.
- the phenolic cyanate resin composition itself has poor flame retardancy, and in order to meet the demand for halogen-free and phosphorus-free flame retardant, it is necessary to add a larger amount of inorganic filler to achieve flame retardancy, which in turn leads to a decrease in workability.
- An object of the present invention is to provide a cyanate resin composition which has good heat resistance and flame retardancy and which can be used for producing a printed wiring board material.
- Another object of the present invention is to provide a prepreg, a laminate, and a metal foil-clad laminate produced using the above cyanate resin composition, a laminate and a metal foil-coated layer produced using the prepreg
- the pressure material also has good flame retardancy without using a compound or a phosphorus compound as a flame retardant, and has a low coefficient of thermal expansion in the X and Y directions, and is suitable for use in a substrate material for producing a high-density printed wiring board.
- the present invention provides a cyanate resin composition
- a cyanate resin composition comprising a cyanate resin, an epoxy resin, and an inorganic filler, and the structural formula of the cyanate resin is as follows:
- n is an integer from 1 to 50. Further, n is an integer of 1 to 10, and when n is in this range, the cyanate resin has a good wettability to the substrate.
- the cyanate resin of the present invention is not particularly limited, and is a cyanate resin or a prepolymer thereof having at least two cyanate groups per molecule and as shown in Formula I.
- the cyanate resin may be used singly or as a mixture of at least two cyanate resins as needed.
- the amount of the cyanate resin to be used is not particularly limited, and it preferably accounts for the cyanate resin in the cyanate resin composition and is not present! 10 to 90% by weight, more preferably 20 to 80% by weight, particularly preferably 30 to 70% by weight, based on the total amount of the epoxy resin.
- the epoxy resin according to the present invention is an epoxy resin containing at least two epoxy groups per molecule and having no halogen atom in its molecular structure. In order to improve the heat resistance and flame retardancy of the cyanate resin composition, this is not! 3 ⁇ 4 epoxy resin is preferably absent as shown in formula II! 3 ⁇ 4 epoxy resin:
- R is a group and R 1() is
- R 2 is an aryl group, such as phenyl, naphthyl, biphenyl, etc.
- R 3 , R 4 are a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a group as shown by the formula
- R 5 , R 6 is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group
- m is an integer of 0 to 5
- c is an integer of 1 to 5
- n is an integer of 1 to 50.
- R 7 is an aryl group
- R 8 is a _0_ or -C- group
- R 9 is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group
- i is 0 or 1
- j is 1 or 2.
- the epoxy resin is further preferably an aralkyl novolac type epoxy resin or an aryl ether type novolac epoxy resin having a structure represented by Formula V:
- R is an O- or R 6 group
- R 2 is an aryl group such as phenyl, naphthyl, biphenyl, etc.
- R 3 , R 5 , R 6 are a hydrogen atom, an alkyl group, an aryl group Or an aralkyl group
- m is an integer of 1 to 5
- c is an integer of 1 to 5
- n is an integer of 1 to 50.
- the above-mentioned epoxy resin may be used singly or in combination of plural kinds as needed.
- the amount of the halogen-free epoxy resin to be used is not particularly limited, and it is preferably 10 to 90% by weight, more preferably 20% by weight based on the total of the cyanate resin and the epoxy resin in the cyanate resin composition. It is -80% by weight, particularly preferably 30 to 70% by weight.
- the inorganic filler according to the present invention is not particularly limited. Among them, fused silica has a low coefficient of thermal expansion and is excellent in flame retardancy and heat resistance of boehmite.
- the amount of the inorganic filler to be used in the present invention is not particularly limited, and the cyanate resin is not contained in the cyanate resin composition!
- the amount of the corresponding inorganic filler is preferably 10 to 300 parts by weight, more preferably 30 to 200 parts by weight, particularly preferably 50 to 150 parts by weight.
- the cyanate resin composition of the present invention may further comprise a maleimide compound.
- the maleimide compound is not particularly limited and is a compound containing at least one maleimide group per molecule.
- the maleimide compound is further preferably a compound containing at least two maleimide groups per molecule.
