CN117597371A - Novel polymer, resin composition containing the same, and molded article thereof - Google Patents

Novel polymer, resin composition containing the same, and molded article thereof Download PDF

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Publication number
CN117597371A
CN117597371A CN202280047695.1A CN202280047695A CN117597371A CN 117597371 A CN117597371 A CN 117597371A CN 202280047695 A CN202280047695 A CN 202280047695A CN 117597371 A CN117597371 A CN 117597371A
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group
formula
resin composition
meth
resin
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山手太轨
河西拓也
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Nippon Soda Co Ltd
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Nippon Soda Co Ltd
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Priority claimed from PCT/JP2022/027125 external-priority patent/WO2023286713A1/en
Publication of CN117597371A publication Critical patent/CN117597371A/en
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Abstract

The present invention addresses the problem of providing a polymer which has excellent heat resistance and dielectric characteristics and can be dissolved in an organic solvent at a high concentration, a resin composition comprising the polymer, and a molded article thereof. The polymer of the present invention has a structure represented by the following formula (I) (wherein X 1 、X 2 Each independently represents a C3-C6 branched alkyl group, a C3-C6 cyclic alkyl group, a C3-C6 branched alkoxy group, or a C3-C6 cyclic alkoxy group, n represents 0 or 1, Z 1 、Z 2 Each independently represents a single bond or a C1-C3 alkylene group, each R independently represents an organic group or a halogenated group, each of m1 and m2 independently represents an integer of 0 to 4, and Y represents a polymerizable functional group. ) A repeating unit of the polymerizable compound represented.

Description

Novel polymer, resin composition containing the same, and molded article thereof
Technical Field
The present invention relates to a polymer which has excellent heat resistance and dielectric characteristics and can be dissolved in an organic solvent at a high concentration, a resin composition containing the polymer, and a molded article thereof.
The present application claims priority from japanese patent application nos. 2021-116330, which are filed on 7/14/2021, and from japanese patent application nos. 2022-90373, which are filed on 6/2022, the contents of which are incorporated herein.
Background
Various known resins are used for manufacturing mobile communication devices such as mobile phones and smartphones, base station devices thereof, network-related electronic devices such as servers and routers, printed wiring boards included in mainframe computers, and the like.
In recent years, in the network-related electronic devices, it has been demanded to transmit and process information of a large capacity at a low loss and high speed, and electric signals handled by printed wiring boards of these products have also been increased in frequency. High-frequency electric signals are easily attenuated, and thus transmission loss in a printed wiring board needs to be made lower. Therefore, the resin used in manufacturing the printed wiring board is required to have a low dielectric constant and a low dielectric loss tangent.
In addition, the following resins are required for use in manufacturing printed wiring boards: high heat resistance (high glass transition temperature), and is dissolved in a high concentration in a usual organic solvent for varnish such as Methyl Ethyl Ketone (MEK), toluene, and cyclohexanone.
For example, patent document 1 discloses a polyarylate resin.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2017-149940
Disclosure of Invention
Problems to be solved by the invention
However, since dielectric characteristics and heat resistance are physical properties in inverse proportion to solubility in an organic solvent, it is very difficult to achieve the above physical properties at the same time.
The purpose of the present invention is to provide a polymer which has a low dielectric constant and a low dielectric loss tangent and has a high glass transition temperature, and which exhibits high solubility in an organic solvent and high compatibility with a thermosetting resin, a resin composition comprising the polymer, and a molded article thereof.
Means for solving the problems
As a result of intensive studies, the inventors of the present application have found that the above problems can be solved by using a novel polymer such as a predetermined polyacrylamide.
That is, the present invention relates to the following inventions.
(1) A polymer having at least 1 of repeating units derived from a polymerizable compound represented by formula (I).
[ chemical formula 1]
(wherein X is 1 、X 2 Each independently represents a C3-C6 branched alkyl group, a C3-C6 cyclic alkyl group, a C3-C6 branched alkoxy group or a C3-C6 cyclic alkoxy group, n represents 0 or 1, Z 1 、Z 2 Each independently represents a single bond or a C1-C3 alkylene group, each R independently represents an organic group or a halogenated group, each of m1 and m2 independently represents an integer of 0 to 4, and Y represents a polymerizable functional group. )
(2) The polymer according to (1), wherein Y is an acryl or methacryl group.
(3) A resin composition comprising the polymer of (1).
(4) The resin composition according to (3), which further comprises a resin other than the polymer according to (1).
(5) The resin composition according to (4), wherein the resin other than the polymer according to (1) is a thermosetting resin.
(6) The resin composition according to (5), wherein the thermosetting resin is an epoxy resin.
(7) The resin composition according to (6), further comprising an active ester compound as a curing agent.
(8) The resin composition according to (5), wherein the thermosetting resin is at least 1 or more selected from the following components:
maleimide compounds having more than one maleimide group,
a polyphenylene ether compound which comprises a polyphenylene ether compound,
polybutadiene with a molar ratio of 1,2 bond structure to 1,4 bond structure of 80:20-100:0,
styrene-butadiene-styrene block copolymer (SBS) having a molar ratio of 1,2 bond structure to 1,4 bond structure in the butadiene block of 80:20 to 100:0, and
a polymer having a repeating unit represented by the formula (V) in the molecule.
[ chemical formula 2]
(in the formula (V), Z 3 Represents a C6-C12 arylene group, R 2 ～R 7 Each independently represents a hydrogen atom or a C1-C6 alkyl group. )
(9) The resin composition according to (8), wherein the polyphenylene ether compound is a polyphenylene ether compound obtained by terminal-modifying a group represented by the formula (VI), an acryl group or a methacryl group.
[ chemical formula 3]
(in the formula (VI): represents a bonding position, p represents an integer of 0 to 10, Z 4 Represents a C6-C12 arylene group, R 8 ～R 10 Each independently represents a hydrogen atom or a C1-C6 alkyl group. )
(10) A molded article obtained by using the cured product of the resin composition according to any one of (3) to (9).
(11) The resin composition according to any one of (3) to (9), which is a resin composition for an insulating layer of a printed wiring board.
(12) A resin varnish comprising the resin composition according to any one of (3) to (9).
(13) A prepreg obtained by impregnating a substrate with the resin composition according to any one of (3) to (9).
(14) An adhesive film comprising a support film and a resin composition layer comprising the resin composition according to any one of (3) to (9) on the support film.
(15) An insulator for a printed wiring board, which is formed from the cured product of the prepreg according to (13).
(16) An insulator for a printed wiring board, which is formed of the cured product of the adhesive film according to (14).
(17) A laminate with a metal foil, comprising a layer formed of the insulator for a printed wiring board described in (15) and a layer formed of a metal foil.
(18) A laminate with a metal foil, comprising a layer formed of the insulator for a printed wiring board described in (16) and a layer formed of a metal foil.
(19) A compound represented by the formula (III).
[ chemical formula 4]
(wherein X is 1 、X 2 Each independently represents a C3-C6 branched alkyl group, a C3-C6 cyclic alkyl group, a C3-C6 branched alkoxy group or a C3-C6 cyclic alkoxy group, n represents 0 or 1, Z 1 、Z 2 Each independently represents a single bond or a C1-C3 alkylene group, each R independently represents an organic group or a halogenated group, each of m1 and m2 independently represents an integer of 0 to 4, and Y represents a polymerizable functional group. )
(20) The compound according to (19), wherein the compound represented by the formula (III) is a compound represented by the formula (IV).
[ chemical formula 5]
(wherein R is 1 Represents a hydrogen atom or a methyl group)
Effects of the invention
The novel polymer of the present invention has a low dielectric constant and a low dielectric loss tangent, and has a high glass transition temperature and shows high solubility in an organic solvent.
Detailed Description
1. A polymer having a repeating unit derived from a polymerizable compound represented by the formula (I)
The polymer of the present invention has a repeating unit derived from a polymerizable compound represented by formula (I).
[ chemical formula 6]
In the formula (I) of the present invention,
X 1 、X 2 each independently represents a C3-C6 branched alkyl group, a C3-C6 cyclic alkyl group, a C3-C6 branched alkoxy group, or a C3-C6 cyclic alkoxy group.
As X 1 X is X 2 Examples of the "C3-C6 branched alkyl" in (a) include isopropyl, sec-butyl, isobutyl, tert-butyl, neopentyl, isopentyl, sec-pentyl, 1-ethylpropyl, tert-pentyl, isohexyl, 3-methylpentyl, 2-dimethylbutyl, and 2, 3-dimethylbutyl.
As X 1 X is X 2 Examples of the "C3-C6 cyclic alkyl" in (a) include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
As X 1 X is X 2 Examples of the "C3-C6 branched alkoxy" in (a) include isopropyl oxy, sec-butyl oxy, isobutyl oxy, tert-butyl oxy, neopentyl oxy, isopentyl oxy, sec-amyl oxy, 1-ethylpropyl oxy, tert-amyl oxy, isohexyl oxy, 3-methylpentyl oxy, 2-dimethylbutyl oxy, 2, 3-dimethylbutyl oxy and the like.
