Classifications

• • 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
  • C08F12/00—Homopolymers and 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
  • C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
• • 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
  • C08F16/00—Homopolymers and 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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F16/12—Homopolymers and 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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
  • C08F16/32—Monomers containing two or more unsaturated aliphatic radicals
• • 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
  • C08K5/13—Phenols; Phenolates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

• the present invention relates to a compound that gives a cured product with excellent heat resistance and dielectric properties, a resin composition, a cured product of the resin composition, and an electric/electronic part that contains the cured product.
• Curable resins which are used as materials for electrical and electronic components such as laminates for electrical and electronic circuits, are required to have a wide range of properties.
• One of the most important properties is low dielectric properties.
• communication frequencies have been increasing in frequency to improve the amount and speed of information transmission, and the increase in transmission loss ( ⁇ ) has become a major issue.
• ⁇ As a method for suppressing the transmission loss ( ⁇ ), a method of reducing the dielectric loss tangent (tan ⁇ ), which is proportional to ⁇ like frequency (f), can be mentioned.
• materials with low dielectric loss tangent (tan ⁇ ) i.e., materials with low dielectric properties, are required, and low dielectric properties at high frequencies are particularly important.
• Patent Document 1 proposes a modified bismaleimide resin using a cinnamyl ether group-containing compound and a bismaleimide resin.
• Patent Document 2 proposes a cinnamyl ether group-containing curable resin composition that has excellent heat resistance and low dielectric properties.
• the cured product using the curable resin composition containing the compound described in Patent Document 1 and Patent Document 2 is a curable resin composition that has excellent physical heat resistance, represented by the glass transition temperature (Tg), and low dielectric properties at 1 GHz, but it was found to be insufficient in terms of chemical heat resistance, represented by thermal decomposition resistance, and low dielectric properties in a higher frequency environment (10 GHz).
• Tg glass transition temperature
• the material when the curable resin composition is cured on an industrial scale and applied to electric or electronic parts, the material may be dissolved in a solvent to adjust the viscosity and used as a varnish, and therefore the material needs to have excellent solvent solubility.
• the present invention has been made in view of the above problems, and an object of the present invention is to provide a compound, a resin composition, a cured product using the same, and an electric/electronic part including a cured product made of the resin composition, which have excellent heat resistance and low dielectric properties and are industrially advantageous.
• X1 and X2 are each independently a group selected from the group consisting of a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, -O-, -S-, -SO2- , -C( CF3 ) 2- and -CO-.
• R1 and R2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
• R3 to R18 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.
• n and m are each independently an integer of 0 to 50, except for compounds represented by the following formulae (2) and (3).
• R 19 and R 20 each independently represent a hydrogen atom, an alkyl group having 3 carbon atoms, or an alkenyl group.
• a resin composition comprising the compound according to [1] and a curable resin having a structure different from that of the compound represented by formula (1).
• the resin composition according to [2], wherein the curable resin having a structure different from that of the compound represented by formula (1) contains a radical polymerizable resin.
• R 3 to R 6 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.
• the present invention it is possible to obtain a compound, a resin composition, a cured product of the resin composition, and an electric/electronic part containing the cured product, which give a cured product having excellent heat resistance and low dielectric properties.
• the compound of the present invention since the compound of the present invention has excellent solvent solubility, it is possible to obtain an industrially advantageous resin composition.
• the resin composition of the present invention is applicable to various fields such as adhesives, paints, civil engineering building materials, various composite materials including carbon fiber reinforced plastics (CFRP), and insulating materials for electric/electronic parts, and is particularly useful as insulating casting, lamination materials, sealing materials, etc. in the electric/electronic field.
• CFRP carbon fiber reinforced plastics
• the resin composition of the present invention can also be suitably used in multilayer printed wiring boards, laminates for electric and electronic circuits such as capacitors, adhesives such as film adhesives and liquid adhesives, semiconductor encapsulation materials, underfill materials, interchip fills for 3D-LSI, insulating sheets, prepregs, heat dissipation substrates, etc.
• X 1 and X 2 are each independently a group selected from the group consisting of a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, -O-, -S-, -SO 2 -, -C(CF 3 ) 2 -, and -CO-.
• R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
• R 3 to R 18 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.
• n and m are each independently an integer of 0 to 50. However, this does not include compounds represented by the following formulas (2) and (3).
• the compound according to this embodiment has excellent solvent solubility, and a resin composition containing the compound and a cured product using the same have the effect of having heat resistance, low dielectric properties, and low thermal expansion properties.
• the reason for this is presumably that the presence of a rigid aromatic ether skeleton (cinnamyl ether) suppresses molecular motion, resulting in excellent heat resistance, low dielectric properties, and low thermal expansion properties, and that the introduction of appropriate substituents on the aromatic ring or between aromatic groups results in excellent solvent solubility.
• X 1 and X 2 each independently represent a group selected from the group consisting of a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, -O-, -S-, -SO 2 -, -C(CF 3 ) 2 -, and -CO-.