- the amount of the maleimide compound to be used in the present invention is not particularly limited, and it is preferably 5 to 80% by weight based on the total amount of the cyanate resin and the maleimide compound in the cyanate resin composition. It is particularly preferably 10 to 70% by weight.
- the present invention also provides a prepreg produced using the above cyanate resin composition, the prepreg comprising a substrate and a cyanate resin composition adhered to the substrate by impregnation and drying.
- the present invention further provides a laminate and a metal-clad laminate produced using the above prepreg.
- the laminate comprises at least one prepreg, which is laminated and cured to obtain a laminate
- the metal foil-clad laminate comprises at least one prepreg, and one or both sides of the prepreg are coated with a metal foil, and the laminate is cured to obtain a metal foil-clad laminate.
- the cyanate resin composition provided by the present invention has good heat resistance and flame retardancy.
- the laminate prepared by using the prepreg obtained from the cyanate resin composition and the metal foil-clad laminate have good flame retardancy without using a compound or a phosphorus compound as a flame retardant.
- the low X, Y direction thermal expansion coefficient is therefore suitable for the substrate material for making high density printed wiring boards.
- the present invention provides a cyanate resin composition
- a cyanate resin composition comprising a cyanate resin, an epoxy-free resin, and an inorganic filler, and the structural formula of the cyanate resin is as follows:
- n is an integer from 1 to 50. More preferably, n is an integer of from 1 to 10, and when n is in this range, the cyanate resin has good wettability to the substrate.
- the cyanate resin of the present invention is not particularly limited, and is a cyanate resin or a prepolymer thereof having at least two cyanate groups per molecule and as shown in Formula I.
- the cyanate resin may be used singly or as a mixture of at least two cyanate resins as needed.
- the amount of the cyanate resin to be used is not particularly limited, and it preferably accounts for the cyanate resin in the cyanate resin composition and is not present! 10 to 90% by weight, more preferably 20 to 80% by weight, particularly preferably 30 to 70% by weight, based on the total amount of the epoxy resin.
- the method for synthesizing the cyanate resin is not particularly limited, and it may be selected from a synthetic method of a usual cyanate resin.
- the method for synthesizing the cyanate resin is as follows: a phenol phenyl aralkyl phenol resin having a structure represented by the following formula IV is reacted with a cyanogen halide in an inert organic solvent in the presence of a basic compound. A cyanate resin is obtained.
- n is an integer of 1 to 50.
- the epoxy resin according to the present invention is an epoxy resin containing at least two epoxy groups per molecule and having no atomic atoms in the molecular structure.
- the epoxy-free epoxy resin is bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic epoxy resin, cresol novolac epoxy resin, bisphenol A phenolic epoxy resin, trifunctional phenol Epoxy resin, tetrafunctional phenol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, fluorene epoxy resin, phenoxy epoxy resin, norbornene epoxy resin, adamantane Epoxy resin, bismuth epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl type epoxy resin, aralkyl novolac type epoxy resin, aryl ether type phenolic ring Oxygen resin, cycloaliphatic epoxy resin, polyol epoxy resin, silicon-containing epoxy resin, nitrogen-containing epoxy resin, compound obtained by double bond epoxidation, glycidylamine epoxy resin
- the epoxy resin is preferably an epoxy resin having a structure as shown in the formula II:
- R is an O—or
- R 2 is an aryl group, such as phenyl, naphthyl, biphenyl, etc.
- R 3 , R 4 are a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a group as shown by the formula
- R 5 , R 6 is a hydrogen atom, an alkyl group, an aryl group or Aralkyl
- m is an integer of 0 ⁇ 5
- an integer n-t is an integer of 1 ⁇ 50
- R 7 is an aryl group
- R 8 is an O- or -C- group
- R 9 is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group
- i is 0 or 1
- j is 1 or 2 .
- the epoxy resin is further preferably an aralkyl novolac type epoxy resin or an aryl ether type novolac epoxy resin having a structure represented by Formula V:
- R is an O- or R 6 group
- R 2 is an aryl group such as phenyl, naphthyl, biphenyl, etc.
- R 3 , R 5 , R 6 are a hydrogen atom, an alkyl group, an aryl group Or an aralkyl group
- m is an integer of 1 to 5
- c is an integer of 1 to 5
- n is an integer of 1 to 50.