As X 1 X is X 2 Examples of the "C3-C6 cyclic alkoxy" in (a) include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy and the like.
X 1 X is X 2 Preferably a C3-C6 branched alkyl group, more preferably a tert-butyl group.
In the formula (I), n represents 0 or 1.
n is preferably 1.
In the formula (I), Z 1 、Z 2 Each independently represents a single bond or a C1-C3 alkylene group.
As Z 1 、Z 2 Examples of the C1-C3 alkylene group include methylene, ethylene, propane-1, 3-diyl and the like.
Z 1 Z is as follows 2 Preferably a single bond.
In the formula (I), each R independently represents an organic group or a halogenated group.
The "organic group" is not particularly limited as long as it is chemically allowed and has the effect of the present invention. Examples of the organic group include C1-6 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, and n-hexyl, C6-10 aryl groups such as phenyl and naphthyl, C1-6 alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, and tert-butoxy, and C1-6 haloalkyl groups such as chloromethyl, chloroethyl, trifluoromethyl, 1, 2-dichloro-n-propyl, 1-fluoro-n-butyl, and perfluoro-n-pentyl.
Examples of the "halo" include fluoro, chloro, bromo and iodo.
In the formula (I), m1 and m2 each independently represent any integer from 0 to 4.
m1 and m2 are preferably 0.
In formula (I), Y represents a polymerizable functional group. Examples of the polymerizable functional group include a polymerizable group having a carbon-carbon double bond such as a vinyl group, an allyl group, an acryl group, a methacryl group, a vinyloxycarbonyl group, a prop-1-en-2-yloxycarbonyl group, and an allyloxycarbonyl group.
In the present invention, Y is preferably an acryl group or a methacryl group, and more preferably an acryl group.
The formula (I) includes a compound represented by the following formula (II).
[ chemical formula 7]
Y, Z in the formula (II) 1 、Z 2 、X 1 R, m1, m2 are the same as described in formula (I).
In the formula (II), X 3 Represents a C3-C6 branched alkyl group, a C3-C6 cyclic alkyl group, a C3-C6 branched alkoxy group, a C3-C6 cyclic alkoxy group, a hydrogen atom, an organic group or a halogen group, preferably a C3-C6 branched alkyl group, a C3-C6 cyclic alkyl group or a C3-C6 branched alkoxy group, more preferably a C3-C6 branched alkyl group, particularly preferably a C3-C6 branched alkyl groupAnd selecting tertiary butyl. X is X 3 Examples of the C3-C6 branched alkyl group, C3-C6 cyclic alkyl group, C3-C6 branched alkoxy group and C3-C6 cyclic alkoxy group in (B) include the same groups as the C3-C6 branched alkyl group, C3-C6 cyclic alkyl group, C3-C6 branched alkoxy group and C3-C6 cyclic alkoxy group in X1 and X2 in the formula (I).
Among the compounds represented by the above formula (II), the compound represented by the formula (IV) is particularly preferable.
[ chemical formula 8]
(in the formula (IV), R 1 Represents a hydrogen atom or a methyl group)
R 1 Preferably a hydrogen atom.
The polymer having a repeating unit derived from a polymerizable compound represented by the following formula (I) used in the present invention is a polymer formed from at least 1 of repeating units derived from a polymerizable compound represented by the following formula (I), or a polymer formed from at least 1 of repeating units and at least 1 of repeating units derived from another radical polymerizable compound.
[ chemical formula 9]
(in the formula (I), each symbol is as described above.)
Specifically, the polymer used in the present invention includes the following polymers.
I) A homopolymer formed of 1 of the repeating units derived from the polymerizable compound represented by the formula (I),
II) a copolymer comprising 2 or more kinds of repeating units derived from a polymerizable compound represented by the formula (I),
III) copolymers formed from at least 1 of the repeating units derived from the polymerizable compound represented by formula (I) and at least 1 of the repeating units derived from other radical polymerizable compounds, and
IV) a copolymer formed from at least 2 or more of repeating units derived from a polymerizable compound represented by formula (I) and at least 1 of repeating units derived from another radically polymerizable compound.
The polymer having a repeating unit derived from the polymerizable compound represented by the formula (I) is preferably I) a homopolymer formed from 1 of the repeating units derived from the polymerizable compound represented by the formula (I), or III) a copolymer formed from at least 1 of the repeating units derived from the polymerizable compound represented by the formula (I) and at least 1 of the repeating units derived from other radical polymerizable compounds, more preferably I) a homopolymer formed from 1 of the repeating units derived from the polymerizable compound represented by the formula (I).
Among the above polymers, the copolymers of II) to IV) may be any of a copolymer in which the respective repeating units are randomly arranged, a copolymer in which the repeating units are alternately arranged, and a copolymer in which the repeating units are arranged in blocks.
In the case of the copolymer of the present invention, the molecular chain may be a straight chain or a branched chain. Examples of the branched chain include a branched chain branched at one point (star type), a branched chain branched at a plurality of points (graft type), and the like.
The weight average molecular weight of the polymer of the present invention is not limited, and examples thereof include copolymers having weight average molecular weights in the range of 1,000 ～ 5,000,000, 5,000 ～ 1,000,000, 10,000 ～ 500,000, 10,000 ～ 200,000, 20,000 ～ 100,000, and the like.
The molecular weight distribution (PDI) of the polymer according to the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and most preferably 1.0 to 3.0 in terms of the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn).
The weight average molecular weight and the number average molecular weight are values obtained by converting data measured by Gel Permeation Chromatography (GPC) using THF as a solvent based on the molecular weight of polymethyl methacrylate used as a standard.
(other radical polymerizable Compound)
The "other radically polymerizable compound" is not particularly limited as long as it is a radically polymerizable compound other than the compound represented by the formula (I) and is appropriately selected in accordance with the physical properties aimed at such as the melting point, viscosity, refractive index, etc., and includes (meth) acrylic acid, (meth) acrylonitrile, styrenes, vinyl compounds, olefin compounds, unsaturated carboxylic acid anhydrides, etc., and 1 or 2 or more of them may be used. Specifically, the same compounds as those exemplified for the radical polymerizable compound of the component (1) can be exemplified.
In the present invention, "(meth) propylene-" means "propylene-" and/or "meth-propylene-".
In particular, the "other radical polymerizable compound" is preferably (meth) acrylic acid such as (meth) acrylic acid ester, (meth) acrylamide, unsaturated dicarboxylic acid anhydride or styrene.
Examples of the (meth) acrylate include alkyl (meth) acrylate, acrylate having an alicyclic hydrocarbon group, (meth) acrylate having an ether skeleton, (meth) acrylate having a cyclic ether skeleton, and (meth) acrylate having an aromatic group.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isononyl (meth) acrylate.
Examples of the (meth) acrylate having an alicyclic hydrocarbon group include cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and methoxylated cyclodextrene (meth) acrylate.
Examples of the (meth) acrylate having an ether skeleton include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and diethylene glycol monomethyl ether (meth) acrylate.
Examples of the (meth) acrylic acid ester having a cyclic ether skeleton include glycidyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 3-ethyl-3-oxetanyl (meth) acrylate, 2-methyl-ethyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, γ -butyrolactone (meth) acrylate, dioxolan (meth) acrylate, oxetane (meth) acrylate, and (meth) acryloylmorpholine.
Examples of the (meth) acrylic acid ester having an aromatic group include phenyl (meth) acrylate, benzyl (meth) acrylate, methylbenzyl (meth) acrylate, ethylbenzyl (meth) acrylate, propylbenzyl (meth) acrylate, methoxybenzyl (meth) acrylate, phenoxyethyl (meth) acrylate, chlorobenzyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, and the like.
Examples of the (meth) acrylamide include methyl (meth) acrylamide, dimethyl (meth) acrylamide, ethyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, diethyl (meth) acrylamide, n-propyl (meth) acrylamide, dipropyl (meth) acrylamide, diisopropyl (meth) acrylamide, isopropyl acrylamide, and n-butyl (meth) acrylamide.
Examples of the unsaturated dicarboxylic anhydride include maleic anhydride, citraconic anhydride, and itaconic anhydride.
Examples of the styrenes include styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, p-t-butoxystyrene, and p-t-butoxycarbonyl styrene.
Examples of the other compounds include vinyl compounds such as vinyl acetate, vinyl chloride, vinylidene chloride, (meth) acrylonitrile, vinyl ether, acrolein, and divinylbenzene; olefin compounds such as ethylene, propylene, butadiene, and the like.
(composition ratio of repeating units)
The content of the repeating unit derived from the polymerizable compound represented by the formula (I) and the repeating unit derived from the other radical-polymerizable anisotropic compound in the polymer used in the present invention is not particularly limited as long as the effect of the present invention is exhibited. The weight ratio of the repeating unit derived from the polymerizable compound represented by the formula (I) to the repeating unit derived from the other radical polymerizable specific compound may be selected from the range of 99.5:0.5 to 0.5:99.5, 99.5:0.5 to 30:70, 99:1 to 30:70, 90:10 to 30:70, 60:40 to 30:70, etc.
