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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/14—Peroxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
  • C08F212/36—Divinylbenzene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
  • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/062—Polyethers
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C08L71/12—Polyphenylene oxides
  • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
• • 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
• • 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

Definitions

• the present invention relates to thermosetting compositions, resin films, prepregs, metal-clad laminates, and printed wiring boards.
• Polyphenylene ether which has excellent dielectric properties (low dielectric constant and low dielectric loss tangent) as a resin for thermosetting compositions, is suitable as an electronic circuit board material that can meet the above requirements, and is attracting attention (Patent Document 1 , 2).
• thermosetting composition containing polyphenylene ether for electronic circuit board materials (hereinafter referred to as a polyphenylene ether composition) is cured and processed at a high temperature of 190°C or higher. If the heat resistance of the cured product obtained by curing the polyphenylene ether composition (hereinafter referred to as the cured polyphenylene ether) is low, the strength of the cured polyphenylene ether decreases during processing, etc., and in more severe and long-term use cannot gain credibility. Therefore, the polyphenylene ether cured product is required to have heat resistance, but the conventional polyphenylene ether cured product as described in Patent Document 1 lacks heat resistance.
• polyphenylene ether Since polyphenylene ether has a high viscosity, it is diluted with a solvent when processing the polyphenylene ether composition. Therefore, a solvent-drying step (a step of subjecting the composition diluted with a solvent to a temperature higher than room temperature) is required later. When the solvent is dried, the organic peroxide is decomposed, gelation occurs, and the fluidity of the composition may be lost. Loss of fluidity of the composition causes voids in the cured polyphenylene ether, resulting in loss of uniformity of the cured product and deterioration in quality.
• the polyphenylene ether composition described in Patent Document 2 has a problem with fluidity during processing, and further improvement is desired.
• the problem to be solved by the present invention is to obtain a polyphenylene ether cured product that has excellent dielectric properties and heat resistance, is difficult to gel even under high temperatures such as the drying process of the contained solvent, and has good fluidity during processing.
• An object of the present invention is to provide an excellent thermosetting composition.
• the present invention provides a thermosetting composition containing polyphenylene ether and an organic peroxide, wherein the polyphenylene ether has an ethylenically unsaturated double bond at the molecular end, and the organic peroxide is the general formula (1): (In the formula (1), R 1 is an alkyl group having 2 to 8 carbon atoms) and a t-alkyl hydroperoxide represented by It relates to a thermosetting composition containing 0.02 parts by mass or more and 10 parts by mass or less of t-alkyl hydroperoxide.
• the present invention provides a resin film formed from the thermosetting composition, a prepreg impregnated or coated with the thermosetting composition on a fibrous base material, the resin film or the prepreg, and a metal foil. and a printed wiring board in which part of the metal foil is removed from the metal-clad laminate.
• the radicals generated by thermal decomposition cause an addition reaction, thereby three-dimensionally curing the polyphenylene ether having an ethylenically unsaturated double bond at the molecular end, and the t-alkyl hydroperoxide is While slightly decomposing during the polyphenylene ether curing reaction and contributing to curing, it functions as a radical trapping agent, so the cured polyphenylene ether obtained by curing the thermosetting composition of the present invention has excellent dielectric properties and heat resistance. It is presumed that the thermosetting composition can maintain its fluidity even at high temperatures such as during the process of drying the contained solvent.
• thermosetting composition of the invention contains a polyphenylene ether and an organic peroxide.
• the polyphenylene ether contains a phenylene ether unit as a repeating structural unit and has an ethylenically unsaturated double bond at the end of the molecule.
• the polyphenylene ethers may be used alone or in combination of two or more.
• polyphenylene ether examples include, for example, 2,6-dimethylphenol and other phenols (eg, 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, 2- allylphenol, etc.); polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols; and poly(2,6-dimethyl-1,4 -Phenylene ether) and phenolic compounds such as bisphenols and trisphenols are heated in a toluene solvent in the presence of an organic peroxide to form a linear or branched structure obtained by a redistribution reaction.