• divalent hydrocarbon groups having 1 to 13 carbon atoms include linear aliphatic hydrocarbon groups such as methylene, 1,1-ethylene, isopropylidene, 1,2-ethylene, 1,3-propylene, and 1,4-butylene groups, cyclic aliphatic hydrocarbon groups such as 1,1-cyclopropylene, 1,1-cyclobutylene, 1,1-cyclopentylene, 1,1-cyclohexylene, 3,3,5-trimethyl-1,1-cyclohexylene, 1,1-cyclododecylene, 1,2-cyclopropylene, 1,2-cyclobutylene, 1,2-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,3-cyclohexylene, and 1,4-cyclohexylene groups, -CHPh-, -C(CH 3 )Ph-, and -CPh 2
• aromatic hydrocarbon groups include 1,2-phenylene, 1,3-
• X1 and X2 are preferably -O- or a divalent hydrocarbon group having 1 to 13 carbon atoms.
• the divalent hydrocarbon group having 1 to 13 carbon atoms preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a methylene group, a 1,1-ethylene group, an isopropylidene group, -CHPh-, -C(CH 3 )Ph-, -CPh 2 -, a 9,9-fluorenylene group, a 1,1-cyclohexylene group, a 3,3,5-trimethyl-1,1-cyclohexylene group, and a 1,1-cyclododecylene group.
• X1 is particularly preferably --O--, a methylene group or an isopropylidene group, and most preferably --O--.
• X2 is particularly preferably -O-, a methylene group, or an isopropylidene group, and most preferably a methylene group or an isopropylidene group.
• the plurality of X1 may be the same or different.
• R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
• alkyl groups include the following: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, cycloheptyl, methylcyclohexyl, n-octyl, cyclooctyl, n-nonyl, 3,3,5-trimethylcyclohexyl, n-decyl, cyclodecyl, n-undecyl, n-dodecyl, cyclododecyl, benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, naphthylmethyl, pheny
• alkoxy groups include the following: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy, tert-pentoxy, cyclopentoxy, n-hexyloxy, isohexyloxy, cyclohexyloxy, n-heptoxy, cycloheptoxy, methylcyclohexyloxy, n-octyloxy, methylcyclohex ...
• cyclohexyloxy examples include cyclohexyloxy, cyclooctyloxy, n-nonyloxy, 3,3,5-trimethylcyclohexyloxy, n-decyloxy, cyclodecyloxy, n-undecyloxy, n-dodecyloxy, cyclododecyloxy, benzyloxy, methylbenzyloxy, dimethylbenzyloxy, trimethylbenzyloxy, naphthylmethoxy, phenethyloxy, and 2-phenylisopropoxy groups.
• Aryl groups include the following: For example, phenyl, o-tolyl, m-tolyl, p-tolyl, ethylphenyl, styryl, xylyl, n-propylphenyl, isopropylphenyl, mesityl, ethynylphenyl, naphthyl, vinylnaphthyl, etc.
• R 1 and R 2 are preferably each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• R 3 to R 18 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.
• alkyl groups include the following: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, cycloheptyl, methylcyclohexyl, n-octyl, cyclooctyl, n-nonyl, 3,3,5-trimethylcyclohexyl, n-decyl, cyclodecyl, n-undecyl, n-dodecyl, cyclododecyl, benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, naphthylmethyl, pheny
• alkoxy groups include the following: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy, tert-pentoxy, cyclopentoxy, n-hexyloxy, isohexyloxy, cyclohexyloxy, n-heptoxy, cycloheptoxy, methylcyclohexyloxy, n-octyloxy, methylcyclohex ...
• cyclohexyloxy examples include cyclohexyloxy, cyclooctyloxy, n-nonyloxy, 3,3,5-trimethylcyclohexyloxy, n-decyloxy, cyclodecyloxy, n-undecyloxy, n-dodecyloxy, cyclododecyloxy, benzyloxy, methylbenzyloxy, dimethylbenzyloxy, trimethylbenzyloxy, naphthylmethoxy, phenethyloxy, and 2-phenylisopropoxy groups.
• Aryl groups include the following: phenyl, o-tolyl, m-tolyl, p-tolyl, ethylphenyl, styryl, xylyl, n-propylphenyl, isopropylphenyl, mesityl, ethynylphenyl, naphthyl, vinylnaphthyl, etc.
• Alkenyl groups include the following: vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, cyclohexenyl group, cyclohexadienyl group, cinnamyl group, naphthylvinyl group, etc.
• Alkynyl groups include the following: ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1,3-butadienyl, phenylethynyl, naphthylethynyl, etc.
• n and m each independently represent an integer between 0 and 50, but from the viewpoint of heat resistance when cured, they are preferably between 0 and 30, and more preferably between 0 and 10.
• the compound represented by formula (1) is preferably a compound represented by formula (4) below, from the viewpoints of its small molecular weight, high crosslink density when cured, and excellent heat resistance and low dielectric properties.
• X 2 is a group selected from the group consisting of a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, -O-, -S-, -SO 2 -, -C(CF 3 ) 2 - and -CO-.
• R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
• R 3 to R 6 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. However, this does not include the compound represented by formula (2).
• R 3 to R 6 are preferably each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, more preferably each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and even more preferably each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. From the viewpoints of excellent solvent solubility and low dielectric properties when formed into a cured product, an alkyl group having 1 to 6 carbon atoms is most preferred.
• the compound represented by the following formula (1) used in the resin composition according to this embodiment can be produced by using a halogenated cinnamyl compound and an arbitrary phenol compound as raw materials and reacting them in the presence of a basic catalyst.
• X1 and X2 are each independently a group selected from the group consisting of a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, -O-, -S-, -SO2- , -C( CF3 ) 2- and -CO-.
• R1 and R2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
• R3 to R18 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.