(preparation of Compound of formula (I))
The compound represented by the formula (I) as a polymerizable compound used in the present invention can be synthesized by the method of examples or other known methods.
For example, when Y in the formula (I) is an acrylic group or a methacrylic group, the compound can be produced by the following method.
[ chemical formula 10]
(wherein X is 1 、X 2 、n、Z 1 、Z 2 R, m1, m2 are as defined for formula (I). )
The secondary amine represented by the formula (I') is reacted with (meth) acryloyl halide such as (meth) acryloyl chloride in the presence of a base in a solvent.
Examples of the solvent include amide solvents such as N, N-Dimethylformamide (DMF) and N, N-dimethylacetamide, ether solvents such as Tetrahydrofuran (THF), 1, 2-dimethoxyethane, diethyl ether and methylcellosolve, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene and benzonitrile, saturated hydrocarbons such as pentane, hexane, octane and cyclohexane, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and 1, 2-dichloroethane, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate and 2-methoxy-1-methylethyl acetate, and a mixed solvent of 1 or 2 or more of them may be used.
Examples of the base include aliphatic amines such as triethylamine and tributylamine, aromatic amines such as pyridine, N-ethylpyridine, N-dimethylaniline and N, N-dimethylaminopyridine, organic bases such as metal alkoxides such as sodium ethoxide and sodium methoxide, and inorganic bases such as alkali metal or alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate and sodium hydrogencarbonate, and alkali metal or alkaline earth metal carbonates.
The reaction temperature is-50 ℃ to 200 ℃.
(polymerization method of Polymer)
The polymer used in the present invention is not particularly limited as long as it is a polymer obtained by polymerizing at least 1 of the polymerizable compounds represented by the formula (I) or polymerizing the compound with another polymerizable compound. The polymerization reaction is not particularly limited, and may be a known method for synthesizing a polyacrylate or the like, and examples thereof include radical polymerization, anionic polymerization, cationic polymerization, ring-opening polymerization, coordination polymerization, and the like. An example of which is shown in the embodiments.
For example, in the case of radical polymerization of a compound in which Y of the formula (I) is an acrylic group or a methacrylic group with a (meth) acrylate, the polymerizable compound represented by the formula (I) and the (meth) acrylate are heated or irradiated with light in the presence of a radical polymerization initiator in a solvent to perform polymerization reaction.
The polymerization solvent is not particularly limited as long as it does not participate in the polymerization reaction and is compatible with the polymer, and specifically, ether compounds such as diethyl ether, tetrahydrofuran (THF), dioxane, trioxane, and the like, ester compounds such as ethyl acetate, ketone compounds such as methyl ethyl ketone, cyclohexanone, and the like, and nonpolar solvents or low-polarity solvents such as aliphatic, aromatic, or alicyclic hydrocarbon compounds such as hexane, toluene, and the like may be exemplified. These solvents may be used alone or in the form of a mixed solvent of 2 or more.
Examples of the radical polymerization initiator include azobisisobutyronitrile, azobis-2, 4-dimethylvaleronitrile, azobishexane carbonitrile, azobis-2-amidinopropane hydrochloride, potassium persulfate, ammonium persulfate, t-butyl hydroperoxide, di-t-butyl hydroperoxide, cumene hydroperoxide, acetyl peroxide, benzoyl peroxide, lauroyl peroxide and the like.
2. Resin composition
The resin composition of the present invention contains the polymer (hereinafter, also referred to as "component (a)") formed of at least 1 of the repeating units derived from the polymerizable compound represented by the formula (I).
The resin composition of the present invention may further contain a curable resin such as an ionizing radiation curable resin or a thermosetting resin (hereinafter also referred to as "component (B)") and other components as components other than the component (a).
(1) Curable resin
As the curable resin, (meth) acrylic resin, vinyl resin, allyl resin, melamine resin, urethane resin, epoxy resin, silicone resin, polyester resin, polyamic acid resin, polyimide resin, styrene maleic acid resin, styrene maleic anhydride resin, maleimide resin, cyanate resin, and the like can be used. Here, the term "ionizing radiation curable resin" refers to a resin cured by irradiation with any one of ionizing radiation including all electromagnetic waves such as infrared rays, visible rays, ultraviolet rays, X-rays, and electron beams.
The ionizing radiation curable resin and the thermosetting resin are not particularly limited, and monomers, prepolymers, oligomers, polymers, and the like having a vinyl group, (meth) acryl group, an epoxy group, an oxetanyl group, and a maleimide group can be used. Among them, a polyfunctional resin is preferably used. In the present invention, "(meth) acryl" means "acryl" and/or "methacryl".
Hereinafter, examples of the thermosetting resin used as the resin composition of the present invention will be specifically described.
1) Epoxy resin (hereinafter, also referred to as "(B-1) component")
Examples of the epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol Novolac type epoxy resin, phenol Novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, t-butyl catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol Novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic type epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, and tetraphenyl ethane type epoxy resin. The epoxy resin may be used alone or in combination of 1 or more than 2.
The epoxy resin preferably contains an epoxy resin having 2 or more epoxy groups in 1 molecule. When the nonvolatile content of the epoxy resin is set to 100 mass%, it is preferable that at least 50 mass% or more is an epoxy resin having 2 or more epoxy groups in 1 molecule. Among them, it is preferable to include an epoxy resin having 2 or more epoxy groups in 1 molecule and being liquid at a temperature of 20 ℃ (hereinafter referred to as "liquid epoxy resin"), and an epoxy resin having 3 or more epoxy groups in 1 molecule and being solid at a temperature of 20 ℃ (hereinafter referred to as "solid epoxy resin"). By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, a resin composition having excellent flexibility can be obtained. In addition, the breaking strength of the cured product of the resin composition is also improved.
The liquid epoxy resin is preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a phenol Novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, or an epoxy resin having a butadiene structure, more preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, an alicyclic epoxy resin having an ester skeleton, or a naphthalene type epoxy resin, and even more preferably a bisphenol a type epoxy resin or a bisphenol AF type epoxy resin, and particularly preferably a bisphenol AF type epoxy resin, from the viewpoint of excellent balance of physical properties of a cured product.
The solid epoxy resin is preferably a naphthalene type 4-functional epoxy resin, a cresol Novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, or a tetraphenylethane type epoxy resin, more preferably a naphthalene type 4-functional epoxy resin, a naphthol type epoxy resin, or a biphenyl type epoxy resin, and particularly preferably a biphenyl type epoxy resin.
(curing agent)
When the above (B-1) is used as the thermosetting resin as the component (B), a curing agent may be contained.
The curing agent for the epoxy resin is not particularly limited, and examples thereof include phenol curing agents, naphthol curing agents, active ester curing agents, benzoxazine curing agents, cyanate curing agents, acid anhydride curing agents, and the like, and from the viewpoint of reducing the dielectric loss tangent, cyanate curing agents and active ester curing agents are preferable. They may be used in 1 kind or in combination of more than 2 kinds.
The phenol-based curing agent and the naphthol-based curing agent are not particularly limited, and examples thereof include phenol-based curing agents having a Novolac structure and naphthol-based curing agents having a Novolac structure, and phenol Novolac resins, triazine skeleton-containing phenol Novolac resins, naphthol aralkyl resins, triazine skeleton-containing naphthol resins, and biphenyl aralkyl type phenol resins are preferable.
The active ester-based curing agent is preferably a compound having 2 or more active ester groups in 1 molecule, and for example, a compound having 2 or more reactive ester groups in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds, is preferably used. The active ester compound may be used alone or in combination of 1 or more than 2.
From the viewpoint of improving heat resistance, an active ester compound obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound is preferable. Among them, an active ester compound obtained by reacting a carboxylic acid compound with 1 or more selected from a phenol compound, a naphthol compound and a thiol compound is more preferable, an aromatic compound having 2 or more active ester groups in 1 molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group is more preferable, and an aromatic compound having 2 or more active ester groups in 1 molecule obtained by reacting a carboxylic acid compound having at least 2 or more carboxyl groups in 1 molecule with an aromatic compound having a phenolic hydroxyl group is more preferable. The active ester compound may be linear or branched.
Examples of the carboxylic acid compound include aliphatic carboxylic acids having 1 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 8), and aromatic carboxylic acids having 7 to 20 carbon atoms (preferably 7 to 10). Examples of the aliphatic carboxylic acid include acetic acid, malonic acid, succinic acid, maleic acid, itaconic acid, and the like. Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable, and isophthalic acid and terephthalic acid are more preferable from the viewpoint of heat resistance.
The thiocarboxylic acid compound is not particularly limited, and examples thereof include thioacetic acid, thiobenzoic acid, and the like.
