WO2011034055A1 - プリプレグ - Google Patents
プリプレグ Download PDFInfo
- Publication number
- WO2011034055A1 WO2011034055A1 PCT/JP2010/065843 JP2010065843W WO2011034055A1 WO 2011034055 A1 WO2011034055 A1 WO 2011034055A1 JP 2010065843 W JP2010065843 W JP 2010065843W WO 2011034055 A1 WO2011034055 A1 WO 2011034055A1
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- WO
- WIPO (PCT)
- Prior art keywords
- glass composition
- glass
- less
- prepreg
- composition filler
- Prior art date
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Classifications
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- 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
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- 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
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- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- 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
- C08K3/40—Glass
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
Definitions
- the present invention relates to a prepreg for electronic materials comprising a glass composition filler, a glass cloth, and a matrix resin. More specifically, the present invention is a prepreg comprising a glass composition filler having an average particle size of 2.0 ⁇ m or less and a CaO content of 5% by mass or more, a glass cloth, and a matrix resin, wherein the prepreg The content of the glass composition filler is 10 vol% or more and 70 vol% or less.
- thermosetting resins such as epoxy resins (hereinafter also referred to as “matrix resins”), inorganic fillers (hereinafter also referred to as “inorganic fillers”), and glass cloths.
- matrix resins epoxy resins
- inorganic fillers inorganic fillers
- glass cloths glass cloths.
- a prepreg consisting of is widely used.
- a laminate is obtained by stacking a plurality of the prepregs and curing and molding them under heating and pressing conditions.
- inorganic fillers include silica, alumina, aluminum hydroxide, magnesium hydroxide, talc, mica, antimony oxide, calcium carbonate, and titanium oxide.
- silica is widely used for printed wiring boards.
- prepregs and laminates using silica filler and aluminum hydroxide have been reported (see Patent Document 1 below).
- the problem to be solved by the present invention is to provide a prepreg for electronic materials that is excellent in flame retardancy and heat resistance.
- the present inventors have found 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.
- a prepreg composed of a glass composition filler, a glass cloth, and a matrix resin having an average particle size of 2.0 ⁇ m or less and a CaO content of 5% by mass or more, the glass composition filler and the matrix resin
- the said prepreg characterized by the filling amount of this glass composition filler with respect to the sum total volume of 10 vol% or more and 70 vol% or less.
- the surface of the glass composition filler has the following general formula (1): XSi (R) 3-n Y n (1) ⁇ Wherein X is an organic functional group, Y is an alkoxy group, n is an integer of 1 to 3, and R is a methyl group, an ethyl group or a hydroxyl group. ⁇
- X is an organic functional group
- Y is an alkoxy group
- n is an integer of 1 to 3
- R is a methyl group, an ethyl group or a hydroxyl group.
- the compound contained in the silane coupling agent is represented by the following general formula (2): ⁇ Wherein R 1 is independently hydrogen, methyl group or ethyl group, R 2 is alkoxy group, and R 3 is independently alkoxy group, hydroxyl group, methyl group or ethyl group. And n is an integer from 1 to 3.
- R 1 is independently hydrogen, methyl group or ethyl group
- R 2 is alkoxy group
- R 3 is independently alkoxy group, hydroxyl group, methyl group or ethyl group.
- n is an integer from 1 to 3.
- the particle size of the glass composition filler is 0.1 ⁇ m or more, the particle content of the glass composition filler is 0.5% or less, and the specific surface area of the glass composition filler is 2 m 2 /
- the raw glass of the glass composition filler used in the present invention is a glass that contains 5% by mass or more of CaO and has a low alkali metal content that can be used for a laminate for electronic materials. E glass, L glass and the like are preferable. Table 1 below shows examples of the composition of the glass material filler glass used in the present invention.
- Glass containing 5% by mass or more of CaO is excellent in workability such as drilling and laser processing, has good insulation and heat resistance, and has a well-balanced laminated plate characteristic. Moreover, since CaO is easily hydrated, good flame retardancy can be obtained.
- the average particle size of the glass composition filler used in the present invention is 2.0 ⁇ m or less.
- the glass composition filler is sufficiently impregnated in the glass cloth yarn bundle in the step of obtaining a prepreg by impregnating a glass cloth with a matrix resin varnish, and further in the step of press-pressing the prepreg.
- a laminated plate uniformly filled with the glass composition filler can be obtained.
- a laminated plate having good flame retardancy can be obtained.
- the average particle diameter is preferably 1.0 ⁇ m or less, more preferably 0.7 ⁇ m or less, and further preferably 0.5 ⁇ m or less.
- the particle size distribution of the glass composition filler preferably has 5% or more, more preferably 10% or more of a cumulative distribution having a particle diameter of 0.5 ⁇ m or less after having the above average particle diameter.
- the glass composition filler is more easily impregnated into the yarn bundle of the glass cloth.
- the maximum particle size is 10 ⁇ m or less because the glass composition filler, which causes a bad influence on the circuit formation when forming a circuit with a narrow pitch, is kept away from the wiring part to improve the insulation reliability. Is preferably 5 ⁇ m or less.
- the average particle diameter is preferably 0.1 ⁇ m or more for the purpose of suppressing an increase in viscosity during varnish blending.
- the particle diameter and particle size distribution can be determined by a general laser diffraction / light scattering method.
- the average particle diameter, yield a cumulative curve of the sample total volume as 100% refers to the volume mean diameter corresponding to 50% of the cumulative distribution, commonly referred to as D 50.
