Classifications

• • 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
  • C08L63/04—Epoxynovolacs
• • 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
• • 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
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
  • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/02—Halogenated hydrocarbons
• • 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
• • 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
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/5399—Phosphorus bound to nitrogen

Definitions

• the present invention relates to a resin composition. Specifically, it contains a specific epoxy resin, a specific phenol resin, and a polytetrafluoroethylene filler having a specific particle size, and does not impair the original properties of the resin, and has a low dielectric constant and heat resistance.
• the present invention relates to a resin composition having a high value.
• Epoxy resin compositions have excellent electrical performance and adhesive strength, and thus have various uses in the electric / electronic field.
• the epoxy resin has a problem that the dielectric constant increases when the epoxy ring is opened and a hydroxyl group is generated during curing.
• it is necessary to use an epoxy resin with a small epoxy equivalent to make the cross-linked structure dense, but since the generation of hydroxyl groups is increased accordingly, the dielectric constant is further increased. There is a tendency.
• polytetrafluoroethylene is useful as an insulating material because it has a dielectric constant of 2.1, which is extremely low among resins, and has excellent insulation and chemical resistance.
• Patent Documents 1 and 2 a resin composition containing biphenyl type epoxy resin and novolac type phenol resin as essential components, and biphenyl type epoxy resin and biphenyl type phenol resin Is disclosed as an essential component (Patent Document 3), but these documents do not describe the use of a combination of polytetrafluoroethylene fillers. As described above, polytetrafluoroethylene is difficult to be used as a resin composition because of poor adhesion and compatibility with other resins, so that there is no example used in this field yet.
• a first object of the present invention is to provide a resin composition having excellent low dielectric constant and heat resistance, as well as not deteriorating the properties of the resin even when a polytetrafluoroethylene filler is blended. is there.
• a second object of the present invention is to provide a build-up insulator excellent in low dielectric constant and heat resistance.
• a third object of the present invention is to provide a printed circuit board prepreg having a low dielectric constant and excellent heat resistance.
• the present inventors have obtained a blend of a specific epoxy resin and a specific phenol resin using a polytetrafluoroethylene filler having a specific particle diameter.
• the present inventors have found that the obtained resin composition can achieve the above object, and have reached the present invention.
• the present invention relates to an epoxy resin represented by the following formula (I), a phenol resin represented by the following formula (II), and polytetrafluoro having an average particle size of 0.01 to 20 ⁇ m by a laser diffraction particle size distribution measurement method.
• n in the above formula is an integer of 0 to 50
• A is at least one divalent group selected from the following group (A)
• Y is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, An alkenyl group having 2 to 10 carbon atoms or a group represented by the following formula (Y).
• X 1 to X 4 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
• T is a direct bond, a methylene group, an ethylidene group, a propylidene group, -O-, -S- or -SO 2- .
• m is an integer of 0 to 400
• A is at least one divalent group selected from the group (A)
• Z is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
• T is a direct bond, a methylene group, an ethylidene group, a propylidene group, -O-, -S- or -SO 2- .
• the epoxy resin is preferably an epoxy resin represented by the following formula (I-1). Wherein n is an integer of 0 to 50, X 1 to X 4 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Y is a hydrogen atom or 1 to 10 carbon atoms. A 10 alkyl group, an alkenyl group having 2 to 10 carbon atoms, or a group represented by the following formula (Y). However, T is a direct bond, a methylene group, an ethylidene group, a propylidene group, -O-, -S- or -SO 2- .
• the phenol resin is preferably a phenol resin represented by the following formula (II-1).
• m is an integer of 0 to 400
• X 1 to X 4 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
• Z is a hydrogen atom or 1 carbon atom.
• T is a direct bond, a methylene group, an ethylidene group, a propylidene group, -O-, -S- or -SO 2- .
• the resin composition may further contain a reactive flame retardant, and the reactive flame retardant is preferably a phosphate amide compound represented by the following general formula (III).
