Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
  • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
• • 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
• • 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
  • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
  • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
• • 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
• • 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
  • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
  • B32B2260/04—Impregnation, embedding, or binder material
  • B32B2260/046—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
  • 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
  • B32B2307/70—Other properties
  • B32B2307/704—Crystalline
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • 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
• • 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
  • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
• • 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 an epoxy resin composition, and more particularly to an epoxy resin composition and a prepreg and a copper clad laminate produced using the same. Background technique
• the epoxy used is also replaced by a conventional brominated bisphenol A type epoxy resin to a more excellent heat resistant phenolic epoxy resin, such as a phenol novolac type epoxy resin, an o-cresol novolac epoxy resin, a bisphenol A type.
• a phenol novolac type epoxy resin such as a phenol novolac type epoxy resin, an o-cresol novolac epoxy resin, a bisphenol A type.
• the phenolic epoxy resin, the dicyclopentadiene type phenolic epoxy resin, etc. can effectively improve the heat resistance of the cured product, but the use of the general novolac epoxy resin and the phenolic resin brings about a large brittleness of the cured product and drilling processability. Declining, leading to the phenomenon of layered blasting in the lead-free process.
• the addition of filler can effectively reduce the thermal expansion coefficient of the cured product, but due to the addition of the filler, the fluidity is deteriorated, and the hole-filling property of the printed circuit board is deteriorated, and appears under the application of the lead-free process condition. Defects such as reduced reliability and cracking of glass yarn.
• An object of the present invention is to provide an epoxy resin composition which has good fluidity, has high glass transition temperature after curing, high heat resistance, low expansion coefficient, and low moisture absorption.
• Another object of the present invention is to provide a prepreg and a copper clad laminate which are prepared by using the above epoxy resin composition, and have high glass transition temperature, high heat resistance, low expansion coefficient, low hygroscopicity, and can satisfy high multi-layer printing. High reliability requirements for circuit boards.
• an epoxy resin composition comprising the following essential components:
• n is an integer from 0 to 10.
• the epoxy resin of the component (A) is a polyfunctional epoxy resin having a functionality of not less than 2 and an epoxy equivalent of not more than 300 g/eq.
• the epoxy resin comprises: o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, alkylation a benzene type epoxy resin, a trifunctional epoxy resin, and a tetrafunctional epoxy resin, the component (A) is at least one of the above epoxy resins, and the structural formula of the trifunctional epoxy resin is as shown in the second formula:
• the epoxy resin composition further comprises a flame retardant, the flame retardant is a bromine flame retardant or a halogen-free flame retardant; the bromine flame retardant is a non-reactive or reactive bromine flame retardant, and the reaction type
• the bromine-based flame retardant is a brominated epoxy resin selected from one or more of a brominated bisphenol A type epoxy resin, a brominated phenolic type epoxy resin, and a brominated isocyanate modified epoxy resin, and is non-reactive.
• the bromine-based flame retardant is one or more selected from the group consisting of decabromodiphenyl ether, decabromodiphenylethane, brominated styrene, ethylene bistetrabromophthalimide, and brominated polycarbonate.
• the brominated epoxy resin has a bromine content of 15 to 55%; and the addition of the brominated epoxy resin is calculated based on 100 parts by weight of the total weight of the component (A) and the component (B) in the epoxy resin composition. The amount is 10 to 50 parts by weight.
• the epoxy resin composition further comprises an inorganic or organic filler having a particle diameter of 0.1 to 10 ⁇ m;
• the inorganic filler is a random or spherical inorganic filler selected from the group consisting of crystalline silica, fused silica, and spherical Silicon oxide, hollow silica, glass powder, aluminum nitride, boron nitride, carbonization One or more of silicon, aluminum hydroxide, titanium dioxide, barium titanate, barium titanate, aluminum oxide, barium sulfate, talc, silicate 4 bow, carbonic acid 4 bow, and mica;
• the organic filler is selected from the group consisting of One or more of polytetrafluoroethylene powder, polyphenylene sulfide, polyethersulfone powder.