Examples of the phenol compound include phenol compounds having 6 to 40 carbon atoms (preferably 6 to 30 carbon atoms, more preferably 6 to 23 carbon atoms, still more preferably 6 to 22 carbon atoms), and specific examples thereof include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, dicyclopentadiene type diphenol, and the like. Further, as the phenol compound, a phosphorus atom-containing oligomer having a phenolic hydroxyl group as described in phenol Novolac and Japanese patent application laid-open No. 2013-40270 may also be used.
Examples of the naphthol compound include naphthol compounds having 10 to 40 carbon atoms (preferably 10 to 30 carbon atoms, more preferably 10 to 20 carbon atoms), and preferred specific examples include α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, and the like. Further, as the naphthol compound, naphthol Novolac may be used.
Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, alpha-naphthol, beta-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, bisphenols, phenol Novolac, phosphorus atom-containing oligomers having phenolic hydroxyl groups, more preferably catechol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, dicyclopentadiene type diphenol, phenol Novolac, phosphorus atom-containing oligomers having phenolic hydroxyl groups, further preferred are 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene type diphenol, phenol Novolac, and phosphorus atom-containing oligomers having a phenolic hydroxyl group, further preferred are 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dicyclopentadiene type diphenol, phenol Novolac, and phosphorus atom-containing oligomers having a phenolic hydroxyl group, and particularly preferred are 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dicyclopentadiene type diphenol, and phosphorus atom-containing oligomers having a phenolic hydroxyl group, and particularly preferred is dicyclopentadiene type diphenol.
The thiol compound is not particularly limited, and examples thereof include benzenedithiol and triazinedithiol.
Preferable examples of the active ester compound include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetyl compound of phenol novolacs, an active ester compound containing a benzoyl compound of phenol novolacs, and an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group, and among these, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, and an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable. In the present invention, the "dicyclopentadiene type diphenol structure" means a 2-valent structural unit formed of phenylene-dicyclopentylene-phenylene.
As the active ester compound, those disclosed in Japanese patent application laid-open No. 2004-277460 and Japanese patent application laid-open No. 2013-40270 may be used, and commercially available active ester compounds may be used. Examples of commercially available active ester compounds include EXB9451, EXB9460S, HPC-8000-65T (DIC), EXB9416-70BK (DIC), DC808 (Mitsubishi chemical Co., ltd.), YLH1026 (Mitsubishi chemical Co., ltd.), and EXB9050L-62M (DIC), which are active ester compounds containing a phosphorus atom.
The cyanate-based curing agent is not particularly limited, and examples thereof include a cyanate-based curing agent of a Novolac type (phenol Novolac type, alkylphenol Novolac type, etc.), a dicyclopentadiene-based cyanate-based curing agent, a bisphenol-based (bisphenol A type, bisphenol F type, bisphenol S type, etc.), a prepolymer obtained by triazinizing a part of these, and the like. The weight average molecular weight of the cyanate ester curing agent is not particularly limited, but is preferably 500 to 4500, more preferably 600 to 3000. Specific examples of the cyanate-based curing agent include 2-functional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1, 5-phenylene cyanate), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2-bis (4-cyanate) phenylpropane, 1-bis (4-cyanate-phenyl methane), bis (4-cyanate-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate-phenyl-1- (methylethylene)) benzene, bis (4-cyanate-phenyl) sulfide, bis (4-cyanate-phenyl) ether, polyfunctional cyanate resins derived from phenol Novolac, novolac, phenol resins containing dicyclopentadiene structures, prepolymers obtained by triazinizing a part of these cyanate resins, and the like, and 1 or 2 or more of these may be used in combination.
Examples of the acid anhydride-based curing agent include, but are not limited to, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5- (2, 5-dioxotetrahydro-3-furyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3'-4,4' -diphenylsulfone tetracarboxylic dianhydride, 1, 3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphtho [1,2-C ] furan-1, 3-dione, ethylene glycol bis (dehydrated trimellitate), and styrene maleic anhydride obtained by copolymerizing styrene and maleic acid.
(curing accelerator)
By further containing a curing accelerator, the epoxy resin and the curing agent can be efficiently cured. The curing accelerator is not particularly limited, and examples thereof include amine-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and phosphonium-based curing accelerators. They may be used in 1 kind or in combination of more than 2 kinds.
The amine-based curing accelerator is not particularly limited, and examples thereof include trialkylamines such as triethylamine and tributylamine, amine compounds such as 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1, 8-diazabicyclo (5, 4, 0) -undecene (hereinafter abbreviated to DBU). They may be used in 1 kind or in combination of more than 2 kinds.
The guanidine-based curing accelerator is not particularly limited, and examples thereof include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1- (o-tolyl) biguanide. They may be used in 1 kind or in combination of more than 2 kinds.
The imidazole-based curing accelerator is not particularly limited, examples thereof include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl s triazine, 2, 4-diamino-6- [2 '-undecylimidazolyl- (1') ] -ethyl s triazine, 2, 4-diamino-6- [2 '-ethyl-4' -methylimidazolyl- (1 ') ] -ethyl-triazine, and 2, 4-diamino-6- [2' -phenylimidazole ] -2 '-ethylimidazolyl-yl-3-yl ] -methyl triazine, and 2-ethyl-2' -diamino-6- [2 '-methylimidazole-methyl ] -methyl-3-yl ] -3-methyl-1' -d-1-ethyl-2-methyl-imidazolyl ] -3-d Imidazole compounds such as 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins. They may be used in 1 kind or in combination of more than 2 kinds.
The metal-based curing accelerator is not particularly limited, and examples thereof include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include cobalt (II) acetylacetonate, organic cobalt complexes such as cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. They may be used in 1 kind or in combination of more than 2 kinds.
Examples of the phosphonium based curing accelerator (phosphorus based curing accelerator) include, but are not particularly limited to, organic phosphines such as triphenylphosphine, diphenyl (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, and alkyldiarylphosphine;
Complexes of organic phosphines and organic boron compounds such as phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate and n-butylphosphonium tetraphenylborate; aromatic phosphonium salts such as (4-methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate and tetrabutyl phosphonium decanoate, and adducts of tertiary phosphines and quinones.
The tertiary phosphine is not particularly limited, and examples thereof include tri-n-butylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-methoxyphenyl) phosphine, and the like. Examples of the quinone include o-quinone, p-quinone, diphenoquinone, 1, 4-naphthoquinone, and anthraquinone. They may be used in 1 kind or in combination of more than 2 kinds.
The curing accelerator used in the resin composition of the present invention is preferably an amine-based curing accelerator.
2) Maleimide compounds having one or more maleimide groups (hereinafter also referred to as "(B-2) component")
The maleimide compound used in the present invention is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule. Specific examples thereof include N-phenylmaleimide, N-hydroxyphenyl maleimide, bis (4-maleimidophenoxy) phenyl ] propane, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, polytetramethyleneoxy-bis (4-maleimidobenzoate), 2-bis [4- (4-maleimidophenoxy) phenyl ] propane, maleimide compounds represented by the following formula (VII), maleimide compounds represented by the following formula (IX), prepolymers of these maleimide compounds, and prepolymers of maleimide compounds and amine compounds. They may be used singly or in combination of two or more kinds as appropriate.
[ chemical formula 11]
In the formula (VII) of the present invention,
R 11 r is R 12 Each independently represents a halo group, a C1-C6 alkyl group, a hydroxy group, a C1-C6 alkoxy group, a formyl group, a carboxy group, a C1-C6 alkoxycarbonyl group, a C6-C10 aryl group, an amino group, a C1-C6 alkyl-substituted amino group, a cyano group or a nitro group,
a1 and a2 each independently represent an integer of 0 to 4, and R is when a1 is 2 or more 11 Can be mutually in phase with each otherWhen a2 is 2 or more, R may be the same as or different from 12 May be the same as or different from each other,
m3 and m4 each independently represent an integer of 1 to 10,
R 13 r is R 14 Each independently is a C1-C6 alkyl group or a C6-C10 aryl group,
a3 represents an integer of 0 to 3, and R is when a3 is 2 or more 13 May be the same as or different from each other,
a4 represents an integer of 0 to 2, and R is when a4 is 2 14 And n1 represents an integer of 1 to 100, which may be the same or different from each other.
As R 11 R is R 12 Examples of the "halo" in (a) include fluoro, chloro, bromo, iodo and the like.
As R 11 R is R 12 The "C1-C6 alkyl" in (a) may be a straight chain or a branched chain. Examples of the C1-C6 alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, 2-methylbutyl, 2-dimethylpropyl, and isohexyl.
As R 11 R is R 12 Examples of the "C1-C6 alkoxy" in (a) include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and the like.
As R 11 R is R 12 Examples of the "C1-C6 alkoxycarbonyl group" in (a) include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group and the like.
As R 11 R is R 12 Examples of the "C6-C10 aryl" in (a) include phenyl, naphthyl and the like.
R 11 R is R 12 The "C1-C6 alkyl-substituted amino group" in (a) may be any of a monosubstituted or a disubstituted one. Examples of the "C1-C6 alkyl-substituted amino" include methylamino, dimethylamino, ethylamino, diethylamino, methylethylamino and the like.
a1 and a2 are preferably 0.
m3 and m4 are preferably 1 to 6, more preferably 1 to 3, still more preferably 1 to 2, particularly preferably 1.