- phenol phenyl aralkyl type epoxy resin a phenol biphenyl aralkyl type epoxy resin, a phenol naphthyl aralkyl type epoxy resin, a naphthol phenyl aralkyl type epoxy resin, naphthalene Phenol biphenyl aralkyl type epoxy resin, naphthol naphthyl aralkyl type epoxy resin, phenol phenyl ether type epoxy resin, phenol biphenyl ether type epoxy resin, phenol naphthyl ether type epoxy Resin, naphthol phenyl ether type epoxy resin, naphthol phenyl ether type epoxy resin, and naphthol naphthyl ether type epoxy resin.
- the I3 ⁇ 4-free epoxy resin may be used singly or in combination of plural kinds as needed.
- the amount of the halogen-free epoxy resin to be used is not particularly limited, and it is preferably 10 to 90% by weight, more preferably 20% by weight based on the total of the cyanate resin and the epoxy resin in the cyanate resin composition. It is -80% by weight, particularly preferably 30 to 70% by weight.
- the inorganic filler according to the present invention is not particularly limited, and is specifically silica (for example, crystalline silica, fused silica, amorphous silica, spherical silica, hollow silica, etc.), Metal hydrates (such as aluminum hydroxide, boehmite, magnesium hydroxide, etc.), molybdenum oxide, zinc molybdate, titanium oxide, barium titanate, barium titanate, barium sulfate, boron nitride, aluminum nitride, silicon carbide , alumina, zinc borate, zinc stannate, clay, kaolin, talc, mica, short glass fibers and hollow glass.
- silica for example, crystalline silica, fused silica, amorphous silica, spherical silica, hollow silica, etc.
- Metal hydrates such as aluminum hydroxide, boehmite, magnesium hydroxide, etc.
- fused silica has a low coefficient of thermal expansion and is excellent in flame retardancy and heat resistance of boehmite.
- the average particle diameter (d50) of the inorganic filler is not particularly limited, but the average particle diameter U50 is preferably from 0.1 to 10 ⁇ m, more preferably from 0.2 to 5 ⁇ m from the viewpoint of dispersibility.
- the inorganic filler materials of different types, different particle size distributions or different average particle diameters may be used singly or in combination as needed.
- the amount of the inorganic filler to be used in the present invention is not particularly limited, and the cyanate resin is not contained in the cyanate resin composition!
- the amount of the corresponding inorganic filler is preferably 10 to 300 parts by weight, more preferably 30 to 200 parts by weight, particularly preferably 50 to 150 parts by weight.
- the surface treatment agent is not particularly limited and is selected from the surface treatment agents commonly used for inorganic treatment. Specific examples thereof include a tetraethyl orthosilicate compound, an organic acid compound, an aluminate compound, a titanate compound, a silicone oligomer, a macromolecular treatment agent, and a silane coupling agent.
- the silane coupling agent is not particularly limited, and is selected from a silane coupling agent commonly used for surface treatment of inorganic materials, and is specifically an aminosilane coupling agent, an epoxy silane coupling agent, a vinyl silane coupling agent, and a phenyl group.
- the wetting and dispersing agent are not particularly limited and are selected from the group consisting of wetting and dispersing agents commonly used in coatings. The present invention may be used alone or in appropriate combination with different types of surface treating agents or wetting and dispersing agents as needed.
- the cyanate resin composition of the present invention may further comprise a maleimide compound.
- the maleimide compound is not particularly limited and is a compound containing at least one maleimide group per molecule.
- the maleimide compound is further preferably a compound containing at least two maleimide groups per molecule.
- the maleimide compound is not particularly limited, and is specifically N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl group).
- Maleimide N-(2,6-dimethylphenyl)maleimide, bis(4-maleimidophenyl)methane, 2,2-di(4-( 4-maleimidophenoxy)-phenyl)propane, two (3,5-Dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, two (3 , 5-diethyl-4-maleimidophenyl)methane, etc., polyphenylmethane maleimide, prepolymer of the above maleimide compound or maleimide a prepolymer of a compound and an amine compound.
- the maleimide compound is preferably bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, Bis(3-ethyl-5-methyl-4-maleimidophenyl)methane.