• 2,6-dimethylphenol and other phenols eg, 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, 2- allylphenol, etc.
• polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols
• the phenylene group in the phenylene ether unit may have a substituent, and the polyphenylene ether may contain other structural units other than the phenylene ether unit to the extent that the effects of the present invention are not impaired. .
• Examples of the ethylenically unsaturated double bond at the end of the polymer include (meth)acryloyl group, styryl group, vinylbenzyl group, vinyl group, allyl group, 1,3-butadienyl group, and the like.
• a (meth)acryloyl group and a vinylbenzyl group are preferable from the viewpoints of high reactivity during thermosetting and excellent dielectric constant and dielectric loss tangent of the cured product.
• the number of ethylenically unsaturated double bonds in one molecule of the polyphenylene ether is preferably 1.5 to 6 on average, more preferably 1.6 to 4 on average, and 1.5 on average. 7 to 3 are more preferred.
• the number of ethylenically unsaturated double bonds in one molecule in the polyphenylene ether is, for example, the number of hydroxyl groups remaining in the polyphenylene ether is measured, and the polyphenylene before modification with a compound having an ethylenically unsaturated double bond It can be measured by calculating the amount of decrease from the number of hydroxyl groups of the ether.
• a method for measuring the number of hydroxyl groups remaining in polyphenylene ether is described in Kobunshi Ronbunshu, vol. 51, No. 7, page 480 (1994), tetraethylammonium hydroxide is added to a methylene chloride solution of polyphenylene ether, and the absorbance of the mixed solution is measured at a wavelength of 318 nm.
• the polyphenylene ether preferably has a structure represented by the following general formula (2).
• X is an a-valent linking group
• Y is an ethylenically unsaturated double bond at the end of the polymer
• a is 1 to 6.
• X in the formula (2) include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxy-3 ,3'5,5'-tetramethylbiphenyl, 4,4'-dihydroxy-2,2',3,3'5,5'-hexamethylbiphenyl, hydroquinone, dihydric phenols such as resorcin, tris- Trihydric or higher phenols represented by (4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol novolak, o-cresol novolak, naphthol novolak and the like can be mentioned.
• the polyphenylene ether preferably has a number average molecular weight of 800 or more and 5000 or less, more preferably 900 or more and 4500 or less, and 1000 or more and 3000 or less, from the viewpoint of dielectric properties and impregnation into a fibrous base material. It is even more preferable to have
• the number average molecular weight may be measured by a general molecular weight measurement method, and examples thereof include a polystyrene equivalent value measured using gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• the method for synthesizing the polyphenylene ether is not particularly limited as long as it can synthesize a modified polyphenylene ether modified with an ethylenically unsaturated double bond.
• polyphenylene ether before modification is reacted with a compound having an ethylenically unsaturated double bond and a chlorine atom.
• compounds having an ethylenically unsaturated double bond and a chlorine atom include (meth)acryloyl chloride and vinylbenzyl chloride.
• polyphenylene ethers may also be used, such as product names "OPE-2St” (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and “Noryl SA9000” (manufactured by SABIC Innovative Plastics).
• the organic peroxide has the general formula (1): (In formula (1), R 1 is an alkyl group having 2 to 8 carbon atoms.) and dialkyl peroxides and t-alkyl hydroperoxides.
• R 1 is, for example, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, neopentyl group, 1-cyclohexyl-1-methylethyl group, n-octyl group and the like. and preferably an ethyl group, an n-propyl group, or a neopentyl group.
• R 1 is 2 or more, the oxygen radicals generated after thermal decomposition of the dialkyl peroxide undergo rapid ⁇ -cleavage to be converted into carbon radicals to initiate the curing reaction, and the radicals introduced into the polyphenylene ether cured product.
• R 1 is 2-5.
