Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
  • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/62—Alcohols or phenols
  • C08G59/621—Phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • 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
  • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
  • B32B2307/202—Conductive
• • 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
  • 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2363/00—Characterised by the use of epoxy resins; 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
  • H05K1/0353—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, a prepreg, a laminate, and a printed wiring board used for the production of a printed wiring board.
• a prepreg which is a material of a printed wiring board
• a prepreg made of a glass composition filler, a glass cloth, and a matrix resin is known (for example, see Patent Document 1).
• a glass composition filler having an average particle diameter of 2.0 ⁇ m or less and a CaO content of 5% by mass or more is used. Further, in this prepreg, the filling amount of the glass composition filler with respect to the total volume of the glass composition filler and the matrix resin is 10 to 70 vol%. Thus, flame retardance, drill workability, and heat resistance are improved by using a specific glass composition filler.
• the present invention has been made in view of the above points, and an object thereof is to provide an epoxy resin composition, a prepreg, a laminated board, and a printed wiring board excellent in drill workability, through-hole connection reliability, and heat resistance. To do.
• the epoxy resin composition according to the present invention includes an epoxy resin, a curing agent having a phenolic hydroxyl group, and an epoxy resin composition containing a filler, and the filling with respect to a total of 100 parts by mass of the epoxy resin and the curing agent.
• the material contains 15-50 parts by weight of a glassy filler and 15-50 parts by weight of a metal hydroxide, and the glassy filler contains 53% by mass or more of SiO 2 and 13 parts by weight of Al 2 O 3. % Of SiO 2 and Al 2 O 3 in a total of 75 to 80% by mass, the average particle size is 0.5 to 10 ⁇ m, and the metal hydroxide has a heat loss at 400 ° C. of 10% by mass. It is the above, It is characterized by the above.
• the epoxy resin composition preferably contains 0.2 to 2.0% by mass of a silane compound having at least one of an amino group, an epoxy group, and an isocyanate group based on the glassy filler.
• the prepreg according to the present invention is characterized in that the epoxy resin composition is impregnated into a base material and semi-cured.
• the laminate according to the present invention is formed by laminating the prepreg.
• the printed wiring board according to the present invention is characterized in that a conductive pattern is provided on the laminated board.
• an epoxy resin composition excellent in drill workability, through-hole connection reliability, and heat resistance can be obtained.
• the epoxy resin composition according to the present invention contains the following epoxy resin, a curing agent having a phenolic hydroxyl group, and a filler as essential components. Furthermore, it is preferable to contain a flame retardant such as a halogen flame retardant and a phosphorus flame retardant. Thereby, sufficient flame retardance can be obtained about a prepreg, a laminated board, and a printed wiring board.
• a flame retardant such as a halogen flame retardant and a phosphorus flame retardant.
• an epoxy resin for example, bromine containing epoxy resins, such as brominated bisphenol A type epoxy resin, phosphorus containing epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol Use novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, biphenyl epoxy resin, alicyclic epoxy resin, diglycidyl ether compound of polyfunctional phenol, diglycidyl ether compound of polyfunctional alcohol, etc. Can do.
• An epoxy resin can use only 1 type, or can use 2 or more types together.
• a preferable epoxy equivalent of the epoxy resin is 100 to 1000 g / eq.
• the curing agent is not particularly limited as long as it has a phenolic hydroxyl group.