• the inorganic filler is a spherical inorganic filler surface-treated with a surface treatment agent, and the surface treatment agent is a silane coupling agent, which is an epoxy silane coupling agent, an aminosilane coupling agent, or a thiosilane coupling agent.
• a silane coupling agent which is an epoxy silane coupling agent, an aminosilane coupling agent, or a thiosilane coupling agent.
• the epoxy resin composition further contains a curing accelerator which is one or more of imidazole and a derivative thereof, a piperidine compound, and triphenylphosphine.
• a curing accelerator which is one or more of imidazole and a derivative thereof, a piperidine compound, and triphenylphosphine.
• the present invention also provides a prepreg prepared using the above epoxy resin composition, which comprises a reinforcing material and an epoxy resin composition adhered to the reinforcing material by impregnation and drying.
• the present invention also provides a copper-clad laminate produced using the above epoxy resin composition, comprising: a plurality of laminated prepregs and a copper foil laminated on one side or both sides of the laminated prepreg
• a copper-clad laminate produced using the above epoxy resin composition, comprising: a plurality of laminated prepregs and a copper foil laminated on one side or both sides of the laminated prepreg
• Each of the cured sheets includes a reinforcing material and an epoxy resin composition adhered to the reinforcing material by impregnation and drying.
• the epoxy resin composition of the present invention has an epoxy resin having a melt viscosity of not more than 0.5 Pa.s at 150 ° C, which has a low melt viscosity, so that the resin composition has good properties.
• Mobility 2
• the epoxy resin composition of the present invention has a phenolic resin as shown in the structural formula 1 as a curing agent, and has a high glass transition temperature after the resin composition is cured, and the curing agent is solidified to form a three-dimensional shape.
• the cross-linking network can meet the high reliability requirements of high-multilayer printed circuit boards. detailed description
• the epoxy resin composition of the present invention comprises the following essential components:
• the epoxy resin in the component (A) is a polyfunctional epoxy resin having a functionality of not less than 2 and an epoxy equivalent of not more than 300 g/eq.
• the optional epoxy resin of component (A) is: o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl type epoxy resin, naphthol type ring An oxy resin, an alkylated benzene type epoxy resin, a trifunctional epoxy resin, and a tetrafunctional epoxy resin, and the component (A) may be at least one of the above epoxy resins.
• n is an integer from 1 to 10;
• n is an integer from 1 to 8.
• the component (B) phenolic resin in the epoxy resin composition of the invention has a phenolic functionality of 3 or more, which serves as a curing agent in the epoxy resin composition, cures and crosslinks the epoxy resin, and cures cross-linking. Thereafter, the cured product has a high glass transition temperature and a low expansion coefficient.
• the component (B) phenol resin is used in an amount of from 0.9 to 1.2, preferably from 0.95 to 1.1, more preferably from 0.98 to 1.05, based on the epoxy equivalent of the epoxy resin to the hydroxyl equivalent ratio of from 0.9 to 1.2.
• the epoxy resin composition of the present invention may further contain other types of epoxy resins, such as a flame retardant, a flame retardant may be added in order to satisfy the flame retardancy of the cured product. It may be a bromine-based flame retardant or a halogen-free flame retardant; the bromine-based flame retardant is a non-reactive or reactive bromine-based flame retardant.
• the reactive bromine-based flame retardant may be a brominated epoxy resin selected from one or more of a brominated bisphenol A type epoxy resin, a brominated phenolic type epoxy resin, and a brominated isocyanate modified epoxy resin.
• the brominated epoxy resin has a bromine content of 15 to 55%.
• the non-reactive brominated flame retardant may be selected from decabromodiphenyl ether, decabromodiphenylethane, brominated styrene, ethylene bistetrabromophthalimide.
• decabromodiphenyl ether decabromodiphenylethane
• brominated styrene ethylene bistetrabromophthalimide.