• dialkyl peroxides include t-amyl peroxide, t-hexyl methyl peroxide, 1,1,3,3-tetramethylbutyl cumyl peroxide, 1-cyclohexyl-1-methylethyl cumyl Peroxides, etc., and t-amyl cumyl peroxide, t-hexyl cumyl peroxide, and 1,1,3,3-tetramethylbutyl cumyl peroxide are preferred. 1,1,3,3-Tetramethylbutylcumyl peroxide is particularly preferred.
• the dialkyl peroxide is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, per 100 parts by mass of the polyphenylene ether. More preferably, it is 0.5 to 2 parts by mass.
• the method for producing the dialkyl peroxide compound is not particularly limited, but for example, general formula (3): (In formula (3), R 1 is an alkyl group having 2 to 8 carbon atoms.) and a t-alkyl hydroperoxide represented by general formula (4): or a t-alkyl hydroperoxide represented by the above general formula (3) and the general formula (5 ):
• a production method including a step of reacting ⁇ -cumyl alcohol represented by (hereinafter also referred to as step (B)).
• the t-alkyl hydroperoxide represented by the general formula (3), the ⁇ -methylstyrene represented by the general formula (4), the ⁇ - Cumyl alcohol may use a commercial item.
• the t-alkyl hydroperoxide represented by the general formula (3) is 1 mol of ⁇ -methylstyrene represented by the general formula (4), or With respect to 1 mol of ⁇ -cumyl alcohol represented by the general formula (5), it is preferable to react 1 mol or more from the viewpoint of increasing the yield of the target product, and from the viewpoint of improving the purity of the target product. It is preferable to react 5 mol or less.
• the reaction temperature in the step (A) and the step (B) is preferably 0° C. or higher, more preferably 10° C. or higher, from the viewpoint of increasing the yield of the target product. From the viewpoint of, the temperature is preferably 60° C. or lower, more preferably 50° C. or lower.
• the reaction time of the steps (A) and (B) varies depending on the raw materials, the reaction temperature, etc., and cannot be unconditionally determined. It is preferably 1 hour or more, and preferably 5 hours or less from the viewpoint of safety.
• the acid catalyst is not particularly limited, and examples thereof include acetic acid, hydrochloric acid, sulfuric acid, perchloric acid and the like.
• the acid catalyst may be used alone or in combination of two or more.
• the amount of the acid catalyst to be used is not particularly limited. It is preferable to use 0.02 mol or more per 1 mol of ⁇ -cumyl alcohol represented by formula (5) from the viewpoint of increasing the yield of the target product, and from the viewpoint of safety, 5 mol or less is used. preferably.
• organic solvent can be used in the step (A) and the step (B).
• the organic solvent is not particularly limited, it is preferably an organic solvent that is inert in the reaction system.
• the organic solvent include non-polar compounds such as pentane, hexane and toluene; and polar compounds such as isopropanol, acetone and acetonitrile.
• the organic solvent may be used alone or in combination of two or more.
• the amount of the organic solvent used is not particularly limited, but usually 3 to 300 parts by mass with respect to 100 parts by mass of ⁇ -methylstyrene or ⁇ -cumyl alcohol. About a part.
• Identification of the target product obtained is carried out using liquid chromatography (LC), gas chromatography (GC), nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR), mass spectrometry (MS), etc. It can be carried out.
• LC liquid chromatography
• GC gas chromatography
• NMR nuclear magnetic resonance spectroscopy
• IR infrared spectroscopy
• MS mass spectrometry
• the t-alkyl hydroperoxide is not particularly limited.
• the generated oxygen radicals undergo rapid ⁇ -cleavage to be converted into carbon radicals to initiate the curing reaction. It is preferable that the number of carbon atoms in the tertiary alkyl group of the hydroperoxide is 5 or more because the radicals introduced into the polyphenylene ether cured product can improve the dielectric properties when the polarity thereof is low.
• the number of carbon atoms in the tertiary alkyl group of the hydroperoxide is preferably 8 or less, since the molecular weight becomes smaller and the amount of radicals generated increases with the same addition amount, thereby improving the heat resistance.