As R 13 R is R 14 Examples of the C1-C6 alkyl group and C6-C10 aryl group in (C1-C10) include those described in R 11 R is R 12 The same groups as exemplified in (a) are the same groups.
a3 and a4 are preferably 0.
n1 is preferably 1 to 50, more preferably 1 to 20, and still more preferably 1 to 5.
The compound represented by the formula (VII) is specifically a compound represented by the formula (VIII).
[ chemical formula 12]
In the formula (VIII), n2 represents an integer of 1 to 100.
n2 is preferably 1 to 50, more preferably 1 to 20, and still more preferably 1 to 5.
[ chemical formula 13]
In the formula (IX), R 15 R is R 16 Each independently represents a hydrogen atom or a C1-C6 alkyl group, n3 represents an integer of 1 to 10, X 4 X is X 5 Each independently represents a C1-C6 alkyl group, S1 and S2 each independently represent any integer from 0 to 2, and X when S1 is 2 4 May be the same or different from each other, X when S2 is 2 5 May be the same as or different from each other.
As R 15 R is R 16 Examples of the "C1-C6 alkyl" in (1) include those mentioned above as R 11 R is R 12 The same groups as exemplified in (a) are the same groups.
R 15 R is R 16 Preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
n3 is preferably an integer of 1 to 7. More preferably an integer of 1 to 3, and still more preferably 1.
As X 4 X is X 5 Examples of the "C1-C6 alkyl" in (1) include those mentioned above as R 11 R is R 12 The same groups as exemplified in (a) are the same groups.
X 4 X is X 5 Preferably methyl or ethyl.
The compound represented by the formula (IX) is preferably 4,4' -diphenylmethane bismaleimide or bis (3-ethyl-5-methyl-4-maleimidophenyl) methane.
The maleimide compound used in the present invention is preferably a maleimide compound represented by the formula (VII) or a maleimide compound represented by the formula (IX), more preferably a compound represented by the formula (VIII) or a maleimide compound represented by the formula (IX).
As the maleimide compound, commercially available ones can be used. Examples of the commercial products include MIR-3000 (manufactured by Japanese chemical Co., ltd.), MIR-3000-70MT (manufactured by Japanese chemical Co., ltd.), BMI (K. I Chemical Industry Co., LTD.), BMI-70 (K. IChemical Industry Co., LTD.), and BMI-80 (K. I Chemical Industry Co., LTD.).
3) Polyphenylene ether Compound (hereinafter, also referred to as "(B-3) component")
The polyphenylene ether compound used in the present invention is not particularly limited as long as it is a polymer having a repeating unit represented by the following formula (X).
[ chemical formula 14]
In the formula (X), R 17 ～R 20 Each independently represents a hydrogen atom, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkylcarbonyl group or a C2-C6 alkenylcarbonyl group.
As R 17 ～R 20 Examples of the "C1-C6 alkyl" in (1) include those mentioned above as R 11 R is R 12 The same groups as exemplified in (a) are the same groups.
As R 17 ～R 20 In (a) and (b)Examples of the "C2-C6 alkenyl group" include vinyl groups and allyl groups.
As R 17 ～R 20 Examples of the "C2-C6 alkynyl" in (a) include ethynyl and 2-propynyl.
As R 17 ～R 20 Examples of the "C1-C6 alkylcarbonyl" in (a) include acetyl.
As R 17 ～R 20 Examples of the "C2-C6 alkenylcarbonyl" in (a) include acryl, methacryl and the like.
R 17 ～R 20 Preferably a hydrogen atom, a C1-C6 alkyl group or a C2-C6 alkenyl group, more preferably a hydrogen atom, a methyl group or an allyl group, and still more preferably a hydrogen atom or a methyl group.
The terminal of the polyphenylene ether compound used in the present invention may be modified. Examples of the polyphenylene ether compound having a terminal modified include a polyphenylene ether compound having a terminal modified with a hydroxyl group and a polyphenylene ether compound having a substituent having a carbon-carbon unsaturated double bond.
Examples of the substituent having a carbon-carbon unsaturated double bond include a group represented by formula (VI), an acryl group, and a methacryl group.
[ chemical formula 15]
In formula (VI), p represents an integer of 0 to 10, Z 4 Represents arylene, R 8 ～R 10 Each independently represents a hydrogen atom or a C1-C6 alkyl group.
As Z 4 Examples of the C6-C12 arylene group include phenylene groups.
As R 8 ～R 10 Examples of the C1-C6 alkyl group in (C1-C6) include those mentioned above as R 11 R is R 12 The same groups as exemplified in (a) are the same groups.
Specifically, the group represented by the formula (VI) may be represented by the formulas (VI-1) and (VI-2).
[ chemical formula 16]
In the formula (VI-1) and the formula (VI-2), the bonding position is represented.
The polyphenylene ether compound modified with a substituent having a carbon-carbon unsaturated double bond is specifically a compound represented by the formula (3) or (4).
[ chemical formula 17]
In the formula (3), X 6 X is X 7 Each independently represents a group represented by formula (VI), an acryl group or a methacryl group, and S3 and S4 each independently represent an integer of 0 to 20. X is X 6 X is X 7 The group represented by formula (VI) in (B) is as described above.
[ chemical formula 18]
In the formula (4), X 8 X is X 9 Each independently represents a group represented by formula (VI), an acryl group or a methacryl group, S5 and S6 each independently represents an integer of 0 to 20, Y 1 Represents a C1-C6 alkylene group. X is X 8 X is X 9 The group represented by formula (VI) in (B) is as described above. As Y 1 Examples of the "C1-C6 alkylene" in (a) include methylene, ethylene, methyl methylene, dimethyl methylene and the like.
The number average molecular weight (Mn) of the polyphenylene ether compound to be used is not particularly limited, and examples thereof include 1,000 to 7,000, 1,000 to 5,000, 1,000 to 3,000, and the like. The number average molecular weight (Mn) is a value obtained by converting data measured by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent based on the molecular weight of standard polystyrene.
The intrinsic viscosity of the polyphenylene ether compound used in the present invention may be, for example, 0.03 to 0.12dl/g, 0.04 to 0.11dl/g, 0.06 to 0.095dl/g, etc. The intrinsic viscosity is the intrinsic viscosity measured in methylene chloride at 25 ℃. More specifically, the measurement was carried out on a methylene chloride solution (liquid temperature: 25 ℃ C.) of 0.18g/45ml by means of a viscometer.
As the polyphenylene ether compound used in the present invention, known polyphenylene ether compounds and commercially available products can be used. Examples of the commercial products include SA90 (manufactured by SABIC), SA9000 (manufactured by SABIC), OPE-2st (manufactured by Mitsubishi Gas Chemical Company), and the like.
In the case of synthesis, the method described in WO2014/203511 and the like can be used for synthesis.
4) Polybutadiene (hereinafter, also referred to as "(B-4) component") having a molar ratio of 1,2 bond structure to 1,4 bond structure of 80:20 to 100:0
The polybutadiene used in the present invention is formed of only the 1,2 bond structure represented by the formula (1), or the 1,2 bond structure represented by the formula (1) and the 1,4 bond structure represented by the formula (2).
[ chemical formula 19]
The ratio of the 1,2 bond structure represented by the formula (1) and the 1,4 bond structure represented by the formula (2) contained in the polybutadiene is not particularly limited, and the molar ratio of the 1,2 bond structure represented by the formula (I) is preferably 80:20 to 100:0 in all the repeating units of the polybutadiene.
The molecular weight of the polybutadiene to be used is not particularly limited, and the weight average molecular weight (Mw) may be selected from the range of 500 to 10,000, 500 to 8,000, 500 to 6,000, 500 to 5,000. The weight average molecular weight (Mw) is a value obtained by converting data measured by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent based on the molecular weight of standard polystyrene.
The polybutadiene may be a polybutadiene having a modified main chain and terminal, or may be a polybutadiene having an unmodified main chain and terminal. Among them, polybutadiene whose main chain and terminal are not modified is preferably used from the viewpoint of obtaining a cured product having high insulation properties.
As the polybutadiene, commercially available ones can be used. As the commercially available polybutadiene, NISSO-PB B-1000 (manufactured by Nippon Caesada Co., ltd.), NISSO-PB B-2000 (manufactured by Nippon Caesada Co., ltd.), NISSO-PB B-3000 (manufactured by Nippon Caesada Co., ltd.), etc. may be mentioned. These polybutadienes may be used singly or in combination of 1 or more than 2.
5) Styrene-butadiene-styrene block copolymer (SBS) (hereinafter, also referred to as "(B-5) component") having a molar ratio of 1,2 bond structure to 1,4 bond structure in the butadiene block of 80:20 to 100:0
The styrene block in the styrene-butadiene-styrene block copolymer (SBS) used in the present invention is a block obtained by polymerizing styrene, and the butadiene block is a block obtained by polymerizing butadiene. The butadiene block is formed of only the 1,2 bond structure represented by formula (1), or of the 1,2 bond structure represented by formula (1) and the 1,4 bond structure represented by formula (2).