• R 1 , R 2 and R 3 are a hydrogen atom, or an alkyl or cycloalkyl group having 1 to 8 carbon atoms, or a halogen atom
• S 1 and S 2 are direct bonds or carbon atoms
• a C 1-4 alkylene group or an alkylidene group, and the ring C is an arylene group, a cycloalkylene group, an arylene-alkylene-arylene group or an arylene-alkylidene-arylene group having 6 to 18 carbon atoms.
• the resin composition of the present invention contains an epoxy resin represented by the following general formula (I).
• n in the above formula (I) is an integer of 0 to 50.
• n exceeds 50 the viscosity becomes too high and it becomes difficult to dissolve in a solvent.
• a in the above formula (I) is at least one divalent group selected from the following group (A).
• X 1 to X 4 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
• Y is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a group represented by the following formula (Y).
• T is a direct bond, a methylene group, an ethylidene group, a propylidene group, -O-, -S- or -SO 2- .
• the epoxy resin represented by the formula (I) used in the resin composition of the present invention may be only one type or two or more types.
• an epoxy resin represented by the following general formula (I-1) as the epoxy resin.
• n, X 1 to X 4 and Y are as described above.
• epoxy resins may be used in combination with the epoxy resin as long as the effects of the present invention are not impaired.
• examples of other epoxy resins include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, bisphenol F, methylene bis (orthocresol), ethylidene bisphenol, Bisphenol A, isopropylidenebis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3- Tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac, orthocresol novolak, ethyl ether
• epoxy resins are those internally crosslinked by a prepolymer of terminal isocyanate, or those having a high molecular weight with polyhydric active hydrogen compounds such as polyhydric phenols, polyamines, carbonyl group-containing compounds, polyphosphates, etc. But you can.
• the resin composition of the present invention contains a phenol resin represented by the following general formula (II).
• the phenol resin is used as a curing agent for the resin composition.
• M in the above formula (II) is an integer of 0 to 400. When m exceeds 400, the viscosity becomes too high and it becomes difficult to dissolve in a solvent.
• a in the formula (II) is at least one divalent group selected from the group (A).
• Z in the above formula (II) is a hydrogen atom, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, or a group represented by the following formula (Z).
• T is a direct bond, a methylene group, an ethylidene group, a propylidene group, -O-, -S- or -SO 2- .
• the phenol resin represented by the formula (II) used in the resin composition of the present invention may be only one type or two or more types.
• M, X 1 to X 4 and Z in the formula (II-1) are as described above.
• phenol resins may be used in combination with the phenol resin as long as the effects of the present invention are not impaired.
• examples of other phenol resins include phenol resins synthesized from phenols and aldehydes.
• the phenols include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, butylphenol, tert-butylphenol, octylphenol, nonylphenol, dodecylphenol, cyclohexylphenol, chlorophenol, bromophenol, resorcin, catechol, hydroquinone.
• the average particle size of the polytetrafluoroethylene filler contained in the resin composition of the present invention by the laser diffraction particle size distribution measurement method needs to be 0.01 to 20 ⁇ m, and preferably 0.03 to 10 ⁇ m.
• the average particle size is less than 0.01 ⁇ m, it becomes difficult to mix a large amount with the resin, and when it exceeds 20 ⁇ m, it is difficult to produce a thin film.
• the amount of the epoxy resin, the phenol resin and the polytetrafluoroethylene filler can be appropriately changed according to the use, but the amount of the total phenol resin used is 5 to 150 parts by mass with respect to 100 parts by mass of the total epoxy resin. It is preferably 10 to 100 parts by mass.
• the polytetrafluoroethylene filler is preferably used in an amount of 5 to 100 parts by weight, particularly preferably 8 to 50 parts by weight, based on 100 parts by weight of the total epoxy resin.
• the resin composition of the present invention preferably further contains a reactive flame retardant.
• the reactive flame retardant that can be used include phosphorus-based reactive flame retardants represented by the following general formulas (III) to (V).