• n and m are each independently an integer of 0 to 50, except for the compounds represented by formulas (2) and (3).
• the phenol compound used as the raw material in this reaction is not particularly limited as long as it is a compound having multiple phenol skeletons, but is preferably one represented by the following formula (5).
• X 1 , X 2 , R 3 to R 18 , n and m have the same meanings as those in the above formula (1). The same also applies to the preferred values of X 1 , X 2 , R 3 to R 18 , n and m.
• the halogenated cinnamyl compound is preferably used in an amount of 1.0 to 4.0 times, and particularly 1.0 to 3.0 times, per mole of hydroxyl groups in the raw phenol compound, from the viewpoint of efficiently proceeding with the reaction while keeping production costs down.
• cinnamyl chloride or cinnamyl bromide is usually used as the halogenated cinnamyl compound.
• the reaction is preferably carried out in the presence of a basic catalyst.
• basic catalysts include alkali metal hydroxides and alkali metal salts such as sodium hydroxide, potassium hydroxide, and potassium carbonate, amines such as diazabicyclononene, diazabicycloundecene, triethylamine, sodium tert-butoxide, potassium tert-butoxide, lithium diisopropylamide, silicon-basic amines, and lithium tetramethylpiperidine.
• alkali metals, diazabicycloundecene, and potassium tert-butoxide are preferred because they are relatively inexpensive and less likely to cause side reactions, and sodium hydroxide, potassium hydroxide, and potassium carbonate are particularly preferred.
• the catalysts may be used alone or in combination of two or more types. These basic catalysts may also be added dropwise as a water or alcohol solution.
• the amount of basic catalyst used is preferably 0.7 to 2.0 times the molar amount of hydroxyl groups in the raw phenol compound, and more preferably 0.8 to 1.5 times the molar amount. If too little catalyst is used, the reaction rate will be slow, and if too much is used, the excess alkali will have to be removed, resulting in reduced productivity.
• polar solvents such as the following:
• polar solvents examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, methanol, ethanol, butanol, ethyl acetate, butyl acetate, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and tetrahydrofuran.
• acetone and N,N-dimethylformamide are preferred because they are relatively inexpensive and have good reactivity.
• the solvent one type may be used alone, or two or more types may be used in combination.
• low polarity solvents such as toluene and xylene may be used in combination.
• the reaction may also be carried out in the presence of water.
• phase transfer catalyst When the reaction is carried out in a non-water-soluble solvent in the presence of water, a phase transfer catalyst can also be used.
• quaternary ammonium salts such as bromides, chlorides, iodides, hydrogen sulfates, and hydroxides of tetramethylammonium, trimethylethylammonium, dimethyldiethylammonium, triethylmethylammonium, tripropylmethylammonium, tributylmethylammonium, trioctylmethylammonium, tetraethylammonium, trimethylpropylammonium, trimethylphenylammonium, benzyltrimethylammonium, benzyltriethylammonium, diallyldimethylammonium, n-octyltrimethylammonium, stearyltrimethylammonium, cetyldimethylethylammonium, tetrapropylammonium, t
• a basic catalyst such as potassium carbonate is added.
• the halogenated cinnamyl compound is added over 0.5 to 10 hours, and the reaction is allowed to proceed for 1 to 20 hours.
• the reaction temperature at this time is not particularly limited as long as it is a temperature at which the hydroxyl group of the raw material phenol compound reacts with the halogenated cinnamyl compound, but 10 to 150°C is preferred, and 40 to 130°C is more preferred.
• inorganic components are removed by a method such as washing with water, and unreacted raw materials are removed by distillation or the like, followed by concentration and purification (recrystallization, reprecipitation, washing, column chromatography, etc.) to obtain the compound of this embodiment.
• concentration and purification concentration and purification
• the compound according to the present embodiment preferably contains a curable resin having a structure different from that of the compound (1) to form a resin composition.
• the curable resin having a structure different from that of the compound (1) is not particularly limited, but specifically includes epoxy resin, phenol resin, amine resin, acid anhydride resin, active ester resin, cyanate ester resin, isocyanate resin, benzoxazine resin, radical polymerizable resin, etc. From the balance of dielectric properties, heat resistance, and other physical properties, it is preferable to contain an epoxy resin, a cyanate ester resin, or a radical polymerizable resin, and a radical polymerizable resin is more preferable.
• the curable resin having a structure different from that of the compound (1) may be used alone or in combination of two or more kinds.
• the curable resin having a structure different from that of compound (1) is preferably contained in an amount of 1 to 1000 parts by weight, more preferably 5 to 800 parts by weight, and even more preferably 10 to 500 parts by weight, per 100 parts by weight of compound (1). If the content is equal to or greater than the lower limit, a cured product having excellent heat resistance and dielectric properties can be obtained. If the content of the curing component is equal to or less than the upper limit, a uniform cured product having excellent curing properties can be produced.
• epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane dimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, etc.
• the epoxy resin may contain a polymeric epoxy resin or a phenoxy resin. These may be used alone or in combination of two or more.
• phenolic resin examples include various polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, resorcin, methylresorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolac resins, cresol novolac resins, phenol aralkyl resins, biphenyl aralkyl resins, naphthol aralkyl resins, terpene phenol resins, dicyclopentadiene phenol resins, bisphenol A novolac resins, trisphenol methane type resins, naphthol novolac resins, brominated bisphenol A, and brominated phenol novolac resins.
• polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, resorcin, methylresorcin, bi
• phenol resin examples include polyhydric phenol resins obtained by the condensation reaction of various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, and glyoxal, polyhydric phenol resins obtained by the condensation reaction of xylene resin and phenols, co-condensation resins of heavy oils or pitches with phenols and formaldehydes, various phenol resins such as phenol-benzaldehyde-xylylene dimethoxide polycondensates, phenol-benzaldehyde-xylylene dihalide polycondensates, phenol-benzaldehyde-4,4'-dimethoxide biphenyl polycondensates, and phenol-benzaldehyde-4,4'-dihalide biphenyl polycondensates. These may be used alone or in combination of two or more.
• aldehydes such as benzaldehyde
• amine resin examples include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines.
• Aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra(hydroxyethyl)ethylenediamine, etc.
• polyetheramines examples include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylene diamine, polyoxypropylene triamine, etc.
• Alicyclic amines include isophorone diamine, methacenediamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, and norbornene diamine.
• Aromatic amines include tetrachloro-p-xylylenediamine, m-xylylenediamine, p-xylylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, triethanolamine, methylbenzylamine, ⁇ -(m-aminophenyl)ethylamine,
• the amine-based resins listed above may be used alone or in combination of two or more.
• acid anhydride resins include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dodecenylsuccinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyloctadecanedioic) anhydride, poly(phenylhexadecanedioic) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhimic anhydride, and trialkyltetrahydrophthalic anhydride.
• amine resins examples include water, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, ethylene glycol bistrimellitate dianhydride, HET anhydride, Nadic anhydride, methylnadic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, etc.
• the amine resins listed above may be used alone or in combination of two or more.
• the active ester resin is not particularly limited, but generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferably used.
• the active ester resin is preferably one obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound.
• an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred.
• Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
• Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type di
• active ester resins containing a dicyclopentadiene-type diphenol structure active ester resins containing a naphthalene structure, active ester resins containing an acetylated product of phenol novolac, and active ester resins containing a benzoylated product of phenol novolac are preferred, and among these, active ester resins containing a naphthalene structure and active ester resins containing a dicyclopentadiene-type diphenol structure are more preferred.
• dicyclopentadiene-type diphenol structure refers to a divalent structural unit consisting of phenylene-dicyclopentalene-phenylene.
• One type of active ester resin may be used alone, or two or more types may be used in combination.
• cyanate ester resin examples include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl)thioether, and bis(4-cyanate phenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which
• the isocyanate resin may be a resin having one or more isocyanate groups in the molecule.
• the isocyanate resin preferably has two or more isocyanate groups in the molecule.
• Examples of the isocyanate resin include 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolylene diisocyanate, and hexamethylene diisocyanate.
• the isocyanate resin may be used alone or in combination of two or more.
• benzoxazine resins examples include 6,6-(1-methylethylidene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6-(1-methylethylidene)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine), and the like.
• the benzoxazine resin may contain a structure in which the oxazine ring is ring-opened and polymerized.
• the benzoxazine resin may be used alone or in combination of two or more kinds.
• radical polymerizable resin component a compound that can be polymerized by radicals generated by heat or light, that is, a compound having a radical polymerizable substituent, can be used.
• radical polymerizable substituent include a group having an ethylenic double bond that exhibits curability by irradiation with active energy rays.
• Such a radical polymerizable substituent is preferably at least one selected from the group consisting of a maleimide group, an acryloyl group, a methacryloyl group, a styryl group, an allyl group, a vinyl group, a propenyl group, and a butadiene group, and more preferably at least one selected from the group consisting of a maleimide group, an acryloyl group, a methacryloyl group, a styryl group, an allyl group, and a butadiene group.
• the radical polymerizable resin preferably has one or more radical polymerizable substituents, more preferably has two or more radical polymerizable substituents. There is no particular limit to the upper limit, but it can be 10 or less, etc.
• the compound having a radically polymerizable substituent preferably contains at least one selected from a radically polymerizable compound containing a maleimide group (maleimide-based radically polymerizable compound), a radically polymerizable compound containing a (meth)acryloyl group ((meth)acrylic-based radically polymerizable compound), a radically polymerizable compound containing a styryl group (styryl-based radically polymerizable compound), a radically polymerizable compound containing an allyl group (allyl-based radically polymerizable compound), and a radically polymerizable compound containing a butadiene skeleton (butadiene-based radically polymerizable compound), more preferably contains at least one of a maleimide-based radically polymerizable compound, a (meth)acrylic-based radically polymerizable compound, a styryl-based radically polymerizable compound, and an allyl-
• the maleimide radical polymerizable compound is a compound having at least one maleimide group in the molecule.
• the maleimide radical polymerizable compound preferably has one or more maleimide groups per molecule, more preferably has two or more maleimide groups.
• the lower limit is not particularly limited, but is preferably 10 or less, more preferably 5 or less.
• maleimide radical polymerizable compound examples include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, and 1,6-bismaleimide(2,2,4-trimethyl)hexane.
• Polyphenylmethanemaleimide is a polymer in which three or more benzene rings substituted with maleimide groups are bonded via methylene groups.
• the maleimide radical polymerizable compound is preferably 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, or 1,6-bismaleimide(2,2,4-trimethyl)hexane, more preferably polyphenylmethane maleimide or 1,6-bismaleimide(2,2,4-trimethyl)hexane.