- the cumulative distribution with a particle size of 0.5 ⁇ m or less being 5% or more means that the particle size at the point where the cumulative curve is 5% is 0.5 ⁇ m or less.
- a value generally referred to as D 5 is 0.5 ⁇ m or less.
- the shape of the glass composition filler may be any shape such as a spherical shape, a crushed shape, a needle shape, or a short fiber shape.
- spherical and crushed fillers having excellent fluidity in the matrix resin and the resin varnish are most preferable.
- the specific surface area of the glass composition filler is preferably 1 m 2 / g or more and 20 m 2 / g or less. When the specific surface area is 1 m 2 / g or more, the amount of adsorbed water on the surface of the glass composition filler also increases, so that flame retardancy is easily obtained.
- the surface of the glass composition filler is preferably treated with a silane coupling agent from the viewpoint of dispersibility in the matrix resin.
- a silane coupling agent the following general formula (1): XSi (R) 3-n Y n (1) ⁇ Wherein X is an organic functional group, Y is an alkoxy group, n is an integer of 1 to 3, and R is a methyl group, an ethyl group or a hydroxyl group. ⁇
- the silane coupling agent containing the compound represented by this is mentioned.
- the alkoxy group is preferably an alkoxy group having 5 or less carbon atoms and more preferably 1 carbon atom from the viewpoint of reactivity with the glass composition filler.
- silane coupling agent from the viewpoint of heat resistance of the laminate, in particular, the following general formula (2): ⁇ Wherein R 1 is independently hydrogen, methyl group or ethyl group, R 2 is alkoxy group, and R 3 is independently alkoxy group, hydroxyl group, methyl group or ethyl group. And n is an integer from 1 to 3. ⁇ A silane coupling agent containing a compound represented by
- Specific examples of the compound represented by the general formula (1) include methylbenzylaminoethylaminopropyltrimethoxysilane, dimethylbenzylaminoethylaminopropyltrimethoxysilane, benzylaminoethylaminopropyltrimethoxysilane, and benzylamino.
- Examples include ethylaminopropyltriethoxysilane. 0.01 mass% or more and 5.0 mass% or less are preferable, and, as for the adhesion amount of the silane coupling agent with respect to a glass composition filler, 0.1 mass% or more and 1.0 mass% or less are more preferable.
- the amount is preferably 0.01% by mass or more for the purpose of maximizing the effect of the surface treatment, and is preferably 5.0% by mass or less for the reason of suppressing aggregation of the glass composition filler and improving dispersibility.
- inorganic fillers such as silica, alumina, aluminum hydroxide, magnesium hydroxide, talc, mica, antimony oxide, calcium carbonate, and titanium oxide may be used in combination.
- a hydroxide such as aluminum hydroxide or magnesium hydroxide and antimony oxide are used in combination, good flame retardancy is easily obtained.
- pulverization methods such as a Henschel mixer, a ball mill, a bead mill, and a jet mill can be used, and both wet pulverization and dry pulverization are possible.
- dry pulverization with an air stream or a medium is most preferable.
- an airflow jet mill, a dry ball mill, a dry bead mill, etc. are most suitable.
- it may be spheroidized by high-temperature heating.
- (B) Glass cloth The glass cloth formed by weaving glass yarn is used for the prepreg of the present invention.
- a glass cloth is composed of warp yarns and weft yarns, and there are gaps between the warp yarns and between the weft yarns, so there is always a place where there is no glass in the glass cloth surface.
- a basket hole usually called a basket hole.
- the size of this basket hole can generally be evaluated by air permeability.
- the air permeability of the glass cloth used for the prepreg of the present invention is preferably 50 cm 3 / cm 2 / sec or less. In the case of 50 cm 3 / cm 2 / sec or less, the basket hole is small, and the number of places where the glass cloth is not present in the laminated sheet is reduced, which is effective for flame retardancy.
- the glass composition filler is less likely to collect in the basket hole portion, and more easily enters the glass yarn bundle.
- the size of the basket hole is preferably 0.005 mm 2 or less.
- the weaving density of the glass cloth is preferably 30 to 200 / inch, more preferably 50 to 100 / inch. When the weaving density is 50 pieces / inch or more, it is easy to make the air permeability 50 cm 3 / cm 2 / sec or less.
- the mass of the glass cloth is preferably 5 to 400 g / m 2 , more preferably 10 to 200 g / m 2 .
- the composition of the glass yarn any of E glass, L glass, D glass, S glass, H glass and the like can be used. In particular, glass having the same composition as the glass composition filler is preferable for improving the uniformity of the substrate.
- a glass yarn containing a glass filament having an average monofilament diameter of 2.5 to 9.0 ⁇ m is preferable in terms of drilling workability and laser workability, and more preferably 4.0 to 7.0 ⁇ m.
- the weave structure is preferably a plain weave structure, but a glass cloth having a weave structure such as Nanako weave, satin weave or twill weave may be used.
- the surface of the glass cloth is preferably surface-treated with a surface treatment agent such as a silane coupling agent or a titanate coupling agent.
- the surface treatment agent may be appropriately selected in consideration of the reactivity with the matrix resin.