• Examples include t-butyl hydroperoxide, t-amyl hydroperoxide, t-hexyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-cumyl hydroperoxide and the like. , t-hexyl hydroperoxide and 1,1,3,3-tetramethylbutyl hydroperoxide are preferred. 1,1,3,3-Tetramethylbutyl hydroperoxide is particularly preferred.
• the t-alkyl hydroperoxide is 0.02 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the dialkyl peroxide.
• the t-alkyl hydroperoxide is preferably 0.05 parts by mass or more, and 0.1 parts by mass or more.
• the t-alkyl hydroperoxide is preferably 8 parts by mass or less, more preferably 5 parts by mass or less, and 3 parts by mass Part or less is more preferable.
• thermosetting composition of the present invention a polymerization initiator other than the dialkyl peroxide and t-alkyl hydroperoxide of the present invention is added to the extent that the effects of the present invention are not impaired in order to improve productivity and cure degree. They may be used together.
• the polymerization initiator is not particularly limited, and those commonly used in this field can be used, but an oil-soluble polymerization initiator that is soluble in the thermosetting composition is preferred.
• the polymerization initiators may be used alone or in combination of two or more.
• polymerization initiator examples include peroxydicarbonates such as bis-(4-t-butylcyclohexyl)peroxydicarbonate, diacyl peroxides such as dibenzoyl peroxide, and t-butylperoxy-2-ethylhexanoate.
• peroxyesters such as t-butyl benzoate, peroxymonocarbonates such as t-butylperoxy 2-ethylhexylmonocarbonate, peroxyketals such as 1,1-bis(t-butylperoxy)cyclohexane, ⁇ , ⁇ '-bis(t -butylperoxy)diisopropylbenzene, dialkyl peroxides such as 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, azo compounds such as 2,2′-azobis(2-methylbutyronitrile), 1-hydroxycyclohexyl phenyl ketone, diphenyl-2,4,6-trimethylbenzoylphosphine oxide, 1-[( ⁇ 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethylidene ⁇ Amino)oxy]ethanone and other photopolymerization initiators
• the thermosetting composition of the present invention may contain a polyfunctional monomer from the viewpoint of improving heat resistance.
• the polyfunctional monomer include ethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.
• polyfunctional (meth)acrylates such as 1,4-divinylbenzene, vinylbenzene derivatives such as 4-vinylbenzoic acid-2-acryloylethyl ester, alkenyl isocyanurate derivatives such as triallyl isocyanurate (TAIC), triallyl cyanide Alkenyl cyanurate derivatives such as nurate (TAC), maleimide derivatives such as 4,4-bismaleimide diphenylmethane, N,N-1,3-phenylene bismaleimide, and polybutadiene having two or more vinyl groups in the molecule A vinyl compound etc. are mentioned. Among these, triallyl isocyanurate, triallyl cyanurate, and polybutadiene are preferable because of their excellent heat resistance.
• the polyfunctional monomers may be used alone or in combination of two or more.
• the polyfunctional monomer is preferably 5 parts by mass to 50 parts by mass, more preferably 7 parts by mass to 40 parts by mass, still more preferably 10 parts by mass to 30 parts by mass, relative to 100 parts by mass of the polyphenylene ether. part by mass.
• a solvent may be further added to the thermosetting composition of the present invention in order to improve the viscosity, the ability to impregnate the glass cloth, and the smoothness of the cured film.
• the solvent is not particularly limited as long as it is capable of dissolving or dispersing the above components and evaporates during drying.
• solvent from the viewpoint of solubility, aromatic solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone; amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Solvents are preferred. These solvents can be used singly or in combination of two or more.
• the amount of the solvent used is 10 to 1000 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition from the viewpoint of the solubility of the thermosetting composition in the solvent and the ease of the volatilization process. is preferred, and 20 to 500 parts by mass is more preferred.
• thermosetting composition of the present invention can further contain other components in appropriate combination.