• One or more of an amine and a brominated polycarbonate may be selected from decabromodiphenyl ether, decabromodiphenylethane, brominated styrene, ethylene bistetrabromophthalimide.
• One or more of an amine and a brominated polycarbonate may be selected from decabromodiphenyl ether, decabromodiphenylethane, brominated styrene, ethylene bistetrabromophthalimide.
• One or more of an amine and a brominated polycarbonate
• the amount of the above-mentioned flame retardant to be added is not particularly limited as long as it can satisfy the UL 94 V-0 level of the cured product. If a bromine-based flame retardant is used as a flame retardant, the amount of addition is calculated according to the bromine content of different bromine-based flame retardants, and the bromine content is calculated based on the total weight of component (A) and component (B) of 100 parts by weight. It is between 10 and 20%.
• the flame retardant is a brominated epoxy resin
• the epoxy resin is added in an amount of 10 to 50 based on the total weight of the component (A) and the component (B) in the epoxy resin composition. Parts by weight.
• the epoxy resin composition of the present invention may further contain a filler.
• the filler is an inorganic or organic filler with an average particle size of 0.1 to 10 microns.
• the inorganic filler is a random or spherical inorganic filler, and may be selected from the group consisting of crystalline silica, fused silica, spherical silica, hollow silica, glass powder, aluminum nitride, boron nitride, silicon carbide, One or more of aluminum hydroxide, titanium dioxide, barium titanate, barium titanate, aluminum oxide, barium sulfate, talc, silicate 4 bow, carbonic acid 4 bow, mica; the organic filler is selected from polytetrafluoroethylene One or more of ethylene powder, polyphenylene sulfide, polyethersulfone powder.
• the inorganic filler is preferably a surface-treated spherical inorganic filler, which uses a surface treatment agent as a silane coupling agent, preferably an epoxy silane coupling agent, an aminosilane coupling agent, a phenylaminosilane coupling agent, a thiosilane.
• a surface treatment agent as a silane coupling agent, preferably an epoxy silane coupling agent, an aminosilane coupling agent, a phenylaminosilane coupling agent, a thiosilane.
• a surface treatment agent as a silane coupling agent, preferably an epoxy silane coupling agent, an aminosilane coupling agent, a phenylaminosilane coupling agent, a thiosilane.
• the filler is added in an amount of 5 to 500 parts by weight, preferably 5 to 300 parts by weight, based on 100 parts by weight of the total of the component (A
• the epoxy resin composition of the present invention may further contain a curing accelerator, and the curing accelerator may be one or more of imidazole and a derivative compound thereof, a piperidine compound, and triphenylphosphine.
• the imidazole compound may be 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or the like.
• the amount of the curing accelerator added is not particularly limited.
• the amount of the curing accelerator is 0.01 to 1.0 part by weight, preferably 0.04%, based on 100 parts by weight of the total of the component (A) and the component (B). 0.5 parts by weight.
• the prepreg prepared by using the above epoxy resin composition includes a reinforcing material and an epoxy resin composition adhered thereto by impregnation and drying, and the reinforcing material is a prior art reinforcing material such as a fiberglass cloth or the like.
• a copper-clad laminate produced using the above epoxy resin composition comprising a plurality of laminated prepregs, and a copper foil laminated on one or both sides of the laminated prepreg, the prepreg using the epoxy resin combination Production.
• the epoxy resin composition of the present invention is made into a certain concentration of a glue, which is impregnated with a reinforcing material, then dried at a certain temperature, and the solvent is removed and semi-cured to obtain a prepreg. Then, one or more of the prepregs described above are stacked in a certain order, The copper foil is respectively pressed on both sides of the prepreg which are superposed on each other, and solidified in a hot press to obtain a copper clad laminate having a curing temperature of 150 to 250 ° C and a curing pressure of 25 to 60 Kg/cm 2 .
• the properties such as the glass transition temperature and the heat and humidity resistance were measured, and the details and descriptions are further given in the following examples.