[ chemical formula 20]
The molar ratio of the 1,2 bond structure represented by the formula (1) to the 1,4 bond structure represented by the formula (2) contained in the styrene-butadiene-styrene block copolymer used in the present invention is 80:20 to 100:0.
The weight ratio of the styrene block to the butadiene block in the styrene-butadiene-styrene block copolymer is not particularly limited, and examples thereof include 10:90 to 80:20, 10:90 to 70:30, 10:90 to 60:40, 20:80 to 80:20, 30:70 to 80:20, and 40:60 to 80:20.
The weight average molecular weight (Mw) of the styrene-butadiene-styrene block copolymer is not particularly limited, and examples thereof include 2,000 ～ 100,000, 2,000 to 80,000, 2,000 to 60,000, and the like. The molecular weight distribution (Mw/Mn) of the styrene-butadiene-styrene block copolymer is not particularly limited, and examples thereof include 1.00 to 3.00, 1.00 to 2.00, and the like. The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) were measured by Gel Permeation Chromatography (GPC) using polystyrene as a standard substance. The measurement conditions are as follows: the mobile phase was THF (tetrahydrofuran), the flow rate of the mobile phase was 1 mL/min, the column temperature was 40 ℃, the sample injection amount was 40. Mu.L, and the sample concentration was 2 wt%.
The method for producing the styrene-butadiene-styrene block copolymer to be used is not particularly limited. For example, the composition can be produced by the methods described in JP-A-6-192502, JP-A-2000-514122, JP-A-2007-302901, WO2021/024679 and the like, and the methods based thereon.
6) Polymer having a repeating unit represented by the formula (V) in the molecule (hereinafter, also referred to as "(B-6) component")
The resin composition of the present invention may contain a polymer having a repeating unit represented by formula (V) in the molecule.
[ chemical formula 21]
In the formula (V), Z 3 Represents a C6-C12 arylene group, R 2 ～R 7 Each independently represents a hydrogen atom or a C1-C6 alkyl group.
As Z 3 Examples of the "C6-C12 arylene group" in (3) include those mentioned above as Z 4 The same groups as exemplified in (a) are the same groups.
As R 2 ～R 7 Examples of the "C1-C6 alkyl" in (1) include those mentioned above as R 11 R is R 12 The same groups as exemplified in (a) are the same groups.
Specifically, the formula (V) is represented by the formula (V-1).
[ chemical formula 22]
The polymer having the repeating unit represented by the formula (V) in the molecule may be a polymer further having the structural unit represented by the formula (5) in the molecule.
In addition, the resin composition may have a repeating unit other than the repeating unit represented by the formula (V) and the repeating unit represented by the formula (5).
That is, the polymer having a repeating unit represented by the formula (V) in the molecule of the component (B-6) includes the following polymers.
I) Polymers formed of 1 or more than 2 of the repeating units represented by formula (V)
II) a polymer formed of 1 or more than 2 of the repeating units represented by the formula (V) and 1 or more than 2 of the repeating units represented by the formula (5)
III) a polymer formed of 1 or more than 2 of the repeating units represented by the formula (V), 1 or more than 2 of the repeating units represented by the formula (5), and the other repeating units
Among these polymers, the copolymer may be a random copolymer or a block copolymer.
[ chemical formula 23]
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In the formula (5), R 21 ～R 23 Each independently represents a hydrogen atom or a C1-C6 alkyl group, ar 1 Represents unsubstituted or C1-C6 alkyl-substituted C6-C12 aryl.
As R 21 ～R 23 Examples of the "C1-C6 alkyl" in (1) include those mentioned above as R 11 R is R 12 The same groups as exemplified in (a) are the same groups.
As Ar 1 Examples of the "C6-C12 aryl" in (a) include phenyl, naphthyl and biphenyl.
Regarding Ar as 1 Examples of the "C1-C6 alkyl" of the substituent on the above-mentioned radical include those mentioned above as R 11 R is R 12 The same groups as exemplified in (a) are the same groups.
Specifically, the formula (5) includes the formulas (5-1) and (5-2).
[ chemical formula 24]
[ chemical formula 25]
Specific examples of the polymer having a repeating unit represented by the formula (V) in a molecule include polymers each having a repeating unit represented by the formula (V-1) in a molecule and further having at least one of a repeating unit represented by the formula (5-1) and a repeating unit represented by the formula (5-2). The polymer may be a block copolymer or a random copolymer.
The weight average molecular weight of the polymer having the repeating unit represented by the formula (V) in the molecule is preferably 1,200 to 40,000, more preferably 1,200 to 35,000. If the weight average molecular weight is too high, moldability and the like tend to be lowered. Therefore, when the weight average molecular weight of the resin composition is within the above range, the resin composition is excellent in heat resistance and moldability. The weight average molecular weight herein may be a weight average molecular weight obtained by measurement by a usual molecular weight measurement, and specifically, a value obtained by measurement by Gel Permeation Chromatography (GPC) or the like may be mentioned.
In the polymer having the repeating unit represented by the formula (V) in the molecule, the molar content of the repeating unit represented by the formula (V) is preferably 2 to 95 mol%, more preferably 8 to 81 mol%, when the total of the repeating units in the polymer having the repeating unit represented by the formula (V) in the molecule is 100 mol%.
In the case where the polymer having the repeating unit represented by the formula (V) in the molecule is a polymer having the repeating unit represented by the formula (V) and the repeating unit represented by the formula (5) in the molecule, the molar content of the repeating unit represented by the formula (V) is preferably 2 to 95 mol%, more preferably 8 to 81 mol%, and the molar content of the repeating unit represented by the formula (5) is preferably 5 to 98 mol%, more preferably 19 to 92 mol%.
7) (meth) acrylate resin (hereinafter, also referred to as "(B-7) component")
As the (meth) acrylate resin, a monofunctional (meth) acrylate monomer, a (meth) acrylate oligomer, or the like can be used. Among them, polyfunctional (meth) acrylates having 2 or more polymerizable unsaturated groups are preferable.
The monofunctional (meth) acrylate monomer is a monomer having 1 (meth) acrylate group in the molecule, and includes alkyl (meth) acrylate, acrylate having an alicyclic hydrocarbon group, (meth) acrylate having an ether skeleton, (meth) acrylate having a cyclic ether skeleton, and (meth) acrylate having an aromatic group.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isononyl (meth) acrylate.
Examples of the (meth) acrylate having an alicyclic hydrocarbon group include cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and methoxylated cyclodextrene (meth) acrylate.
Examples of the (meth) acrylate having an ether skeleton include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and diethylene glycol monomethyl ether (meth) acrylate.
Examples of the (meth) acrylic acid ester having a cyclic ether skeleton include glycidyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 3-ethyl-3-oxetanyl (meth) acrylate, 2-methyl-ethyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, γ -butyrolactone (meth) acrylate, dioxolan (meth) acrylate, oxetane (meth) acrylate, and (meth) acryloylmorpholine.
Examples of the (meth) acrylic acid ester having an aromatic group include phenyl (meth) acrylate, benzyl (meth) acrylate, methylbenzyl (meth) acrylate, ethylbenzyl (meth) acrylate, propylbenzyl (meth) acrylate, methoxybenzyl (meth) acrylate, phenoxyethyl (meth) acrylate, chlorobenzyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, and the like.
The multifunctional (meth) acrylate is a compound having 2 or more (meth) acrylate groups in the molecule, examples thereof include neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, dicyclopentadienyl diacrylate, di (meth) acryl isocyanurate, alkylene oxide modified bisphenol di (meth) acrylate, 2-bis (4- (meth) acryloxyphenyl) propane, 2-bis (4- (meth) acryloxyethoxyphenyl) propane 2-functional (meth) acrylates such as 2, 2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2-bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2-bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, and 2, 2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane; trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxy penta (meth) acrylate, alkyl-modified dipentaerythritol pentaacrylate, dipentaerythritol hexa (meth) acrylate and the like, 3-functional or more (meth) acrylates of polybutadiene skeleton, (meth) acrylates of hydrogenated polybutadiene skeleton, (meth) acrylates of polycarbonate skeleton, (meth) acrylates of polyether skeleton, (meth) acrylates of polyester skeleton, (meth) acrylates of castor oil skeleton, (meth) acrylates of isoprene-based (meth) acrylates, hydrogenated isoprene-based (meth) acrylates, epoxy (meth) acrylates, and (meth) acrylates of polyphenylene ether skeleton.
Examples of the (meth) acrylate oligomer include urethane (meth) acrylate of polybutadiene skeleton, urethane (meth) acrylate of hydrogenated polybutadiene skeleton, urethane (meth) acrylate of polycarbonate skeleton, urethane (meth) acrylate of polyether skeleton, urethane (meth) acrylate of polyester skeleton, urethane (meth) acrylate of castor oil skeleton, isoprene (meth) acrylate, hydrogenated isoprene (meth) acrylate, epoxy (meth) acrylate, and (meth) acrylate oligomer of polyphenylene ether skeleton.