- the matrix resin is an epoxy resin, a urethane resin, a thermosetting polyimide resin, a melamine resin, an epoxy acrylate, or a resin that cures unsaturated polyester, ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane and its hydrochloride, N- ⁇ - (N-benzyl) Silane compounds such as (aminoethylaminopropyl) trimethoxysilane and its hydrochlor
- the surface treatment on the glass cloth may be performed by a known surface treatment method at a stage where the sizing agent necessary for weaving is removed. Further, the glass cloth may be opened by a high-pressure water flow such as a columnar flow or ultrasonic waves by a high-frequency vibration method in water.
- thermosetting resin As the matrix resin used in the prepreg of the present invention, a thermosetting resin or a thermoplastic resin may be mentioned, but a thermosetting resin and a thermoplastic resin may be used in combination.
- thermosetting resin A compound having an epoxy group and a compound having an amino group, a phenol group, an acid anhydride group, a hydrazide group, an isocyanate group, a cyanate group, or a hydroxyl group that reacts with the epoxy group, without catalyst, or imidazole An epoxy resin to which a catalyst having a reaction catalytic ability such as a compound, a tertiary amine compound, a urea compound, or a phosphorus compound is added and reacted to be cured; (B) a radical polymerization type curable resin in which a compound having an allyl group, a methacryl group, or an acrylic group is cured using a thermal decomposition catalyst or a photodecomposition catalyst as
- thermoplastic resins include polyphenylene ether, modified polyphenylene ether, polyphenylene sulfide, polysulfone, polyether sulfone, polyarylate, aromatic polyamide, polyether ether ketone, thermoplastic polyimide, insoluble polyimide, polyamideimide, fluororesin, etc. Can be mentioned.
- the prepreg of the present invention is composed of the glass composition filler, glass cloth, and matrix resin described above.
- the total adhesion amount of the matrix resin and the glass composition filler to the glass cloth is preferably 30% by mass or more because it can be easily formed into a plate, and also facilitates the preparation of the prepreg and maximizes the reinforcing effect of the glass cloth. For this reason, the content is preferably 90% by mass or less.
- the filling amount of the glass composition filler in the matrix resin is preferably 10 vol% or more and 70 vol% or less with respect to the total volume of the matrix resin and the glass composition filler. If the filling amount of the glass composition filler is less than 10 vol%, no effect on flame retardancy is observed, while if it is 70 vol% or more, it becomes difficult to ensure the moldability of the laminate.
- the prepreg of the present invention can be produced according to a conventional method. For example, by impregnating glass cloth into a varnish obtained by diluting a surface-treated glass composition filler and a matrix resin with an organic solvent, and then heating in a dryer usually at 100 to 200 ° C. for 1 to 30 minutes, etc. A prepreg can be obtained by semi-curing the matrix resin (B-stage) and volatilizing the organic solvent. After impregnation, excess varnish may be removed with a slit or the like, and the thickness may be adjusted as appropriate.
- a halogen-based flame retardant In order to obtain sufficient flame retardancy of the prepreg, it is preferable to appropriately use a halogen-based flame retardant, a phosphorus-based flame retardant, or the like. In particular, it is most preferable to use a phosphorus-based flame retardant in order to suppress the burden on the environment.
- acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, toluene, xylene, tetrahydrofuran (THF) or N-methylpyrrolidone (NMP) is preferable, and arbitrarily and arbitrarily. You may mix and use.
- the total amount of the surface-treated glass composition filler and the matrix resin in the varnish is preferably 30% by mass or more and 90% by mass or less.
- the flame retardancy and heat resistance of a laminate using a prepreg containing 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 are evaluated by the following methods. did.
- the glass composition filler was applied to a specific surface area measuring device (BELSOAP28SA manufactured by Nippon Berber Soap Co., Ltd.) to determine the specific surface area of the filler.
- BELSOAP28SA manufactured by Nippon Berber Soap Co., Ltd.
- Style 1078 glass cloth manufactured by Asahi Kasei E-Materials Corporation, glass type: E glass
- N- (vinylbenzyl) - ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane hydrochloride SZ6032 manufactured by Toray Dow Corning
- Single yarn diameter 5 ⁇ m
- Number of single yarns constituting the yarn 200
- Weaving method Plain weave
- Weaving density 54 vertical / inch
- Horizontal 54 / inch Air permeability: 9 cm 3 / cm 2 / sec
- Mass 47.0 g / m 2 (hereinafter referred to as “glass cloth A”)
- style 1080 glass cloth manufactured by Asahi Kasei E-Materials Co., Ltd., glass type: E glass, single yarn diameter: 5 ⁇ m, number of single yarns constituting the yarn) : 200 this, weave: plain weave, weave density:
- ⁇ Matrix resin varnish composition Bisphenol A novolac type epoxy resin (Japan Epoxy Resin Epicoat 157S70B75) 48.5 parts by mass, Bisphenol A type epoxy resin (Japan Epoxy Resin Epicoat 1001B80) 10 parts by mass, bisphenol A novolac (Japan Epoxy Resin Epicure YLH129B65) 30 parts by mass Part, cyclophosphazene (SPB100, manufactured by Otsuka Chemical Co., Ltd.) 11.5 parts by mass and 0.1 part by mass of 2-ethyl 4-methylimidazole are mixed and referred to as matrix resin varnish (hereinafter “matrix resin varnish A”). )
- ⁇ Production method of laminated plate> Four prepregs were stacked, and a copper foil having a thickness of 12 ⁇ m was stacked on top and bottom, and heated and pressed at 195 ° C. and 40 kg / cm 2 for 60 minutes to obtain a laminate.