• phenol type phenolic epoxy resin PN177 (Taiwan Changchun Synthetic Resin Factory) 53 parts by weight, brominated bisphenol A type epoxy resin DER530 (Dow Chemical, bromine content 18% ⁇ 20%) 20 parts by weight, 27 parts by weight of high bromine epoxy resin BEB400 (Taiwan Changchun Synthetic Resin Factory, bromine content 46% ⁇ 50%), then added with phenolic curing agent MEH-7500 (Japan Minghe Chemical, hydroxyl equivalent 96g/mol) 28 parts by weight, and solvent Butanone is stirred for a certain period of time to obtain a transparent glue solution, and then an appropriate amount of 2-methylimidazole is added, and stirring is continued to form a glue.
• MEH-7500 Japanese Minghe Chemical, hydroxyl equivalent 96g/mol
• the above-mentioned glue was impregnated with a glass cloth (model 7628, thickness 0.16 mm) and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg.
• a plurality of prepregs obtained by lamination were laminated on each other, and a copper foil was laminated on both sides thereof, and placed in a hot press to be cured to form the copper clad laminate.
• the physical property data is shown in Table 1.
• Tg(DMA)/°C 195 190 210 215 175 165 Good hole filling, poor heat resistance 260 270 260 265 260 250 Water absorption, % 0.09 0.095 0.075 0.10 0.011 0.14 Resistance to damp heat '! ⁇ 3/3 3/3 3/3 3/3 3/3 3/3 coefficient of thermal expansion,
• N740 phenol formaldehyde type novolac epoxy resin, melt viscosity (ICI/150 ° C, Pa.s ): 0.15; N670: o-cresol novolac epoxy resin, melt viscosity (ICI/150 ° C, Pa.s ) :0.2;
• N865 bisphenol A type phenolic epoxy resin, melt viscosity (ICI / 150 ° C, Pa.s): 0.25;
• HP-7200H Dicyclopentadiene type novolac epoxy resin, melt viscosity (ICI/150 °C, Pa.s): 0.35;
• HP-7200HH dicyclopentadiene type novolac epoxy resin, melt viscosity (ICI/150 °C, Pa.s): 1.0;
• EPPN-501 trifunctional phenolic epoxy resin, melt viscosity (ICI/150
• BEB400 brominated epoxy resin, bromine content: 45 ⁇ 49%;
• BREN-S brominated phenolic epoxy resin, bromine content: 18 ⁇ 20%;
• BT-93W Non-reactive brominated flame retardant, bromine content: 67.2%
• MEH7500 trifunctional phenolic resin, hydroxyl equivalent: 96g/eq;
• TD-2090 Novolac resin, hydroxyl equivalent: 105 g/eq.
• Glass transition temperature (Tg) Measured according to the DMA test method specified in IPC-TM-650 2.4.24 using DMA test.
• the phenolic resin-cured epoxy resin is used in Examples 1 to 9, and the laminate material has a high glass transition temperature and excellent heat resistance; and at the same time, a melt viscosity is low.
• the functional group epoxy resin can provide excellent filling property to the through hole in the multi-layer plate pressing process while ensuring high glass transition temperature and heat resistance.
• Comparative Example 3 when the phenolic curing was carried out, although a high glass transition temperature was obtained, the filling property was lowered due to high viscosity and high filler content, and Comparative Example 3 was used.
• the existing phenolic resin is cured, and the obtained laminate material has a low glass transition temperature.
• the copper-clad laminate of the present invention has higher glass transition temperature, through-hole filling property, and good heat and humidity resistance as compared with a general copper foil substrate, and is suitable for a high-multilayer printed wiring board field. .

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Laminated Bodies (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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Cited By (3)

Citations (4)

• 2012
  • 2012-04-05 WO PCT/CN2012/073546 patent/WO2013149386A1/fr not_active Ceased

Patent Citations (4)

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