- the maleimide compound can be used singly or in combination of plural kinds as needed.
- the amount of the maleimide compound to be used in the present invention is not particularly limited, and it is preferably 5 to 80% by weight based on the total amount of the cyanate resin and the maleimide compound in the cyanate resin composition. It is particularly preferably 10 to 70% by weight.
- the cyanate resin composition of the present invention may be used in combination with a cyanate resin other than the cyanate resin represented by Formula I as long as it does not impair the inherent properties of the cyanate resin composition. It may be selected from bisphenol A type cyanate resin, bisphenol F type cyanate resin, bisphenol M type cyanate resin, bisphenol S type cyanate resin, bisphenol E type cyanate resin, bisphenol P-type cyanate resin, novolac type cyanate resin, cresol novolac type cyanate resin, naphthol novolac type cyanate resin, dicyclopentadiene type cyanate resin, tetramethyl bisphenol F A prepolymer of the above cyanate resin, such as a cyanate resin, a phenolphthalein type cyanate resin, a naphthol type cyanate resin, an aralkyl type cyanate resin, or the like. These cyanate resins may be used singly or in combination of plural kinds as needed.
- the cyanate resin composition of the present invention can also be used in combination with various high polymer and organic filler materials as long as it does not impair the inherent properties of the cyanate resin composition.
- it is a different liquid crystal polymer, a thermosetting resin, a thermoplastic resin and oligomers and rubber bodies thereof, different flame retardant compounds or additives, and the like. They can be used singly or in combination of plural kinds as needed. Silicone powders are preferred because they have good flame retardant properties.
- the cyanate resin composition of the present invention can also be used in combination with a curing accelerator as needed to control the curing reaction rate.
- the curing accelerator is not particularly limited, and may be selected from curing accelerators commonly used for promoting curing of cyanate resins, epoxy resins or epoxy-free epoxy resins, specifically copper, zinc, cobalt, nickel, manganese.
- Organic salts of metals such as imidazole and its derivatives, tertiary amines, and the like.
- the present invention further provides a prepreg, a laminate, and a metal foil-clad laminate produced using the above cyanate resin composition.
- the prepreg includes a substrate and a cyanate resin composition adhered thereto by impregnation and drying.
- the laminate comprises at least one prepreg which is laminated to obtain a laminate.
- the metal-clad laminate comprises at least one prepreg, and a metal foil is coated on one or both sides of the prepreg, and the metal foil laminate is cured by lamination.
- the laminate and the metal foil-clad laminate produced by using the prepreg have good heat resistance and a low X, Y direction thermal expansion coefficient, and are not used! When a compound or a phosphorus compound is used as a flame retardant, it also has good flame retardancy, and thus is suitable for use as a substrate material for producing a high-density printed wiring board.
- the substrate of the present invention is not particularly limited and may be selected from known substrates for producing various printed wiring board materials. Specifically, it is inorganic fiber (for example, E glass, D glass, M glass, S glass, T glass, NE glass, quartz glass fiber, etc.), organic fiber (such as polyimide, polyamide, polyester, liquid crystal polymer, etc.) .
- the form of the substrate is usually a woven fabric, a nonwoven fabric, a roving, a staple fiber, a fiber paper or the like.
- the substrate of the present invention is preferably a glass cloth.
- the prepreg according to the present invention is produced by combining a cyanate resin composition with a substrate, and the laminate of the present invention can be obtained by laminating and curing using the above prepreg.
- the metal foil-clad laminate of the present invention is prepared by: placing one of the above prepregs or stacking two or more prepregs, as needed in the prepreg or stacking prepreg A metal foil is placed on one or both surfaces and laminated to obtain a metal foil laminate.
- the metal foil is not particularly limited and may be selected from metal foils for printed wiring board materials.
- the lamination conditions can be selected from laminates for printed wiring boards and general lamination conditions for multilayer boards.