- ⁇ Flame retardant evaluation method for laminates The laminate was cut into 13 mm ⁇ 130 mm to prepare five test pieces. Each test piece was contacted with a gas burner for 10 seconds, and then the time until the laminate stopped burning was measured. When the combustion did not stop and the test piece was burnt out, it was completely burned. Flame retardancy was determined according to UL standards.
- a 500 mm x 500 mm laminate is first placed in an atmosphere of 20 ° C and 60% RH for 24 hours, and further exposed to an atmosphere of 121 ° C and 100% RH for 1 to 24 hours, and then moisture on the surface is removed. Then, it was dipped in a solder bath at 288 ° C. and pulled up, and the degree of swelling was visually evaluated. The number of samples was 5 for each test time.
- Table 3 as evaluation results, blisters of less than 5 mm are indicated by “ ⁇ ”, and blisters of 5 mm or more are indicated by “x”.
- Example 1 An E glass composition filler (specific surface area: 12 m 2 / g, wet pulverized product) having an average particle size of 0.5 ⁇ m treated with methyltrimethoxysilane and a cumulative distribution of particle size of 0.5 ⁇ m or less of 32% is used as a matrix.
- a matrix resin varnish prepared by dispersing resin varnish A and ethylene glycol monomethyl ether so that the total solid content of the matrix resin and the glass composition filler is 70% by mass and the concentration of the glass composition filler in the solid content is 30 vol%. Glass cloth A was impregnated and dried at 160 ° C. for 1 minute to obtain a prepreg.
- Example 2 E glass composition filler (specific surface area; 10 m 2 / g, wet pulverized product) having an average particle size of 0.7 ⁇ m treated with aminopropyltriethoxysilane and a cumulative distribution of particle size of 0.5 ⁇ m or less of 15%, A matrix resin varnish dispersed in matrix resin varnish A and ethylene glycol monomethyl ether so that the total solid content of the matrix resin and the glass composition filler is 70% by mass and the concentration of the glass composition filler in the solid content is 30 vol%.
- the glass cloth A was impregnated and dried at 160 ° C. for 1 minute to obtain a prepreg.
- Example 3 E glass composition filler (specific surface area; 10 m 2 / g, wet pulverized product) having an average particle size of 0.7 ⁇ m treated with aminopropyltriethoxysilane and a cumulative distribution of particle size of 0.5 ⁇ m or less of 15%, A matrix resin varnish dispersed in matrix resin varnish A and ethylene glycol monomethyl ether so that the total solid content of the matrix resin and the glass composition filler is 70% by mass and the concentration of the glass composition filler in the solid content is 30 vol%.
- the glass cloth B was impregnated and dried at 160 ° C. for 1 minute to obtain a prepreg.
- Example 4 E glass composition filler (specific surface area; 3 m 2 / g, wet pulverized product) having an average particle size of 1.8 ⁇ m treated with aminopropyltriethoxysilane and a cumulative distribution of particle size of 0.5 ⁇ m or less is 5%, A matrix resin varnish dispersed in matrix resin varnish A and ethylene glycol monomethyl ether, adjusted so that the total solid content of the matrix resin and glass composition filler is 70% by mass, and the concentration of the glass composition filler in the solid content is 30 vol%. The glass cloth A was impregnated and dried at 160 ° C. for 1 minute to obtain a prepreg.
- E glass composition filler (specific surface area; 21 m 2 / g, wet pulverized product) having an average particle size of 0.2 ⁇ m treated with aminopropyltriethoxysilane and a cumulative distribution of particle size of 0.5 ⁇ m or less is 80%, A matrix resin varnish dispersed in matrix resin varnish A and ethylene glycol monomethyl ether so that the total solid content of the matrix resin and the glass composition filler is 70% by mass and the concentration of the glass composition filler in the solid content is 30 vol%.
- the glass cloth A was impregnated and dried at 160 ° C. for 1 minute to obtain a prepreg.
- E glass composition filler (specific surface area; 2 m 2 / g, dry pulverized product) having an average particle size of 1.8 ⁇ m treated with aminopropyltriethoxysilane and a cumulative distribution of particle size of 0.5 ⁇ m or less is 5%, A matrix resin varnish dispersed in matrix resin varnish A and ethylene glycol monomethyl ether so that the total solid content of the matrix resin and the glass composition filler is 70% by mass and the concentration of the glass composition filler in the solid content is 30 vol%.
- the glass cloth A was impregnated and dried at 160 ° C. for 1 minute to obtain a prepreg.
- Example 7 E glass composition filler (specific surface area; 2 m 2 / g, wet pulverized product) having an average particle size of 1.8 ⁇ m treated with aminopropyltriethoxysilane and a cumulative distribution of 3% or less of particle size of 0.5 ⁇ m or less, A matrix resin varnish dispersed in matrix resin varnish A and ethylene glycol monomethyl ether so that the total solid content of the matrix resin and the glass composition filler is 70% by mass and the concentration of the glass composition filler in the solid content is 30 vol%.
- the glass cloth A was impregnated and dried at 160 ° C. for 1 minute to obtain a prepreg.
- An E glass composition filler (specific surface area: 3 m 2 / g) having an average particle size of 2.6 ⁇ m treated with aminopropyltriethoxysilane and a cumulative distribution of 0.5% or less of the particle size of 0.5 ⁇ m or less is used as a matrix resin.