• maleimide radical polymerizable compounds may be used.
• Commercially available maleimide radical polymerizable compounds include, for example, "BMI-1100” (4,4'-diphenylmethane bismaleimide) and “BMI-2300” (polyphenylmethane maleimide) manufactured by Yamato Chemical Industry Co., Ltd., "BMI-TMH” (1,6-bismaleimide(2,2,4-trimethyl)hexane) represented by the following formula (6), “BMI-689” manufactured by Designer Molecules, represented by the following formula (7), and " Examples of the compounds include “BMI-1500", "BMI-1700” represented by the following formula (9), “BMI-3000” and “BMI-5000” represented by the following formula (10), “BMI-6100” represented by the following formula (11), “MIR-3000” manufactured by Nippon Kayaku Co., Ltd. represented by the following formula (12), “MIR-5000” represented by the following formula (13), "BMI-70” manufactured by
• a1 is an integer from 1 to 10.
• a2 is an integer from 1 to 10.
• a3 is an integer from 1 to 10.
• a4 and a5 are each independently an integer from 10 to 35.
• a6 is an integer from 1 to 10.
• the (meth)acrylic radical polymerizable compound is a compound containing an acryloyl group and a methacryloyl group.
• the (meth)acrylic radical polymerizable compound preferably has one acryloyl group and one methacryloyl group per molecule, and more preferably has two or more acryloyl groups and two or more methacryloyl groups per molecule.
• the lower limit is not particularly limited, but is preferably 10 or less, more preferably 5 or less.
• (meth)acrylic radical polymerizable compounds may be used, and examples thereof include “SA9000” manufactured by SABIC, "A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd., “DCP-A” manufactured by Kyoeisha Chemical Co., Ltd., “NPDGA”, “FM-400”, “R-687”, “THE-330”, “PET-30”, and “DPHA” manufactured by Nippon Kayaku Co., Ltd., and "NK Ester DCP” manufactured by Shin-Nakamura Chemical Co., Ltd., which are represented by the following formula (16).
• a7 and a8 are each independently an integer from 0 to 300.
• the styryl radical polymerizable compound is a compound having at least one styryl group represented by the following formula (17) in the molecule.
• the styryl radical polymerizable compound preferably has one or more styryl groups per molecule, more preferably has two or more styryl groups.
• the lower limit is not particularly limited, but is preferably 10 or less, more preferably 5 or less.
• the styryl radical polymerizable compound is not particularly limited, but examples include polycondensates of the above-mentioned phenolic resin and chloromethylstyrene.
• styryl radical polymerizable compound a commercially available product may be used, for example, "OPE-2St” manufactured by Mitsubishi Gas Chemical Company, Inc., which is represented by the following formula (18).
• the styryl radical polymerizable compound may be used alone or in combination of two or more types.
• a9 and a10 each independently represent an integer from 0 to 300.
• the allyl radical polymerizable compound is a compound having at least one allyl group in the molecule.
• the allyl radical polymerizable compound preferably has one or more allyl groups per molecule, more preferably has two or more allyl groups.
• the lower limit is not particularly limited, but is preferably 10 or less, more preferably 5 or less.
• allyl radical polymerizable compound one or more resins selected from the group consisting of phenolic hydroxyl group-containing allyl radical polymerizable compounds, carboxyl group-containing allyl radical polymerizable compounds, epoxy group-containing allyl radical polymerizable compounds, benzoxazine ring-containing allyl radical polymerizable compounds, isocyanuric ring-containing allyl radical polymerizable compounds, and ester group-containing allyl radical polymerizable compounds are more preferred.
• Allyl radical polymerizable compounds may be commercially available products, such as "MEH-8000H” and "MEH-8005" manufactured by Meiwa Kasei Co., Ltd., "DABPA” (phenolic hydroxyl group-containing allyl radical polymerizable compound) manufactured by Daiwa Kasei Co., Ltd., "RE-810NM” (epoxy group-containing allyl radical polymerizable compound) manufactured by Nippon Kayaku Co., Ltd., "ALP-d” (benzoxazine ring-containing allyl radical polymerizable compound) manufactured by Shikoku Kasei Corporation, “L-DAIC” manufactured by Shikoku Kasei Corporation, “TAIC” (isocyanuric ring-containing allyl radical polymerizable compound) manufactured by Nissan Chemical Industries, Ltd., “MDAC” manufactured by Osaka Soda Co., Ltd., “DAD” manufactured by Nisshoku Techno Fine Chemical Co., Ltd., and "Daiso DAP Mono
• the butadiene radical polymerizable compound is a compound having at least one butadiene skeleton in the molecule.
• the butadiene structure may be included in the main chain or in the side chain.
• the butadiene structure may be partially or entirely hydrogenated.
• the butadiene radical polymerizable compound one or more resins selected from the group consisting of hydrogenated polybutadiene skeleton-containing resin, hydroxyl group-containing butadiene resin, phenolic hydroxyl group-containing butadiene resin, carboxyl group-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, isocyanate group-containing butadiene resin, and urethane group-containing butadiene resin are more preferable.
• butadiene-based radical polymerizable compounds include “JP-100” manufactured by Nippon Soda Co., Ltd., and "Ricon100”, “Ricon150”, “Ricon130MA8”, “Ricon130MA13”, “Ricon130MA20”, “Ricon131MA5", “Ricon131MA10”, “Ricon131M A17”, “Ricon131MA20”, and “Ricon184MA6” manufactured by Cray Valley.