• R 1 , R 2 and R 3 in the formula are a hydrogen atom or an alkyl or cycloalkyl group having 1 to 8 carbon atoms, or a halogen atom
• S 1 and S 2 are direct bonds, or 1 carbon atom.
• An alkylene group or an alkylidene group of ⁇ 4, and ring C is an arylene group, cycloalkylene group, arylene-alkylene-arylene group or arylene-alkylidene-arylene group having 6 to 18 carbon atoms.
• R 1 in the formula is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, or a halogen atom.
• R 1 in the formula is a hydrogen atom, an alkyl group or a cycloalkyl group having 1 to 8 carbon atoms, or a halogen atom.
• a phosphoric acid amide compound represented by the general formula (III) in order to lower the dielectric constant.
• the amount of the reactive flame retardant used is 5 to 100 parts by mass, preferably 8 to 50 parts by mass with respect to 100 parts by mass of the total epoxy resin.
• another epoxy resin curing agent may be used in combination with the phenol resin as long as the effects of the present invention are not impaired.
• the viscosity and curing characteristics of the resulting curable composition, or the physical properties after curing can be controlled.
• other curing agents include latent curing agents, acid anhydrides, polyamine compounds, and the like.
• the resin composition of the present invention is a one-component curable composition that is easy to handle. From the viewpoint of producing a product, it is preferable to use a latent curing agent.
• latent curing agent examples include dicyandiamide, hydrazide, imidazole compound, amine adduct, sulfonium salt, onium salt, ketimine, acid anhydride, and tertiary amine.
• acid anhydride examples include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, 2 , 2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride and the like.
• polyamine compound examples include aliphatic polyamines such as ethylenediamine, diethylenetriamine, and triethylenetetramine; mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, bis (aminomethyl) cyclohexane, 3, Alicyclic polyamines such as 9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro [5,5] undecane, aliphatic amines having an aromatic ring such as m-xylenediamine; m-phenylene Diamine, 2,2-bis (4-aminophenyl) propane, diaminodiphenylmethane, diaminodiphenylsulfone, ⁇ , ⁇ -bis (4-aminophenyl) -p-diisopropylbenzene, 2,2-bis (4-aminophenyl) Aromatic polyamines such as -1,1,1,3,3,
• other fillers can be used in combination with the polytetrafluoroethylene filler as long as the effects of the present invention are not impaired.
• other fillers include glass fillers, calcium carbonate, aluminum hydroxide, magnesium hydroxide, alumina, silicon nitride, silicon carbide, mica, talc, kaolin clay, silica, barium sulfate, and other various organic materials.
• Conventional fillers such as filler, glass fiber, wollastonite, alumina fiber, ceramic fiber, and various whisker fillers can be used.
• other additives can be added to the resin composition of the present invention.
• the other additives include plasticizers such as natural waxes, synthetic waxes and metal salts of long chain fatty acids, release agents such as acid amides, esters and paraffins, nitrile rubber, butadiene rubber, acrylic Stress relaxation agents such as rubber and silicon rubber, silane coupling agents, titanate coupling agents, aluminum coupling agents, coupling agents such as zirconium coupling agents, coloring agents such as dyes and pigments, oxidation stabilizers , Light stabilizers, moisture resistance improvers, thixotropy imparting agents, ion adsorbents, diluents, antifoaming agents, other various resins, tackifiers, antistatic agents, lubricants, ultraviolet absorbers, and alcohols, Ethers, acetals, ketones, esters, alcohol esters, ketone alcohols, ether alcohols, ketone ethers, ketones N'esuteru
• the insulator for build-up of the present invention can be obtained by applying the resin composition of the present invention to a base film and drying it to make the resin composition semi-cured.
• the prepreg for a printed circuit board of the present invention is obtained by applying the resin composition of the present invention to a substrate such as a glass cloth by a known method and then drying it to make the resin composition semi-cured.