- a matrix resin varnish that is dispersed in varnish A and ethylene glycol monomethyl ether and adjusted so that the total solid content of the matrix resin and the glass composition filler is 70% by mass, and the concentration of the glass composition filler in the solid content is 30 vol%.
- the cloth A was impregnated and dried at 160 ° C. for 1 minute to obtain a prepreg.
- Comparative Example 2 Disperse silica filler (specific surface area; 9 m 2 / g) having an untreated average particle size of 0.5 ⁇ m and a cumulative distribution of particle size of 0.5 ⁇ m or less in matrix resin varnish A and ethylene glycol monomethyl ether Then, the matrix resin varnish adjusted so that the total solid content of the matrix resin and the silica filler is 70% by mass and the concentration of the silica filler in the solid content is 30 vol% is impregnated with the glass cloth A, and at 160 ° C. for 1 minute. A prepreg was obtained after drying.
- the prepreg of the present invention can be suitably used for electronic materials.
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Abstract
Description
無機フィラーとしては、シリカ、アルミナ、水酸化アルミニウム、水酸化マグネシウム、タルク、マイカ、酸化アンチモン、炭酸カルシウム、酸化チタンなどが挙げられるが、特に耐熱性、絶縁信頼性、難燃性の点で、プリント配線板にはシリカが広く使用されている。実際にシリカフィラー、及び水酸化アルミニウムを応用した多くのプリプレグ、積層板例が報告されている(以下の特許文献1参照)。
すなわち、本願発明は以下の通りである。
XSi(R)3-nYn (1)
{式中、Xは、有機官能基であり、Yは、アルコキシ基であり、nは、1~3の整数であり、そしてRは、メチル基、エチル基又はヒドロキシル基である。}で表される化合物を含むシランカップリング剤で処理されている、前記[1]~[5]のいずれかに記載のプリプレグ。
(A)ガラス組成フィラー
本発明で用いるガラス組成フィラーの原料ガラスは、電子材料用途の積層板に使用可能な、CaOを5質量%以上含み、かつ、アルカリ金属含量の低い組成を有するガラスであり、Eガラス、Lガラス等が好ましい。
本発明で用いるガラス組成フィラーの原料ガラスの組成例を以下の表1に示す。
ガラス組成フィラーの比表面積は、1m2/g以上20m2/g以下であることが好ましい。比表面積が1m2/g以上の場合、ガラス組成フィラーの表面の吸着水も増えるため、難燃性が得られやすい。一方、比表面積が20m2/g以下の場合、マトリックス樹脂中での分散性に優れ、得られた積層板は耐熱性、難燃性に優れる。
ガラス組成フィラーの表面は、シランカップリング剤で処理されていることが、マトリックス樹脂中での分散性の観点から好ましい。分散性が良い場合、積層板の難燃性、及び耐熱性は向上する。シランカップリング剤としては、下記一般式(1):
XSi(R)3-nYn (1)
{式中、Xは、有機官能基であり、Yは、アルコキシ基であり、nは、1~3の整数であり、そしてRは、メチル基、エチル基又はヒドロキシル基である。}で表される化合物を含むシランカップリング剤が挙げられる。アルコキシ基としては、ガラス組成フィラーとの反応性の点で、炭素数5以下のアルコキシ基が好ましく、炭素数1がより好ましい。
ガラス組成フィラーに対するシランカップリング剤の付着量は、0.01質量%以上5.0質量%以下が好ましく、0.1質量%以上1.0質量%以下がより好ましい。表面処理の効果を最大にする理由から、0.01質量%以上が好ましく、またガラス組成フィラーの凝集を抑え分散性を良くする理由から、5.0質量%以下が好ましい。
本発明のプリプレグには、ガラス糸を製織してなるガラスクロスを使用する。ガラスクロスは、たて糸とよこ糸からなり、各たて糸間、よこ糸間には隙間があるため、必ずガラスクロス面内にガラスの無い場所が存在する。通常、バスケットホールと呼ばれる。このバスケットホールの大きさは一般に通気度で評価できる。本発明のプリプレグに用いるガラスクロスの通気度は、50cm3/cm2/sec以下であることが好ましい。50cm3/cm2/sec以下の場合、バスケットホールが小さく、積層板内のガラスクロスが存在しない場所が少なくなり、難燃性に有効である。また、ガラス組成フィラーがバスケットホール部分にたまり難くなり、よりガラス糸束内に入りやすくなる。バスケットホールの大きさとしては、0.005mm2以下であることが好ましい。