8) Vinyl resin (hereinafter, also referred to as "(B-8) component")
Examples of the vinyl compound include a trialkenyl isocyanurate compound such as styrene, triallyl isocyanurate (TAIC), a divinylbenzene, a divinylnaphthalene, a modified polyphenylene ether resin having vinyl groups at both ends, a polybutadiene having a total of 1,2 units of 50% or more based on the total of all carbon-carbon double bonds, a styrene-butadiene copolymer having a polybutadiene having a total of 1,2 units of 50% or more based on the total of all carbon-carbon double bonds, a vinyl compound (polyfunctional vinyl compound) having 2 or more vinyl groups in the molecule, a modified polyphenylene ether resin having a vinylbenzyl group at both ends, a polydivinylbenzene-styrene copolymer, and a vinylbenzyl compound having 2 or more vinylbenzyl groups in the molecule. As the vinyl compound, the above-mentioned compound having 2 or more unsaturated double bonds in the molecule and the compound having 1 unsaturated double bond in the molecule may be used in combination. Specific examples of the compound having 1 unsaturated double bond in the molecule include a compound having 1 vinyl group in the molecule (monovinyl compound), and the like.
The thermosetting resin as the component (B) is preferably at least 1 or more selected from the group consisting of components (B-3) to (B-5).
(crosslinking agent)
When at least 1 or more selected from the above (B-2) to (B-8) is used as the thermosetting resin as the component (B), the resin composition of the present invention may further contain a crosslinking agent. The crosslinking agent is a substance that reacts with an unsaturated carbon bond contained in the component (B) to form a three-dimensional crosslink.
Examples of the crosslinking agent include polyfunctional vinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl; vinyl benzyl ether compounds synthesized by the reaction of phenol and vinyl benzyl chloride; allyl ether compounds synthesized from the reaction of styrene monomer, phenol and allyl chloride; triallyl isocyanurate (TAIC (registered trademark)), triallyl cyanurate (TAC) and other trialkenyl isocyanurates;
(meth) acrylate compounds (methacrylate compounds and acrylate compounds) such as trimethylolpropane;
compounds having acenaphthylene skeleton, and the like. When these crosslinking agents are used, heat resistance can be improved. The crosslinking agent may be used in an amount of 1 or 2 or more.
Examples of the compound having an acenaphthylene skeleton include:
Acenaphthylene;
hydroxy acenaphthylene compounds such as 3-hydroxy acenaphthylene, 4-hydroxy acenaphthylene, 5-hydroxy acenaphthylene, and 5, 6-dihydroxy acenaphthylene;
alkyl acenaphthylene compounds such as 3-methyl acenaphthylene, 3-ethyl acenaphthylene, 3-propyl acenaphthylene, 4-methyl acenaphthylene, 4-propyl acenaphthylene, 5-methyl acenaphthylene, 5-ethyl acenaphthylene, 5-propyl acenaphthylene, 3, 8-dimethyl acenaphthylene, 5, 6-dimethyl acenaphthylene, etc., alkoxy acenaphthylene compounds such as 3-methoxy acenaphthylene, 3-ethoxy acenaphthylene, 3-butoxy acenaphthylene, 4-methoxy acenaphthylene, 4-ethoxy acenaphthylene, 4-butoxy acenaphthylene, 5-methoxy acenaphthylene, 5-ethoxy acenaphthylene, 5-butoxy acenaphthylene, etc.;
halogenated acenaphthylene compounds such as 3-chloracenaphthylene, 3-bromoacenaphthylene, 4-chloracenaphthylene, 4-bromoacenaphthylene, 5-chloracenaphthylene, and 5-bromoacenaphthylene.
(polymerization initiator)
When at least 1 or more selected from the group consisting of (B-2) to (B-8) is used as the thermosetting resin as the component (B), the resin composition of the present invention may contain a polymerization initiator.
The polymerization initiator used in the resin composition of the present invention includes azo-based polymerization initiators, peroxide-based polymerization initiators, and the like.
As the azo-based polymerization initiator, for example, examples thereof include azobisisobutyronitrile, 1' -azobis (cyclohexane-1-carbonitrile), 2' -azobis { 2-methyl-N- [1, 1-bis (hydroxymethyl) ethyl ] propionamide }, 2' -azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide ], 2' -azobis [2- (hydroxymethyl) propionitrile }, and 2,2' -azobis (2, 4-dimethylvaleronitrile), 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile), dimethyl 2,2' -azobisisobutyrate, 2' -azobis [2- (2-imidazolin-2-yl) propane ], 2' -azobis { 2-methyl-N- [1, 1-bis (hydroxymethyl) -2-hydroxyethyl ] propionamide }, and the like.
Examples of the peroxide-based polymerization initiator include, but are not limited to, peroxides such as benzoyl peroxide, cumene hydroperoxide, 2, 5-dimethyl-2, 5-dihydrohexane peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne, di-t-butyl peroxide, t-butylcumyl peroxide, α' -di (t-butylperoxy-m-isopropyl) benzene, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, dicumyl peroxide, di-t-butyl peroxyisophthalate, t-butyl peroxybenzoate, 2-bis (t-butylperoxy) butane, 2-bis (t-butylperoxy) octane, 2, 5-dimethyl-2, 5-di (benzoyl peroxy) hexane, bis (trimethylsilyl) peroxide, trimethylsilyl triphenylsilyl peroxide, and dicumyl peroxide. In addition, 2, 3-dimethyl-2, 3-diphenylbutane may be used as a radical polymerization initiator (or polymerization catalyst) although it is not a peroxide. However, the polymerization initiator used in curing the resin composition of the present invention is not limited to these examples.
The polymerization initiator used in the resin composition of the present invention is preferably a peroxide-based polymerization initiator.
(composition ratio of resin composition)
When the (B-1) epoxy resin is used as the component (B), the content of the component (A) in the resin composition of the present invention is not particularly limited, and 1 to 99% by weight, 1 to 50% by weight, 1 to 30% by weight, and the like can be given as the amount of the component (B).
When at least 1 or more selected from the group consisting of (B-2) to (B-8) is used as the component (B), the content of the component (A) in the resin composition of the present invention is not particularly limited, and 1 to 99% by weight, 10 to 70% by weight, 10 to 50% by weight, and the like can be mentioned relative to the total amount of the component (B) and the crosslinking agent.
The content ratio of the component (B) to the crosslinking agent in the resin composition of the present invention is not particularly limited, and examples thereof include the component (B) having a crosslinking agent=99:1 to 1:99, 90:10 to 30:70, 90:10 to 50:50, and the like in terms of weight ratio.
The content of the polymerization initiator in the resin composition of the present invention is not particularly limited, and may be 0.1 to 10% by weight based on the total amount of the component (B) and the crosslinking agent.
(2) Other ingredients
The resin composition of the present invention may contain other components as necessary within a range that does not impair the effects of the present invention. Examples of the other component include an organic solvent, a thermoplastic resin, an inorganic filler, an organic filler, a flame retardant, and other additives.
1) Organic solvents
Examples of the organic solvent include amide-based solvents, ether-based solvents, ester-based solvents, aliphatic-based solvents, aromatic-based solvents, ketone-based solvents, and organic halide-based solvents.
Examples of the amide-based organic solvent include N, N-Dimethylformamide (DMF) and N, N-dimethylacetamide; examples of the ether-based organic solvent include diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, and tetrahydrofuran; examples of the ester-based organic solvent include ethyl acetate, propyl acetate, butyl acetate, amyl acetate, heptyl acetate, ethyl butyrate, isoamyl isovalerate, and propylene glycol methyl ether acetate; examples of the aliphatic hydrocarbon-based organic solvent include n-hexane, n-heptane and cyclohexane; examples of the aromatic hydrocarbon-based organic solvent include toluene and xylene; examples of the ketone-based organic solvent include methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; examples of the organic solvents of the organic halide system include trichloroethane and trichloroethylene; etc. In addition, relatively inert organic solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, and the like may also be used.
2) Thermoplastic resin
Examples of the thermoplastic resin include polyacrylate resins, polymethacrylate resins, polystyrene resins, polyphenylene ether resins, polyetherimide resins, polyethersulfone resins, polyphenylene sulfide resins, polycyclopentadiene resins, polycycloolefin copolymer resins, polyarylate resins, polyether resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polycarbonate resins, polyetheretherketone resins, polyester resins, liquid crystal polyester resins, fluororesins, and the like, known thermoplastic elastomers such as styrene-ethylene-propylene copolymers, styrene-ethylene-butylene copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, hydrogenated styrene-butadiene copolymers, hydrogenated styrene-isoprene copolymers, (meth) acrylonitrile-butadiene- (meth) acrylic acid methyl ester copolymers, (meth) acrylic acid-butadiene-styrene copolymers (MBS), and (meth) acrylonitrile-butadiene rubber (NBR), fluorine-based rubber, vinyl-butadiene rubber, and the like.