• a copper-clad laminate is obtained by laminating the prepreg of the present invention and a copper foil, and heating and pressing so that the resin composition is completely cured by a known method.
• the number of prepregs can be changed as required.
• Example 1 The resin composition having the compounding ratio shown in Table 1 was dispersed using a bead mill, applied to an IPC standard 1037 glass cloth so as to have a thickness of 45 ⁇ m, and dried at 130 ° C. for 10 minutes to prepare a prepreg.
• surface represents a mass part.
• MEK methyl ethyl ketone
• a copper foil was laminated on both surfaces of the obtained prepreg, and then cured by pressurizing at a pressure of 30 kg / cm 2 and a final temperature of 190 ° C. for 90 minutes using a vacuum press machine to obtain a laminate.
• the copper foil peeling strength of the obtained laminate was measured according to JIS C6481.
• the glass transition point, thermal expansion coefficient, dielectric constant and dielectric loss tangent of the substrate were measured by the following methods.
• ⁇ Glass transition point (Tg)> Using a DMS 6100 manufactured by SII (SII Nanotechnology Inc.), the measurement range was 30 ° C. to 350 ° C. (temperature increase at 5 ° C./min), and the peak of tan ⁇ was taken as the glass transition point.
• CTE Cost of thermal expansion
• ⁇ Dielectric constant and dielectric loss tangent> The measurement was performed under the conditions of an applied voltage of 500 mV and a frequency of 1 GHz by using an impedance / material analyzer E4991A manufactured by Agilent Technologies.
• ⁇ Combustion test> Panasonic Electric Works R-1566 from which the copper foil has been removed, the prepreg laminated on the top and bottom of the 0.8 mm substrate, and further sandwiched by the copper foil, using a vacuum press machine, pressure 30 kgf / cm 2 , 190 ° C., The laminate was obtained by applying pressure and curing for 90 minutes. The copper foil of the obtained laminate was completely removed using an etching solution, and a combustion test was performed under conditions according to UL-94.
• Epoxy resin 1 NC-3000H (biphenylene aralkyl epoxy resin manufactured by Nippon Kayaku Co., Ltd.)
• Epoxy resin 2 HP-7200 (Dicyclopentadiene type epoxy resin manufactured by DIC Corporation)
• Epoxy resin 3 EP-4100E (bisphenol A type epoxy resin made by ADEKA)
• Phenolic resin 1 MEH-7851H (biphenylene aralkyl type phenolic resin manufactured by Meiwa Kasei Co., Ltd.)
• Phenolic resin 2 GDP-6115H (dicyclopentadiene type phenolic resin manufactured by Gunei Chemical Industry Co., Ltd.)
• Phenolic resin 3 PSM-4326 (Novolac type phenolic resin manufactured by Gunei Chemical Industry Co., Ltd.)
• PTFE filler 1 TFW-3000 (polytetrafluoroethylene filler manufactured by Seishin Co., Ltd .: average particle size 3 ⁇ m)
• Tables 3 and 4 show the test results of the examples and comparative examples.
• composition (Comparative Example 4) containing polypropylene filler instead of polytetrafluoroethylene filler is not suitable for use as an electronic material because the polypropylene filler melts when dried at 130 ° C. It was. Further, when a resin composition in which polytetrafluoroethylene having a particle size exceeding 20 ⁇ m was blended as a filler (Comparative Example 5), it was difficult to produce a thin film.
• the resin composition of the present invention can be used for electronic materials such as pastes, B-stage films, resin-coated copper foils or prepregs for printed circuit boards, particularly high-frequency multilayer boards, build-up insulating materials, etc. It is extremely useful.

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• 2011
  • 2011-10-04 JP JP2011219996A patent/JP2013079326A/ja active Pending
• 2012
  • 2012-09-05 TW TW101132303A patent/TW201315751A/zh unknown
  • 2012-10-01 WO PCT/JP2012/006265 patent/WO2013051227A1/ja not_active Ceased

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