ガラスクロスの織り密度は、30~200本/インチが好ましく、さらに好ましくは50~100本/インチである。織り密度を50本/インチ以上にすると、通気度を50cm3/cm2/sec以下にすることが容易になる。
ガラス糸の組成はEガラス、Lガラス、Dガラス、Sガラス、Hガラスなどいずれも使用可能である。特に、ガラス組成フィラーと同組成であるガラスが、基板の均一性向上のため好ましい。
ガラス糸としては、平均モノフィラメント径が2.5~9.0μmのガラスフィラメントを含むガラス糸がドリル加工性、及びレーザ加工性の点で好ましく、より好ましくは4.0~7.0μmである。
織り構造については平織り構造が好ましいが、ななこ織り、朱子織り、綾織り等の織り構造を有するガラスクロスでもよい。
本発明のプリプレグに用いるマトリックス樹脂としては、熱硬化性樹脂又は熱可塑性樹脂が挙げられるが、熱硬化性樹脂と熱可塑性樹脂とを併用してもよい。
熱硬化性樹脂の例としては、
(a)エポキシ基を有する化合物と、エポキシ基と反応するアミノ基、フェノール基、酸無水物基、ヒドラジド基、イソシアネート基、シアネート基、又は水酸基等を有する化合物とを、無触媒で、又はイミダゾール化合物、3級アミン化合物、尿素化合物、又は燐化合物等の反応触媒能を持つ触媒を添加して、反応させて硬化させるエポキシ樹脂、
(b)アリル基、メタクリル基、又はアクリル基を有する化合物を、熱分解型触媒又は光分解型触媒を反応開始剤として使用して、硬化させるラジカル重合型硬化樹脂、
(c)シアネート基を有する化合物と、マレイミド基を有する化合物とを反応させて硬化させるマレイミドトリアジン樹脂、
(d)マレイミド化合物とアミン化合物とを反応させて硬化させる熱硬化性ポリイミド樹脂、
(e)ベンゾオキサジン環を有する化合物を加熱重合により架橋硬化させるベンゾオキサジン樹脂、
等が挙げられる。
本発明のプリプレグは、前記したガラス組成フィラー、ガラスクロス、及びマトリックス樹脂から構成される。
ガラスクロスに対するマトリックス樹脂とガラス組成フィラーの合計付着量は、容易に板成型にできる理由から、30質量%以上であることが好ましく、またプリプレグの作製を容易にし、ガラスクロスの補強効果を最大にする理由から、90質量%以下であることが好ましい。
本発明のプリプレグは、常法に従って製造することができる。例えば、表面処理されたガラス組成フィラーとマトリックス樹脂とを有機溶剤で希釈したワニスにガラスクロスを含浸させた後、通常100~200℃の乾燥機中で、1~30分加熱させる方法などにより、マトリックス樹脂を半硬化(Bステージ化)させるとともに有機溶剤を揮発させて、プリプレグを得ることができる。含浸させた後に、スリットなどで余分なワニスを除去し、厚みを適宜調節してもよい。
上記ワニスにおける有機溶剤としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、エチレングリコールモノメチルエーテル、ジメチルホルムアミド、ジメチルアセトアミド、トルエン、キシレン、テトラヒドロフラン(THF)又はN-メチルピロリドン(NMP)が好ましく、適宜、任意に混合して使用してもよい。そのワニス中に、表面処理されたガラス組成フィラーとマトリックス樹脂の合計量は、30質量%以上90質量%以下が好ましい。
以下の実施例によって本発明をさらに詳細に説明するが、本発明はこれらの実施例によって何ら限定されるものではない。
ガラス組成フィラーを水溶媒に分散させたスラリーの状態でレーザ回折器(日機装(株)製マイクロトラックMT3300EXII)にかけ、フィラーの粒度分布を測定し、平均体積粒子径を求めた。
ガラス組成フィラーを比表面積測定装置(日本ベルベルソープ(株)製BELSOAP28SA)にかけ、フィラーの比表面積を求めた。
N-(ビニルベンジル)-β-アミノエチル-γ-アミノプロピルトリメトキシシラン塩酸塩(東レダウコーニング製SZ6032)で処理した、スタイル1078ガラスクロス(旭化成イーマテリアルズ株式会社製、ガラス種:Eガラス、単糸径:5μm、糸を構成する単糸本数:200本、織り方:平織り、織り密度:タテ54本/インチ、ヨコ54本/インチ、通気度:9cm3/cm2/sec、質量47.0g/m2)(以下「ガラスクロスA」という。)、スタイル1080ガラスクロス(旭化成イーマテリアルズ株式会社製、ガラス種:Eガラス、単糸径:5μm、糸を構成する単糸本数:200本、織り方:平織り、織り密度:タテ60本/インチ、ヨコ47本/インチ、通気度:65cm3/cm2/sec、質量48.0g/m2)(以下「ガラスクロスB」という。)。
ビスフェノールAノボラック型エポキシ樹脂(ジャパンエポキシレジン製エピコート157S70B75)48.5質量部、ビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン製エピコート1001B80)10質量部、ビスフェノールAノボラック(ジャパンエポキシレジン製エピキュアYLH129B65)30質量部、シクロフォスファゼン(大塚化学製SPB100)11.5質量部、2エチル4メチルイミダゾール0.1質量部を混合してマトリックス樹脂ワニス(以下「マトリックス樹脂ワニスA」)という。)を得た。
プリプレグ4枚を重ね、さらに上下に厚さ12μmの銅箔を重ね、195℃、40kg/cm2で60分間加熱加圧して積層板を得た。
積層板を13mm×130mmにカットして試験片を5枚作製し、各試験片にガスバーナーで10秒接炎した後、積層板の燃焼が止まるまでの時間を計測した。燃焼が止まらず、試験片が燃えきった場合、全焼とした。UL規格に準じて難燃性判定を行った。
500mm×500mmの積層板を、温度20℃湿度60%RHの雰囲気下に、まず24時間置き、さらに温度121℃湿度100%RHの雰囲気下に1~24時間曝した後、表面の水分を除去し、288℃のハンダ浴に浸漬して引き上げ、膨れ度合いを目視により評価した。サンプル数は試験時間ごとに5個とした。以下の表3中、評価結果として、5mm未満の膨れを「○」で、5mm以上の膨れを「×」で示す。