• the resin composition according to the present embodiment may contain an elastomer.
• the elastomer include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, and silicone-based elastomers.
• These elastomers are composed of a hard segment component and a soft segment component, and generally, the hard segment component contributes to heat resistance and strength, and the soft segment component contributes to flexibility and toughness.
• the elastomer may be used alone or in combination of two or more types.
• a styrene-based elastomer is preferred, and a styrene-based thermoplastic elastomer is more preferred.
• the styrene-based elastomer it is sufficient if it has a structural unit derived from a styrene-based compound, and from the viewpoints of dielectric loss tangent (Df), adhesion to a conductor, heat resistance, and low thermal expansion, one or more types selected from the group consisting of hydrogenated styrene-butadiene-styrene block copolymers (SEBS, SBBS), hydrogenated styrene-isoprene-styrene block copolymers (SEPS), and styrene-maleic anhydride copolymers (SMA) are preferred, one or more types selected from the group consisting of hydrogenated styrene-butadiene-styrene block copolymers (SEBS) and hydrogenated styrene-isoprene-styrene block copolymers (SEPS) are more preferred, and hydrogenated styrene-buta
• the resin composition according to the present embodiment preferably contains a curing accelerator.
• a curing accelerator By containing the curing accelerator, it is possible to shorten the curing time and lower the curing temperature, and it is possible to easily obtain a desired cured product. From the same viewpoint, it is preferable that the compound according to the present embodiment contains a curing accelerator to form a resin composition.
• curing accelerator there are no particular limitations on the curing accelerator, but specific examples include radical polymerization initiators, imidazole compounds, phosphines, phosphorus compounds such as phosphonium salts, amines, amine compounds such as ammonium salts, transition metal compounds, etc.
• radical polymerization initiators include cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, di-tert-amyl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, and 2,3-dimethyl-2,3-diphenylbutane.
• imidazole compounds include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methyl-imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-phenylimidazole.
• phosphorus compounds include phosphines such as triphenylphosphine, and quaternary phosphonium salts such as triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, and tetrabutylphosphonium salts.
• phosphines such as triphenylphosphine
• quaternary phosphonium salts such as triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, and tetrabutylphosphonium salts.
• amine compounds include tertiary amines such as 2-(dimethylaminomethyl)phenol and 1,8-diaza-bicyclo(5,4,0)undecene-7, and quaternary ammonium salts such as triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, and hexadecyltrimethylammonium hydroxide.
• tertiary amines such as 2-(dimethylaminomethyl)phenol and 1,8-diaza-bicyclo(5,4,0)undecene-7
• quaternary ammonium salts such as triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, and hexadecyltrimethylammonium hydroxide.
• transition metal compounds include zinc compounds (transition metal salts) such as tin octoate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristylates), and zinc phosphates (zinc octylphosphate, zinc stearylphosphate, etc.).
• transition metal salts such as tin octoate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristylates), and zinc phosphates (zinc octylphosphate, zinc stearylphosphate, etc.).
• radical polymerization initiators imidazole compounds, and phosphorus compounds are preferred, and radical polymerization initiators are most preferred.
• the curing accelerator may be used alone or in any combination and ratio of two or more of the above.
• the curing accelerator is preferably used in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the resin composition. More preferably, it is 0.05 parts by weight or more, and even more preferably, it is 0.1 parts by weight or more, while it is more preferably 5 parts by weight or less, and even more preferably, it is 3 parts by weight or less.
• the content of the curing accelerator is equal to or more than the lower limit, a good curing acceleration effect can be obtained, while when the content is equal to or less than the upper limit, it is preferable because the desired curing properties are easily obtained.
• the resin composition according to the present embodiment may be diluted with any solvent in order to adjust the viscosity appropriately.
• the solvent is used to ensure the handling and workability in molding the epoxy resin composition, and there is no particular limit to the amount used.
• solvent used to ensure the handling and workability in molding the epoxy resin composition, and there is no particular limit to the amount used.
• solvent and the above-mentioned term “solvent” are used separately depending on the form of use, but the same or different types of solvents may be used independently.
• Solvents include, for example, ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, etc., esters such as ethyl acetate, ethers such as ethylene glycol monomethyl ether, amides such as N,N-dimethylformamide, N,N-dimethylacetamide, etc., alcohols such as methanol, ethanol, etc., alkanes such as hexane, cyclohexane, etc., aromatics such as toluene, xylene, anisole, etc.
• the above-mentioned solvents may be used alone or in any combination and ratio of two or more.
• the resin composition according to the present embodiment may contain components other than those listed above (sometimes referred to as "other components" in the present invention) for the purpose of further improving its functionality.
• other components include ultraviolet protection agents, antioxidants, coupling agents, plasticizers, fluxes, flame retardants, colorants, dispersants, emulsifiers, elasticity reducing agents, diluents, antifoaming agents, ion trapping agents, inorganic fillers, and organic fillers.
• the cured product obtained by curing the resin composition according to this embodiment has an excellent balance between heat resistance and low dielectric properties, and exhibits good cured physical properties.
• the term "curing” used here means intentionally curing the resin composition with heat and/or light, and the degree of curing may be controlled according to the desired physical properties and applications. The degree of progress may be complete curing or semi-curing.