- the metal foil-clad laminate prepared by the cyanate resin composition of the present invention is tested for X, Y direction thermal expansion coefficient (X-CTE/Y-CTE), dipping resistance and flame retardancy, and the test results thereof
- X-CTE/Y-CTE Y direction thermal expansion coefficient
- dipping resistance and flame retardancy dipping resistance and flame retardancy
- a phenol phenyl aralkyl type cyanate resin obtained in the synthesis example 30 parts by weight of a naphthol naphthyl ether type epoxy resin (EXA-7311, supplied by DIC Corporation), and 0.02 parts by weight of zinc octoate Dissolve in methyl ethyl ketone and mix well, then add 100 parts by weight of boehmite (APYRAL AOH 30, supplied by Nabaltec), 5 parts by weight of silicone powder (KMP-605, supplied by Shin-Etsu Chemical), 1 part by weight of epoxy silane Coupling agent (Z-6040, supplied by Dow Corning), 1 part by weight of dispersant (BYK-W903, supplied by BYK), adjusted to the appropriate viscosity with methyl ethyl ketone, and stirred and mixed to obtain a glue.
- boehmite AOH 30, supplied by Nabaltec
- silicone powder KMP-605, supplied by Shin-Etsu Chemical
- Z-6040 epoxy silane Co
- the prepreg was prepared by dipping the above glue with a 1078, 2116 glass fiber cloth, and then drying the solvent to remove the solvent.
- the above prepregs of 2 x 1078, 4 x 2116, and 8 x 2116 were laminated, and 18 ⁇ m thick electrolytic copper foil was pressed on both sides thereof, and solidified in a press for 2 hours, and the curing pressure was 45.
- Kg/cm 2 curing temperature was 220 ° C, and copper clad laminates having thicknesses of 0.1, 0.4, and 0.8 mm were obtained, respectively.
- Example 2 35 parts by weight of bisphenol A type cyanate resin prepolymer (BA-3000, supplied by LONZA) was used instead of 35 parts by weight of phenol phenyl aralkyl type cyanate resin used in Example 2, and other implementations were carried out.
- the same method as in Example 1 obtained a copper clad laminate having a thickness of 0.1, 0.4, and 0.8 mm.
- Example 3 40 parts by weight of the phenol phenyl aralkyl type cyanate resin used in Example 3 was replaced with 40 parts by weight of a dicyclopentadiene type cyanate resin (DT-4000, supplied by LONZA), and other examples were as follows. The same method was used to obtain a copper clad laminate having a thickness of 0.1, 0.4, and 0.8 mm.
- the X, Y-direction thermal expansion coefficient (X-CTE/Y-CTE), the solderability and the flame retardancy physical property test data of the metal foil-clad laminates obtained in the above Examples and Comparative Examples are shown in Table 1.
- Dip resistance A 50 x 50 mm sample was immersed in a solder pot at 288 °C, and the stratified foaming was observed and the corresponding time was recorded.
- Test sample thickness 0.4 mm.
- Flame retardancy Judging according to the UL94 vertical burning test standard. Test sample thickness: 0.4 mm.
- X, Y-CTE Y direction along the warp direction of the fiberglass cloth, X direction in the weft direction; Test equipment and conditions: TMA, the temperature rise from room temperature 25 °C to 300 °C at a heating rate of 10 °C/min Thermal expansion coefficient (CTE) in the plane direction from 50 °C to 150 °C. Test sample thickness: 0.1 mm.
- the examples achieved flame retardancy of V-0 and a lower X, Y direction thermal expansion coefficient.
- the cyanate resin composition of the present invention has good heat resistance and flame retardancy, and a laminate and a metal coating made of a prepreg obtained by using the cyanate resin composition.
- Foil laminate not in use!
- a compound or a phosphorus compound as a flame retardant it also has good flame retardancy and a low coefficient of thermal expansion in the X and Y directions, and is suitable for use as a substrate material for producing a high-density printed wiring board.