• Polyfunctional phenol resins, bromine-containing phenol resins, phosphorus-containing phenol resins and the like can be used. Only one type of curing agent can be used, or two or more types can be used in combination.
• the curing agent contains halogen or phosphorus, an epoxy resin composition excellent in flame retardancy can be obtained.
• the preferred hydroxyl equivalent of the curing agent is 50 to 1000 g / eq.
• the epoxy resin and the curing agent are preferably reacted so that the equivalent ratio is 0.5 to 1.5, more preferably the equivalent ratio is 0.8 to 1.2.
• the equivalent ratio of the curing agent to the epoxy resin is within the above range, insufficient curing and deterioration of physical properties of the epoxy resin composition can be suppressed.
• a glassy filler and a metal hydroxide are used as the filler.
• SiO 2 53% by mass or more, Al 2 O 3 of 13 wt% or more, SiO 2 and Al 2 O 3 contains a total of 75-80 wt%, an average particle size of 0 Use 5-10 ⁇ m.
• SiO 2 is a component that forms the skeleton of the glass structure of the vitreous filler, and the content of SiO 2 needs to be 53% by mass or more in order to sufficiently obtain the strength of the glass structure.
• Al 2 O 3 is a component effective to obtain a chemical and mechanical stability in the glass structure of the glass filler, in order to obtain a chemical and mechanical properties of the glass structure sufficient Al 2 O The content of 3 needs to be 13% by mass or more.
• the coefficient of thermal expansion tends to increase, and heat resistance such as through-hole connection reliability and reflow heat resistance decreases.
• the total content of SiO 2 and Al 2 O 3 exceeds 80% by mass, the drill workability is lowered and the drill is likely to be worn.
• B 2 O 3 , CaO, MgO and the like may be contained in the glass filler.
• the average particle diameter of the glassy filler is less than 0.5 ⁇ m, the viscosity of the epoxy resin composition increases, and sufficient moldability cannot be obtained.
• the average particle size means the particle size at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method.
• the glassy filler as described above is a glass raw material containing SiO 2 and Al 2 O 3 in the above content in the above average particle size in a wet manner using a ball mill or a bead mill in distilled water or ion-exchanged water. It can be obtained by grinding until Moisture adhering to the pulverized glass filler is removed by heat drying.
• the metal hydroxide one having a heat loss at 400 ° C. of 10% by mass or more (the upper limit is 50% by mass) is used.
• aluminum hydroxide or magnesium hydroxide can be used.
• boehmite a material with a weight loss of less than 10% by mass such as boehmite is used, the drill workability is lowered and the drill is easily worn.
• boehmite alumina monohydrate represented by the composition of AlOOH or Al 2 O 3 ⁇ H 2 O .
• the glass filler is contained in an amount of 15 to 50 parts by mass and the metal hydroxide is contained in an amount of 15 to 50 parts by mass with respect to 100 parts by mass in total of the epoxy resin and the curing agent.
• the glass filler content is less than 15 parts by mass, the coefficient of thermal expansion tends to increase, and heat resistance such as through-hole connection reliability and reflow heat resistance decreases.
• the content of the glass filler exceeds 50 parts by mass, the moldability of the prepreg deteriorates.
• the content of the metal hydroxide is less than 15 parts by mass, the drill workability is lowered and the drill is easily worn. Conversely, when the content of the metal hydroxide exceeds 50 parts by mass, the moldability of the prepreg is lowered.
• the epoxy resin composition contains 0.2 to 2.0% by mass of a silane compound (coupling agent) having at least one of an amino group, an epoxy group, and an isocyanate group with respect to the glassy filler.
• a silane compound (coupling agent) having at least one of an amino group, an epoxy group, and an isocyanate group with respect to the glassy filler.
• the silane compound is not particularly limited as long as it has at least one of an amino group, an epoxy group, and an isocyanate group.
• aminosilane such as 3-aminopropyltriethoxysilane, ⁇ -glycidpropyl Epoxy silanes such as methyldiethoxysilane and isocyanate silanes such as 3-isocyanatopropyltriethoxysilane can be used.