• Other components include elastomers such as polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, fluororubber and silicone rubber, natural silica, fused silica, synthetic silica, amorphous silica, hollow silica, alumina, clay, talc and Inorganic fillers such as short glass fibers, silane coupling agents such as ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -(meth)acryloxypropyltrimethoxysilane, flame retardants, polymerization inhibitors agents, ultraviolet absorbers, light stabilizers, surfactants, lubricants, thickeners, antifoaming agents, antistatic agents, pigments, dyes and the like.
• elastomers such as polyisoprene
• the resin film of the present invention is formed from the thermosetting composition.
• the resin film contains a thermosetting composition before curing, a part of the thermosetting composition may be cured.
• the resin film is formed, for example, by drying a resin varnish that is a mixture of the thermosetting composition and the solvent alone, or by coating the resin varnish on a support such as a support film and then drying it. can be obtained by Drying removal of the solvent is performed with a hot air dryer or the like at, for example, 20°C to 180°C.
• the drying temperature is preferably 20 to 150°C, more preferably 50 to 130°C.
• the support for the resin film examples include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polycarbonates, polyimides, ethylenetetrafluoroethylene copolymers, copper foils, aluminum foils, and the like.
• metal foil, release paper, and the like A resin-coated metal foil is obtained by applying the thermosetting composition to a metal foil and then removing the solvent by drying with a hot air dryer or the like.
• the support may be subjected to chemical or physical treatment such as mud treatment, corona treatment, mold release treatment and the like.
• the resin film is suitable as an interlayer insulating sheet, an adhesive film, etc. for laminates such as multilayer printed wiring boards.
• the prepreg of the present invention is a composite of a fibrous base material and the thermosetting composition.
• the prepreg contains a thermosetting composition before curing, a part of the thermosetting composition may be cured.
• the prepreg is preferably a composite of a fibrous base material and a thermosetting composition impregnated or applied to the fibrous base material. Even when the thermosetting composition is applied to the surface of the fibrous base material to form a layer, the base material is impregnated with the cured thermosetting composition by press molding for curing the prepreg. structure can be obtained.
• the prepreg can be obtained, for example, by impregnating or applying a resin varnish, which is a mixture of the thermosetting composition of the present invention and a solvent, onto a substrate such as glass cloth, and then removing the solvent by drying. It is also possible to repeat the impregnation or application multiple times. Furthermore, by repeating the impregnation or application using a plurality of thermosetting compositions having different concentrations and compositions, it is possible to adjust the impregnation amount to a desired one. Drying removal of the solvent is performed with a hot air dryer or the like at, for example, 20°C to 180°C. The drying temperature is preferably 20 to 150°C, more preferably 50 to 130°C.
• the fibrous base material examples include glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, pulp paper, and linter paper. Among these, glass cloth is preferable, and flattened glass cloth is more preferable, because the mechanical strength of the printed wiring board is excellent.
• These fibrous base materials can be used individually by 1 type or in combination of 2 or more types.
• the thickness of the fibrous base material for example, one having a thickness of 1 to 300 ⁇ m can be used.
• the solid content of the thermosetting composition in the solid content of the prepreg is preferably 30 to 80% by mass, more preferably 40 to 70% by mass. If the above ratio is less than 30% by mass, insulation reliability tends to be poor when the prepreg is used for electronic substrates and the like. On the other hand, if the above proportion is more than 80% by mass, mechanical properties such as bending elastic modulus tend to deteriorate when used for electronic substrates and the like.
• the metal-clad laminate of the present invention is a laminate in which the resin film or the prepreg and metal foil are laminated.
• the laminate is produced by stacking one or more of the resin films and/or prepregs on a substrate such as a metal foil and then curing the thermosetting composition by press molding to form an insulating layer. can be manufactured. It is also possible to use the resin-coated metal foil instead of the metal foil. Heat molding can be performed, for example, at a temperature of 180° C. to 240° C., a heating time of 30 minutes to 300 minutes, and a surface pressure of 20 kgf/cm 2 to 40 kgf/cm 2 .