メチルトリメトキシシラン処理された平均粒子径0.5μmであり、粒子径0.5μm以下の累積分布が32%であるEガラス組成フィラー(比表面積;12m2/g、湿式粉砕品)を、マトリックス樹脂ワニスAとエチレングリコールモノメチルエーテルに分散させて、マトリックス樹脂とガラス組成フィラーの合計固形分が70質量%、固形分中のガラス組成フィラーの濃度が30vol%となるよう調整したマトリックス樹脂ワニスに、ガラスクロスAを含浸させ、160℃で1分間乾燥後プリプレグを得た。
アミノプロピルトリエトキシシラン処理された平均粒子径0.7μmであり、粒子径0.5μm以下の累積分布が15%であるEガラス組成フィラー(比表面積;10m2/g、湿式粉砕品)を、マトリックス樹脂ワニスAとエチレングリコールモノメチルエーテルに分散させて、マトリックス樹脂とガラス組成フィラーの合計固形分が70質量%、固形分中のガラス組成フィラーの濃度が30vol%となるよう調整したマトリックス樹脂ワニスに、ガラスクロスAを含浸させ、160℃で1分間乾燥後プリプレグを得た。
アミノプロピルトリエトキシシラン処理された平均粒子径0.7μmであり、粒子径0.5μm以下の累積分布が15%であるEガラス組成フィラー(比表面積;10m2/g、湿式粉砕品)を、マトリックス樹脂ワニスAとエチレングリコールモノメチルエーテルに分散させて、マトリックス樹脂とガラス組成フィラーの合計固形分が70質量%、固形分中のガラス組成フィラーの濃度が30vol%となるよう調整したマトリックス樹脂ワニスに、ガラスクロスBを含浸させ、160℃で1分間乾燥後プリプレグを得た。
アミノプロピルトリエトキシシラン処理された平均粒子径1.8μmであり、粒子径0.5μm以下の累積分布が5%であるEガラス組成フィラー(比表面積;3m2/g、湿式粉砕品)を、マトリックス樹脂ワニスAとエチレングリコールモノメチルエーテルに分散させて、マトリックス樹脂とガラス組成フィラーの合計固形分が70質量%、固形分中のガラス組成フィラーの濃度が30vol%となるよう調整したマトリックス樹脂ワニスに、ガラスクロスAを含浸させ、160℃で1分間乾燥後プリプレグを得た。
アミノプロピルトリエトキシシラン処理された平均粒子径0.2μmであり、粒子径0.5μm以下の累積分布が80%であるEガラス組成フィラー(比表面積;21m2/g、湿式粉砕品)を、マトリックス樹脂ワニスAとエチレングリコールモノメチルエーテルに分散させて、マトリックス樹脂とガラス組成フィラーの合計固形分が70質量%、固形分中のガラス組成フィラーの濃度が30vol%となるよう調整したマトリックス樹脂ワニスに、ガラスクロスAを含浸させ、160℃で1分間乾燥後プリプレグを得た。
アミノプロピルトリエトキシシラン処理された平均粒子径1.8μmであり、粒子径0.5μm以下の累積分布が5%であるEガラス組成フィラー(比表面積;2m2/g、乾式粉砕品)を、マトリックス樹脂ワニスAとエチレングリコールモノメチルエーテルに分散させて、マトリックス樹脂とガラス組成フィラーの合計固形分が70質量%、固形分中のガラス組成フィラーの濃度が30vol%となるよう調整したマトリックス樹脂ワニスに、ガラスクロスAを含浸させ、160℃で1分間乾燥後プリプレグを得た。
アミノプロピルトリエトキシシラン処理された平均粒子径1.8μmであり、粒子径0.5μm以下の累積分布が3%であるEガラス組成フィラー(比表面積;2m2/g、湿式粉砕品)を、マトリックス樹脂ワニスAとエチレングリコールモノメチルエーテルに分散させて、マトリックス樹脂とガラス組成フィラーの合計固形分が70質量%、固形分中のガラス組成フィラーの濃度が30vol%となるよう調整したマトリックス樹脂ワニスに、ガラスクロスAを含浸させ、160℃で1分間乾燥後プリプレグを得た。
アミノプロピルトリエトキシシラン処理された平均粒子径2.6μmであり、粒子径0.5μm以下の累積分布が0.5%であるEガラス組成フィラー(比表面積;3m2/g)を、マトリックス樹脂ワニスAとエチレングリコールモノメチルエーテルに分散させて、マトリックス樹脂とガラス組成フィラーの合計固形分が70質量%、固形分中のガラス組成フィラーの濃度が30vol%となるよう調整したマトリックス樹脂ワニスに、ガラスクロスAを含浸させ、160℃で1分間乾燥後プリプレグを得た。
未処理の平均粒子径0.5μmであり、粒子径0.5μm以下の累積分布が30%であるシリカフィラー(比表面積;9m2/g)を、マトリックス樹脂ワニスAとエチレングリコールモノメチルエーテルに分散させて、マトリックス樹脂とシリカフィラーの合計固形分が70質量%、固形分中のシリカフィラーの濃度が30vol%となるよう調整したマトリックス樹脂ワニスに、ガラスクロスAを含浸させ、160℃で1分間乾燥後プリプレグを得た。
未処理の平均粒子径2.1μmであり、粒子径0.5μm以下の累積分布が1%である水酸化アルミニウムフィラー(比表面積;4m2/g)を、マトリックス樹脂ワニスAとエチレングリコールモノメチルエーテルに分散させて、マトリックス樹脂と水酸化アルミニウムフィラーの合計固形分が70質量%、固形分中の水酸化アルミニウムフィラーの濃度が30vol%となるよう調整したマトリックス樹脂ワニスに、ガラスクロスAを含浸させ、160℃で1分間乾燥後プリプレグを得た。
上記実施例及び比較例で得られたプリプレグから作製した積層板の難燃性の評価結果を、以下の表2に、そして耐熱性の評価結果を、以下の表3に示す。
Claims (11)
- 平均粒子径が2.0μm以下であり、かつ、CaO含量が5質量%以上であるガラス組成フィラー、ガラスクロス、及びマトリックス樹脂からなるプリプレグであって、該ガラス組成フィラーと該マトリックス樹脂の合計体積に対する該ガラス組成フィラーの充填量が10vol%以上70vol%以下であることを特徴とする前記プリプレグ。