• the adhesion between organic substances (epoxy resins and curing agents, etc.) and inorganic substances (fillers, etc.) is strengthened, and heat resistance such as reflow heat resistance. Can be further improved.
• the effect of improving the heat resistance is saturated when the content of the silane compound is about 2.0% by mass.
• the epoxy resin composition may contain a curing accelerator such as 2-ethyl-4-methylimidazole (2E4MZ) in order to promote the reaction between the epoxy resin and the curing agent.
• a curing accelerator such as 2-ethyl-4-methylimidazole (2E4MZ) in order to promote the reaction between the epoxy resin and the curing agent.
• the epoxy resin composition is blended with the above epoxy resin, curing agent, filler, silane compound and curing accelerator as necessary, diluted with an appropriate solvent, and stirred with a stirrer such as a disper.
• a stirrer such as a disper.
• It can be prepared as a resin varnish by mixing and homogenizing.
• the solvent for example, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol, aromatic hydrocarbons such as benzene and toluene, and the like can be used.
• the dilution with a solvent is preferably carried out so that the solid content (non-solvent component) concentration is 60 to 80% by mass.
• the prepreg is obtained by impregnating a substrate such as a glass cloth with the resin varnish of the epoxy resin composition obtained as described above, and drying by heating at 130 to 170 ° C. to remove the solvent in the resin varnish. It can be produced by semi-curing the epoxy resin composition. Heat drying is preferably performed so that the gel time of the prepreg is 115 to 125 seconds.
• the gel time of the prepreg is the time from immediately after placing the resin collected from the prepreg on a plate heated to 170 ° C. until the resin is gelled.
• the amount of resin in the prepreg is preferably 65 to 300 parts by mass with respect to 100 parts by mass of the base material.
• the laminated plate is formed by laminating a plurality of prepregs obtained as described above.
• a laminate is manufactured as a metal-clad laminate such as a copper-clad laminate by laminating a plurality of prepregs and a metal foil such as a copper foil on the outside and laminating the laminate by heating and pressing it.
• the heating and pressing conditions are, for example, 140 to 200 ° C., 0.5 to 5.0 MPa, and 40 to 240 minutes.
• the printed wiring board is formed by providing a conductor pattern on the laminated board obtained as described above.
• a printed wiring board can be manufactured by forming a conductor pattern on the surface of a metal-clad laminate using a subtractive method.
• this printed wiring board is used as a core material (inner layer material)
• a multilayer printed wiring board can be manufactured. That is, the conductor pattern (inner layer pattern) of the core material is roughened by black oxidation or the like, and then a metal foil is stacked on the surface of the core material via a prepreg, and this is heated and pressed to be laminated.
• the heating and pressing conditions at this time are, for example, 140 to 200 ° C., 0.5 to 5.0 MPa, and 40 to 240 minutes.
• a subtractive method is used to form a conductor pattern (outer layer pattern) and plating the inner wall of the hole to form a through hole.
• a printed wiring board can be manufactured.
• the number of layers of the printed wiring board is not particularly limited.
• the insulating layer is formed using an epoxy resin composition containing a predetermined curing agent and filler, the drill is less likely to be worn when drilling. Moreover, since the above-mentioned epoxy resin composition has a small coefficient of thermal expansion, the resistance value of the through hole hardly changes and the connection reliability is high. Furthermore, the printed wiring board described above is less prone to blistering when soldering components at a high temperature by, for example, a reflow method.
• Epoxy resin “Epiclon 1121” (epoxy equivalent: 450 to 530 g / eq, bromine content: 19 to 22% by mass, about 2 intramolecular average epoxy group content, molecule, brominated bisphenol A type epoxy resin manufactured by DIC Corporation In which nitrogen is not contained).