• the method for curing the resin composition according to this embodiment varies depending on the components and amounts in the resin composition, but typically involves heating at 80 to 280°C for 1 to 360 minutes. This heating is preferably performed in two stages, with a primary heating at 80 to 180°C for 1 to 90 minutes and a secondary heating at 120 to 220°C for 60 to 300 minutes. Performing secondary heating in this manner is preferable from the viewpoint of reducing poor curing and residual solvent.
• the resin composition contains a solvent, most of the solvent is usually removed by methods such as heating, reducing pressure, and air drying, but up to 5 parts by weight of the solvent may remain in the semi-cured resin product.
• the resin composition according to the present embodiment has the effect of providing a cured product excellent in heat resistance and low dielectric properties. For this reason, it is applicable to various fields such as adhesives, paints, civil engineering and construction materials, and insulating materials for electrical and electronic parts, and is particularly useful as insulating casting, lamination materials, sealing materials, etc. in the electrical and electronic fields.
• Examples of applications of the resin composition of the present invention include multilayer printed wiring boards, laminates for electrical and electronic circuits such as capacitors, adhesives such as film adhesives and liquid adhesives, semiconductor sealing materials, underfill materials, interchip fills for 3D-LSI, insulating sheets, prepregs, heat dissipation substrates, etc., but are not limited thereto. Among these, it is particularly useful for electrical and electronic parts.
• the resin composition according to this embodiment can be suitably used for the application of laminates for electric and electronic circuits.
• the laminate for electric and electronic circuits using the resin composition according to this embodiment is a laminate in which a layer containing the resin composition of the present invention and a conductive metal layer are laminated, and as long as a layer containing the resin composition of the present invention and a conductive metal layer are laminated, it is used as a concept including, for example, a capacitor, even if it is not an electric or electronic circuit.
• layers made of two or more resin compositions may be formed in the laminate for electric and electronic circuits, and it is sufficient that the resin composition of the present invention is used in at least one layer.
• two or more conductive metal layers may be formed.
• the thickness of the layer made of the resin composition in the laminate for electric and electronic circuits is usually about 10 to 200 ⁇ m.
• the thickness of the conductive metal layer is usually about 0.2 to 70 ⁇ m.
• conductive metals in the laminate for electric/electronic circuits include metals such as copper and aluminum, and alloys containing these metals.
• metal foils of these metals, or metal layers formed by plating or sputtering can be used.
• a nonwoven fabric or cloth made of inorganic and/or organic fiber materials such as glass fiber, polyester fiber, aramid fiber, cellulose, nanofiber cellulose, etc. is impregnated with the resin composition of the present invention to form a prepreg, and a conductive metal layer is provided by conductive metal foil and/or plating, after which a circuit is formed using a photoresist or the like, and the required number of such layers are stacked to form a laminate.
• the prepreg of (1) above is used as a core material, and a layer of a resin composition and a conductive metal layer are laminated on one or both sides of the core material (build-up method).
• the layer of the resin composition may contain organic and/or inorganic fillers.
• No core material is used, and only layers of a resin composition and conductive metal layers are alternately laminated to form a laminate for electric/electronic circuits.
• Example 1 A 500 mL four-neck flask equipped with a thermometer, a stirrer, and a cooling tube was charged with 35.0 g of tetramethylbisphenol F (Deepak), 34.0 g of potassium carbonate, and 100 g of N,N-dimethylformamide, and the reaction temperature was raised to 125 ° C., and then 50.0 g of cinnamyl chloride was added over 3 hours, and the reaction was carried out for 1 hour. After cooling to 80 ° C., 58.1 g of toluene was added, and the mixture was washed four times with 100 g of water.
• Deepak tetramethylbisphenol F
• Example 2 A 500 mL four-neck flask equipped with a thermometer, a stirrer, and a cooling tube was charged with 30.0 g of bisphenol C (manufactured by Honshu Chemical Co., Ltd.), 29.1 g of potassium carbonate, and 85.4 g of N,N-dimethylformamide, and the reaction temperature was raised to 125° C., after which 42.9 g of cinnamyl chloride was added over 3 hours and reacted for 1 hour. After cooling to 80° C., 49.8 g of toluene was added, and the mixture was washed four times with 100 g of water.
• Example 3 A 500 mL four-neck flask equipped with a thermometer, a stirrer, and a cooling tube was charged with 25.0 g of tetramethylbisphenol A (manufactured by Tokyo Chemical Industry Co., Ltd.), 22.2 g of potassium carbonate, and 71.2 g of N,N-dimethylformamide, and the reaction temperature was raised to 125 ° C., and then 32.7 g of cinnamyl chloride was added over 3 hours, and the reaction was carried out for 1 hour. After cooling to 80 ° C., 40.1 g of toluene was added, and the mixture was washed four times with 100 g of water.
• Example 4 A 500 mL four-neck flask equipped with a thermometer, a stirrer, and a cooling tube was charged with 36.0 g of tetramethylbiphenol (manufactured by Mitsubishi Chemical Corporation), 37.0 g of potassium carbonate, and 205 g of N,N-dimethylformamide, and the reaction temperature was raised to 125° C., after which 49.9 g of cinnamyl chloride was added over 3 hours and reacted for 1 hour. After cooling to 80° C., 100 g of water was added, and the precipitated solid was separated by filtration. The obtained crystals were washed three times with 100 g of water and dried to obtain 65.3 g (yield 93%) of a compound represented by the following formula (22) (hereinafter referred to as "compound (1-4)").