• the metal foil is not particularly limited, examples thereof include aluminum and copper foil, among which copper foil is preferable because of its low electrical resistance.
• a metal foil having a thickness of, for example, 1 to 50 ⁇ m can be used.
• the resin film and prepreg to be combined with the metal foil may be one sheet or a plurality of sheets, and depending on the application, the metal foil is laminated on one side or both sides and processed into a laminate.
• a metal-clad laminate is particularly suitable as a printed wiring board.
• the printed wiring board of the present invention is obtained by partially removing the metal foil on the surface of the metal-clad laminate by etching or the like, forming wiring, and forming a circuit on the surface of the resin film or prepreg. can get.
• the printed wiring board is excellent in dielectric properties such as dielectric constant and dielectric loss tangent, moldability, and heat resistance.
• thermosetting composition is used for applications such as molding, lamination, adhesives, and composite materials such as copper-clad laminates.
• applications such as molding, lamination, adhesives, and composite materials such as copper-clad laminates.
• prepregs obtained by semi-curing resins and laminates obtained by curing these prepregs are typically used.
• an epoxy body a typical example of its use is for a semiconductor encapsulant.
• the structure of the above dialkyl peroxide was identified by 1 H-NMR measurement, 13 C-NMR measurement and TOFMS (manufactured by JEOL Ltd.) using an AVANCEN NMR spectrometer (manufactured by BRUCKER). Purity was calculated by a simple area method in GC (GC-2014 series manufactured by Shimadzu Corporation).
• the dielectric constant and dielectric loss tangent at 1 GHz of the obtained cured product were measured by a method based on IPC-TM-650-2.5.5.9 and evaluated according to the following criteria.
• x Dielectric constant (Dk) and dielectric loss tangent (Df) are other than the above ⁇ or ⁇ .
• the glass transition temperature of the above cured product was measured by the DSC measurement method based on IPC-TM-650-2.4.25 at a heating rate of 10° C./min and evaluated according to the following criteria.
• OPE-2St 2200 is a polyphenylene ether having an average of two ethylenically unsaturated double bonds at the molecular ends (number average molecular weight of 2200), manufactured by Mitsubishi Gas Chemical Company);
• OPE-2St 1200 is a polyphenylene ether having an average of two ethylenically unsaturated double bonds at the molecular ends (number average molecular weight of 1200), manufactured by Mitsubishi Gas Chemical Company, Inc.);
• SA9000 is a polyphenylene ether having an average of 2 ethylenically unsaturated double bonds at the molecular end (number average molecular weight of 2756), manufactured by SABIC Innovative Plastics); 1,1,3,3-Tetramethylbutylcumyl peroxide is produced in Production Example 1 (purity 90.8%); t-hexylyl peroxide is produced in Production Example 2 (purity 94.3%); t-Amilyl peroxide (Production Example 3, purity 89.
• t-butyl cumyl peroxide is manufactured by NOF Corporation (purity 90.2%); 1,1,3,3-tetramethylbutyl hydroperoxide is manufactured by NOF Corporation (purity 90.3%); t-hexyl hydroperoxide is manufactured by NOF Corporation (purity 85.2%); t-amyl hydroperoxide was from United Initiators (84.8% purity); t-butyl hydroperoxide is manufactured by NOF Corporation (purity 68.9%); 1,4-hydroquinone is manufactured by Tokyo Chemical Industry Co., Ltd. (purity 99.9%); TAIC (Triallyl Isocyanurate) is manufactured by Tokyo Chemical Industry Co., Ltd. (96.0% purity); 1,4-divinylbenzene is manufactured by Tokyo Chemical Industry Co., Ltd. (98.0% purity).
• thermosetting composition in Examples 1 to 10, the fluidity of the thermosetting composition could be maintained, and a cured polyphenylene ether exhibiting excellent physical properties could be obtained.
• thermosetting composition lost its fluidity.

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