- 前記ガラス組成フィラーの比表面積が1m2/g以上20m2/g以下である、請求項1に記載のプリプレグ。
- 前記ガラスクロスの平均モノフィラメント径が7μm以下である、請求項1又は2に記載のプリプレグ。
- 前記ガラスクロスの通気度が50cm3/cm2/sec以下である、請求項1又は2に記載のプリプレグ。
- 前記ガラス組成フィラーのガラス組成がEガラス又はLガラスである、請求項1又は2に記載のプリプレグ。
- 前記ガラス組成フィラーの表面が、下記一般式(1):
XSi(R)3-nYn (1)
{式中、Xは、有機官能基であり、Yは、アルコキシ基であり、nは、1~3の整数であり、そしてRは、メチル基、エチル基又はヒドロキシル基である。}で表される化合物を含むシランカップリング剤で処理されている、請求項1又は2に記載のプリプレグ。 - 前記ガラス組成フィラーの粒子径0.5μm以下の粒子含量が5%以上である、請求項1又は2に記載のプリプレグ。
- 前記ガラス組成フィラーが乾式粉砕により得られたものである、請求項1又は2に記載のプリプレグ。
- 前記ガラス組成フィラーの粒子径が0.1μm以上であり、前記ガラス組成フィラーの粒子径0.5μm以下の粒子含量が10%以上であり、前記ガラス組成フィラーの比表面積が2m2/g以上20m2/g以下である、請求項1に記載のプリプレグ。
- 前記ガラスクロスの通気度が50cm3/cm2/sec以下であり、前記ガラス組成フィラーが乾式粉砕により得られたものである請求項1又は10に記載のプリプレグ。
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MY192276A (en) * | 2018-09-12 | 2022-08-16 | Aica Kogyo Co Ltd | Decorative laminate |
KR102540056B1 (ko) * | 2021-11-29 | 2023-06-05 | 주식회사 현대폴리텍 | 난연성능이 향상된 선박용 부품의 제조방법 |
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- 2010-09-14 JP JP2011531930A patent/JP5584692B2/ja active Active
- 2010-09-14 KR KR1020127006635A patent/KR101384947B1/ko active IP Right Grant
- 2010-09-14 CN CN201080041159.8A patent/CN102498163B/zh active Active
- 2010-09-14 US US13/496,062 patent/US20120177911A1/en not_active Abandoned
- 2010-09-14 TW TW099131081A patent/TWI534185B/zh active
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JP2008222986A (ja) * | 2007-03-16 | 2008-09-25 | Asahi Kasei Electronics Co Ltd | プリプレグとその製造方法 |
Cited By (8)
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CN102936097A (zh) * | 2011-08-16 | 2013-02-20 | 苏州锦艺新材料科技有限公司 | 一种玻璃微粉及其制备方法 |
JP2013216741A (ja) * | 2012-04-05 | 2013-10-24 | Panasonic Corp | エポキシ樹脂組成物、プリプレグ、積層板、プリント配線板 |
KR20200009140A (ko) * | 2015-04-27 | 2020-01-29 | 아사히 가세이 가부시키가이샤 | 유리 클로스 |
KR102458088B1 (ko) * | 2015-04-27 | 2022-10-24 | 아사히 가세이 가부시키가이샤 | 유리 클로스 |
JP2019019431A (ja) * | 2017-07-19 | 2019-02-07 | 旭化成株式会社 | ガラスクロス、プリプレグ、及びプリント配線板 |
JP2022001690A (ja) * | 2017-07-19 | 2022-01-06 | 旭化成株式会社 | ガラスクロス、プリプレグ、及びプリント配線板 |
JP7169053B2 (ja) | 2017-07-19 | 2022-11-10 | 旭化成株式会社 | ガラスクロス、プリプレグ、及びプリント配線板 |
JP7321222B2 (ja) | 2017-07-19 | 2023-08-04 | 旭化成株式会社 | ガラスクロス、プリプレグ、及びプリント配線板 |
Also Published As
Publication number | Publication date |
---|---|
CN102498163A (zh) | 2012-06-13 |
TWI534185B (zh) | 2016-05-21 |
KR20120055686A (ko) | 2012-05-31 |
CN102498163B (zh) | 2014-07-30 |
JPWO2011034055A1 (ja) | 2013-02-14 |
KR101384947B1 (ko) | 2014-04-11 |
US20120177911A1 (en) | 2012-07-12 |
TW201113315A (en) | 2011-04-16 |
JP5584692B2 (ja) | 2014-09-03 |
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