• VH4170 (hydroxyl equivalent: 118 g / eq, resin softening point 105 ° C., bifunctional bisphenol A content is about 25%), which is a bisphenol A type novolac resin, manufactured by DIC Corporation was used.
• the glassy filler (1) is SiO 2 (55% by mass), Al 2 O 3 (15% by mass), B 2 O 3 (7% by mass), CaO (20% by mass), MgO (3% by mass). Was obtained by pulverizing for 1 hour in a distilled water using a ball mill until the average particle size became 2 ⁇ m.
• the glassy filler (2) is a distilled glass raw material containing SiO 2 (58% by mass), Al 2 O 3 (17% by mass), B 2 O 3 (12% by mass), and CaO (13% by mass). It was obtained by wet milling in water using a ball mill for 1 hour until the average particle size reached 2 ⁇ m.
• the glassy filler (3) is a distilled glass raw material containing SiO 2 (62% by mass), Al 2 O 3 (18% by mass), B 2 O 3 (12% by mass), and CaO (8% by mass). It was obtained by wet milling in water using a ball mill for 1 hour until the average particle size reached 2 ⁇ m.
• the glassy filler (4) is composed of a glass raw material containing SiO 2 (65% by mass), Al 2 O 3 (25% by mass), and MgO (10% by mass) in an average particle size by using a ball mill in distilled water. It was obtained by grinding for 1 hour until the diameter reached 2 ⁇ m.
• metal hydroxide aluminum hydroxide (“C-303” manufactured by Sumitomo Chemical Co., Ltd., loss of heat of 35% by mass at 400 ° C., average particle size of about 4 ⁇ m), magnesium hydroxide (manufactured by Sakai Chemical Industry Co., Ltd.) “MGZ-6R”, heat loss of 31% by mass at 400 ° C., average particle size of about 1.5 ⁇ m, boehmite (“AOH60” manufactured by Navaltech), heat loss of 5% by mass at 400 ° C., average particle size of about 0.9 ⁇ m ) was used.
• isocyanate silane “KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd., which is 3-isocyanatopropyltriethoxysilane, was used.
• vinyl silane “KBE-1003” manufactured by Shin-Etsu Chemical Co., Ltd., which is vinyltriethoxysilane, was used.
• the prepreg is impregnated with the resin varnish of the above epoxy resin composition into a glass cloth (“7628 type cloth” manufactured by Nitto Boseki Co., Ltd.) as a base material, and is heated and dried at 170 ° C. by a non-contact type heating unit Then, the solvent in the resin varnish was removed and the epoxy resin composition was semi-cured.
• the amount of resin in the prepreg is 100 parts by mass with respect to 100 parts by mass of the base material.
• the laminated plate is composed of 5 sheets of prepreg (340mm x 510mm) and copper foil (Nikko Gould Foil Co., Ltd., thickness 35 ⁇ m, JTC foil) with a roughened surface on both sides. It was manufactured as a copper clad laminate by pressurizing and molding. The heating and pressing conditions are 170 ° C., 2.94 MPa, and 90 minutes.
• a core material (inner layer material) was manufactured by forming a conductor pattern (inner layer pattern) on the surface of the copper clad laminate using a subtractive method. Furthermore, after roughening the inner layer pattern of this core material with multibond (manufactured by Nihon McDermid Co., Ltd.), copper foil (made by Nikko Gould Foil Co., Ltd., thickness 35 ⁇ m) on both sides of this core material via prepreg , JTC foil), and this was heated and pressed to form a laminate. The heating and pressing conditions at this time are also 170 ° C., 2.94 MPa, and 90 minutes.
• a four-layer printed wiring board was manufactured by forming a through hole by performing 25 ⁇ m).

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Manufacturing & Machinery (AREA)
• Inorganic Chemistry (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Reinforced Plastic Materials (AREA)
• Epoxy Resins (AREA)
• Laminated Bodies (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=49300256

Family Applications (1)

Country Status (4)

Cited By (1)

Citations (3)

Family Cites Families (5)

• 2012
  • 2012-04-05 JP JP2012086751A patent/JP5891435B2/ja active Active
• 2013
  • 2013-03-29 WO PCT/JP2013/002161 patent/WO2013150753A1/ja active Application Filing
  • 2013-03-29 CN CN201380018074.1A patent/CN104220521A/zh active Pending
  • 2013-04-03 TW TW102112163A patent/TWI537320B/zh active

Patent Citations (3)

Also Published As

Similar Documents

Legal Events