• compound (1-4) a compound represented by the following formula (22)
• Example 5 A 1000 mL four-neck flask equipped with a thermometer, a stirrer, and a cooling tube was charged with polyphenylene ether (manufactured by SABIC, trade name "SA90") represented by the following formula (23), a thermometer, a stirrer, 8.1 g of sodium hydroxide aqueous solution (48.5 wt%), 100 g of toluene, and 1.0 g of tetrabutylammonium bromide, and the reaction temperature was raised to 80 ° C., and then 10.9 g of cinnamyl chloride was added over 3 hours, and the reaction was carried out for 3 hours. It was washed four times with 100 g of water.
• SA90 polyphenylene ether
• Example 6 A 500 mL four-neck flask equipped with a thermometer, a stirrer, and a cooling tube was charged with 53.4 g of xylene-modified phenol novolak resin (manufactured by Fudow Co., Ltd., product name "HP-100") represented by the following formula (25), 22.0 g of sodium hydroxide aqueous solution (48.5 wt%), 40.1 g of toluene, and 5.5 g of tetrabutylammonium bromide, and the reaction temperature was raised to 80 ° C., and then 40.7 g of cinnamyl chloride was added over 3 hours and reacted for 3 hours.
• Examples 7 to 15, Comparative Examples 3 and 4 The compounds produced in Examples 1 to 5 or Comparative Examples 1 and 2, 1,6-bismaleimide-(2,2,4-trimethyl)hexane (manufactured by Daiwa Kasei Co., Ltd., product name "BMI-TMH") as a maleimide resin, phenylmethane type maleimide (manufactured by Daiwa Kasei Co., Ltd., product name "BMI-2300”), and di-tert-amyl peroxide (DTAP), dicumyl peroxide (DCP), and 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., product name "2E4MZ”) as a curing accelerator were mixed as shown in Table 2 to obtain a resin composition.
• BMI-TMH 1,6-bismaleimide-(2,2,4-trimethyl)hexane
• BMI-2300 phenylmethane type maleimi
• the obtained resin composition was heated at 180°C for 2 hours and then at 220°C for 2 hours to obtain a cured product.
• the resulting cured product was subjected to measurements of Tg (tan ⁇ ), dielectric constant, dielectric tangent and 5% weight loss temperature by the methods described below. The results are shown in Table 2.
• Tg (tan ⁇ )> The cured product was cut into a length of 5 cm, width of 1 cm, and thickness of 4 mm, and the obtained test piece was measured in a three-point bending mode using a dynamic viscoelasticity measuring device (DMA: Hitachi High-Tech Science Corporation DMA7100) (frequency: 1 GHz, heating rate: 5°C/min, measurement temperature range: 30°C to 300°C).
• DMA Dynamic Viscoelasticity measuring device
• Examples 16 and 17, Comparative Example 5 The compound produced in Example 6, or a methacrylic radical polymerizable compound (manufactured by SABIC, trade name "SA9000"), a phenylmethane type maleimide (manufactured by Daiwa Kasei, trade name "BMI-2300") as a maleimide resin, or 1,6-bismaleimide-(2,2,4-trimethyl)hexane (manufactured by Daiwa Kasei, trade name "BMI-TMH”) as a curing accelerator, and dicumyl peroxide (DCP) were added to toluene and mixed in the blending ratios shown in Table 3 so that the solid content concentration was 50% by weight, to obtain a varnish-like resin composition.
• SA9000 methacrylic radical polymerizable compound
• BMI-2300 phenylmethane type maleimide
• BMI-TMH 1,6-bismaleimide-(2,2,4-trimethyl)hexan
• the obtained resin composition was applied to a separator (polyethylene terephthalate film treated with silicone) using an applicator to form a coating film, and heated at 120°C for 1 hour and then at 200°C for 2 hours to obtain a film-like cured product.
• the Tg (DSC) of the resulting cured product was measured by the method described below, and the results are shown in Table 3.
• Tg (DSC)> The glass transition temperature was measured by heating from 30 to 280°C at 10°C/min using a differential scanning calorimeter "DSC7020" manufactured by SII Nano Technology Co., Ltd. The glass transition temperature was measured based on the "midpoint glass transition temperature: Tmg" described in JIS K7121 "Method for measuring transition temperature of plastics.” The higher the Tg (DSC) value, the more excellent the physical heat resistance.
• Example 18 Comparative Example 6
• a resin composition was obtained by mixing the compound produced in Example 1, 1,6-bismaleimide-(2,2,4-trimethyl)hexane (manufactured by Daiwa Kasei Co., Ltd., product name "BMI-TMH”) as a maleimide-based radical polymerizable compound, and 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., product name "2E4MZ”) as a curing accelerator as shown in Table 4.
• the resulting resin composition was heated at 120°C for 2 hours and then at 200°C for 6 hours to obtain a cured product.
• Tg (tan ⁇ ) was measured by the method described above, and the linear expansion coefficient was measured by the method described below. The results are shown in Table 4.
• thermomechanical analyzer Hitachi High-Tech Science Corporation, TMA7100
• measurement load 30 mN
• heating rate 5°C/min twice
• measurement temperature range 30°C to 300°C
• the linear expansion coefficient in the temperature range of 50°C to 250°C was calculated. The lower this value, the better the low thermal expansion property was evaluated.

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