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CN2012/083184 WO2014059653A1 (en) | 2012-10-19 | 2012-10-19 | Cyanate ester resin composition, and prepreg, laminate, and metal-clad laminate that are fabricated by using the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CN2012/083184 WO2014059653A1 (en) | 2012-10-19 | 2012-10-19 | Cyanate ester resin composition, and prepreg, laminate, and metal-clad laminate that are fabricated by using the same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014059653A1 true WO2014059653A1 (en) | 2014-04-24 |
Family
ID=50487468
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2012/083184 WO2014059653A1 (en) | 2012-10-19 | 2012-10-19 | Cyanate ester resin composition, and prepreg, laminate, and metal-clad laminate that are fabricated by using the same |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2014059653A1 (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101967265A (en) * | 2010-08-31 | 2011-02-09 | 广东生益科技股份有限公司 | High-frequency resin composition and high-frequency circuit substrate manufactured by using same |
CN101980862A (en) * | 2008-03-26 | 2011-02-23 | 住友电木株式会社 | Resin sheet with copper foil, multilayer printed wiring board, method for manufacturing multilayer printed wiring board and semiconductor device |
CN102504201A (en) * | 2011-10-18 | 2012-06-20 | 广东生益科技股份有限公司 | Epoxy resin composition and high-frequency circuit board manufactured thereby |
CN102532801A (en) * | 2010-12-24 | 2012-07-04 | 广东生益科技股份有限公司 | Cyanate resin composition as well as prepreg and laminated material manufactured using same |
-
2012
- 2012-10-19 WO PCT/CN2012/083184 patent/WO2014059653A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101980862A (en) * | 2008-03-26 | 2011-02-23 | 住友电木株式会社 | Resin sheet with copper foil, multilayer printed wiring board, method for manufacturing multilayer printed wiring board and semiconductor device |
CN101967265A (en) * | 2010-08-31 | 2011-02-09 | 广东生益科技股份有限公司 | High-frequency resin composition and high-frequency circuit substrate manufactured by using same |
CN102532801A (en) * | 2010-12-24 | 2012-07-04 | 广东生益科技股份有限公司 | Cyanate resin composition as well as prepreg and laminated material manufactured using same |
CN102504201A (en) * | 2011-10-18 | 2012-06-20 | 广东生益科技股份有限公司 | Epoxy resin composition and high-frequency circuit board manufactured thereby |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI434871B (en) | Resin composition, prepreg and laminate using the same | |
CN107254144B (en) | Resin composition, and prepreg and laminate using same | |
TWI228388B (en) | Prepreg and laminate | |
JP4997727B2 (en) | Flame retardant resin composition, and prepreg and laminate using the same | |
TWI506067B (en) | Prepreg and laminate board | |
KR101738291B1 (en) | Cyanate resin composition and application thereof | |
TW201420675A (en) | Cyanate ester resin composition, prepreg manufactured by using cyanate ester resin composition, laminated material and metal-clad laminated material | |
EP2716709A1 (en) | Resin composition, prepreg and laminate | |
TWI565752B (en) | Resin composition, prepreg, and laminated sheet | |
JP2006193607A (en) | Resin composition and prepreg therewith and laminated sheet | |
CN102558759B (en) | Cyanate ester resin composition and prepreg and laminated material manufactured by using same | |
JPWO2015105109A1 (en) | Insulating layer for printed wiring board and printed wiring board | |
WO2016019595A1 (en) | Epoxy resin composition, and prepreg and copper clad laminate made therefrom | |
TW201420676A (en) | Cyanate ester resin composition and prepreg prepared from same, laminate and metal foil plated laminate produced by using prepreg | |
US20120164463A1 (en) | Cyanate ester resin composition, and prepreg and laminate made therefrom | |
CN109749440B (en) | Cyanate ester resin composition and use thereof | |
JP2004175925A (en) | Prepreg and laminate | |
WO2016107068A1 (en) | Halogen-free thermosetting resin composition, and prepreg and printed circuit laminate using same | |
KR101738292B1 (en) | Cyanate resin composition and application thereof | |
CN109970952B (en) | Cyanate ester resin composition and use thereof | |
WO2018098908A1 (en) | Thermosetting resin composition | |
CN109825039B (en) | Cyanate ester resin composition and use thereof | |
WO2014059653A1 (en) | Cyanate ester resin composition, and prepreg, laminate, and metal-clad laminate that are fabricated by using the same | |
CN109971130B (en) | Cyanate ester resin composition and use thereof | |
WO2014059654A1 (en) | Cyanate ester resin composition, and prepreg, laminate, and metal-clad laminate that are fabricated by using the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12886801 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12886801 Country of ref document: EP Kind code of ref document: A1 |
|
32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12886801 Country of ref document: EP Kind code of ref document: A1 |