3) Inorganic filler
The material of the inorganic filler is not particularly limited, and examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate. Among them, silica is particularly preferred. In addition, spherical silica is preferable as silica. The inorganic filler may be used alone or in combination of 1 or more than 2.
The inorganic filler is preferably treated with a surface treatment agent of at least 1 kind selected from an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an organosilane compound, a titanate-based coupling agent, a vinylsilane-based coupling agent, a methacryloxysilane-based coupling agent, an acryloxysilane-based coupling agent, and a styrylsilane-based coupling agent.
4) Organic filler
Examples of the organic filler include rubber particles, fluororesin particles (fluorine-based polymer particles), polyamide fine particles, and silicone particles.
As the rubber particles, commercially available products may be used, and examples thereof include "EXL-2655" manufactured by Dow Chemical Japan co., ltd., and "AC3816N" manufactured by Aica Kogyo co., ltd.
Examples of the fluororesin particles (fluorine-based polymer particles) include Polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene propylene copolymer (FEP), ethylene tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluorodioxole copolymer (TFE/PDD), polyvinylidene fluoride (PVDF), polytrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polyvinyl fluoride (PVF). These resins may be used alone or in combination of 1 or more than 2.
The fluororesin particles (fluorine-based polymer particles) may be commercially available ones. Specific examples of the commercially available PTFE particles of the fluorine-based polymer particles include "LUBRON (registered trademark) L-2" manufactured by Ltd, daikin Industries, "LUBRON L-5" manufactured by Ltd, daikin Industries, ltd, "LUBRON L-5F" manufactured by Asahi Kabushiki Kaisha, "Fluon PTFE L-172JE" manufactured by Asahi Kaisha, and "Fluon PTFE L-173JE" manufactured by Asahi Kaisha, and "KTL-500F" manufactured by Sonchi Kaisha, kyowa Kaisha, KTKL-2N "manufactured by Kaisha, KTL-1N" manufactured by Sonchi Kaisha, dupont-Mitsui Fluorochemicals Co., ltd.
Surface treated particles may also be included. As the surface treatment, for example, surface treatment with a surface treatment agent can be cited. The surface treatment agent is not particularly limited. The surface treatment agent includes inorganic fine particles and the like in addition to surfactants such as nonionic surfactants, amphoteric surfactants, cationic surfactants, and anionic surfactants. From the viewpoint of affinity, a fluorine-based surfactant is preferably used as the surface treatment agent. Specific examples of the fluorine-based surfactant include "Surflon (registered trademark) S-243" (perfluoroalkyl ethylene oxide adduct), "MEGAFACE (registered trademark) F-251" made by DIC, MEGAFACE F-477 "made by DIC, MEGAFACE F-553" made by DIC, MEGAFACE R-40 "made by DIC, MEGAFACE R-43" made by DIC, MEGAFACE R-94 "made by DIC, FTX-218" made by NEOS, ftergent (registered trademark) 610FM "made by NEOS, and Ftergent 730 made by NEOS).
5) Flame retardant
The flame retardant is not particularly limited, and known flame retardants can be used.
Specifically, in the field of using halogen flame retardants such as brominated flame retardants, for example, ethylene bis pentabromobenzene (ethylene dipentabromobenzene), ethylene bis tetrabromoimide, decabromodiphenyl ether and tetradecylbromodiphenoxybenzene having a melting point of 300 ℃ or higher are preferable. It is considered that the use of the halogen-based flame retardant can suppress the release of halogen at high temperature and can suppress the decrease in heat resistance. In addition, in the field where no halogen is required, phosphorus flame retardants such as phosphate flame retardants, phosphazene flame retardants, and phosphonate flame retardants are exemplified. Specific examples of the phosphate flame retardant include condensed phosphates of xylyl phosphate. As concrete examples of the phosphazene flame retardant, phenoxyphosphazene is given. Specific examples of the phosphonate-based flame retardant include metal phosphonate salts of dialkylaluminum phosphonate. The exemplified flame retardants may be used alone, or 2 or more kinds may be used in combination.
6) Other additives
Examples of the other additives include defoaming agents such as silicone-based defoaming agents and acrylate-based defoaming agents, organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, adhesion aids such as leveling agents and silane coupling agents, adhesion promoters such as tackifiers, heat stabilizers, antistatic agents, storage stabilizers such as BHT, antioxidants, light stabilizers, ultraviolet absorbers, dyes, pigments, lubricants, wetting dispersants, heavy metal deactivators, ion capturing agents, emulsifiers, water-dispersible stabilizers, mold release agents, waxes, rheology modifiers, surfactants, and the like.
(3) Mode of use of resin composition
The resin composition of the present invention can be used in a wide range of applications requiring a resin composition, such as solder resist, underfill material, die bonding material, semiconductor sealing material, hole-embedding resin, component-embedding resin, insulating material for printed wiring board, and the like. The resin composition of the present invention is preferably a resin composition for an insulating layer of a printed wiring board. The printed wiring board includes a single-sided printed board, a double-sided printed board, a multilayer printed board, a flexible printed board, a build-up board, and the like. The form of the resin composition of the present invention is not particularly limited, and the resin composition can be applied to a sheet-like laminate such as an adhesive film and a prepreg, and a printed wiring board. The resin composition of the present invention may be applied to a printed wiring board in a varnish state to form an insulating layer, but is industrially used for forming an insulating layer usually in the form of a sheet laminate such as an adhesive film or a prepreg.
3. Cured product (molded body)
The cured product obtained by curing the resin composition of the present invention can be used in the form of molded articles, insulators for printed wiring boards, laminates with metal foils, castings, adhesives, coating films, and films. For example, the cured product of the semiconductor sealing material is a cast product or a molded product, and as a method for obtaining a cured product for this purpose, the curable resin composition may be molded by casting, a transfer molding machine, an injection molding machine, or the like, and further heated at 80 to 230 ℃ for 0.5 to 10 hours, thereby obtaining a cured product.
4. Resin varnish
The resin composition of the present invention can be prepared in the form of a varnish for the purpose of impregnating a substrate (fibrous substrate) for forming a prepreg, for the purpose of coating a support film for forming an adhesive film, or for the purpose of forming a printed wiring board, to thereby prepare a resin varnish.
The resin varnish is particularly suitable for use in printed wiring boards, and can be used as a varnish for printed wiring boards.
The resin varnish can be prepared, for example, as follows.
The components are put into an organic solvent and dissolved. At this time, heating may be performed as needed. Then, if necessary, an organic solvent-insoluble component such as an inorganic filler is added, and dispersed using a ball mill, a bead mill, a planetary mixer, a roll mill, or the like, to thereby prepare a varnish-like curable resin composition.
An inorganic high dielectric powder such as barium titanate or an inorganic magnet such as ferrite is blended in the curable resin composition or the resin varnish, and is thus excellent as a material for electronic parts, particularly a material for high-frequency electronic parts.
5. Sheet-like laminate
The resin composition of the present invention can be used for a sheet-like laminate. Examples of the sheet-like laminate include prepregs and adhesive films.
6. Prepreg
The prepreg of the present invention is characterized in that the resin composition of the present invention is impregnated into a substrate.
Examples of the substrate include fibrous substrates such as glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, and cotton linter paper.
The prepregs of the present invention can be manufactured using known methods. For example, a method of impregnating a substrate with the resin varnish of the present invention and then drying the impregnated substrate is mentioned.
The prepreg in a semi-cured state (B stage) can be obtained by heating the resin varnish-impregnated substrate with a desired heating condition (for example, 80 to 170 ℃ for 1 to 10 minutes) to remove the solvent.
7. Adhesive film
The adhesive film of the present invention is characterized by having a resin composition layer containing the resin composition of the present invention on a support film. The adhesive film of the present invention can be produced by a known method. For example, it can be manufactured by: the resin varnish of the present invention is applied to a support film using a die coater or the like, and the organic solvent is dried by heating, hot air blowing, or the like, to form a resin composition layer.
The drying conditions are not particularly limited, and the resin composition layer is dried so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. Although the amount of the organic solvent in the varnish and the boiling point of the organic solvent vary depending on each other, the varnish containing 30 to 60 mass% of the organic solvent may be dried at 50 to 150 ℃ for about 3 to 10 minutes, for example, to form a resin composition layer.
The thickness of the resin composition layer formed in the adhesive film is preferably set to be equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70. Mu.m, the resin composition layer preferably has a thickness of 10 to 100. Mu.m. From the viewpoint of film formation, it is more preferably 15 to 80. Mu.m.
Examples of the support film include films of polyolefin such as polyethylene, polypropylene, and polyvinyl chloride, films of polyester such as polyethylene terephthalate (hereinafter, sometimes simply referred to as "PET"), films of polyester such as polyethylene naphthalate, and various plastic films such as polycarbonate films and polyimide films. In addition, a release paper, a copper foil, a metal foil such as an aluminum foil, or the like may be used. Among them, from the viewpoint of versatility, a plastic film is preferable, and a polyethylene terephthalate film is more preferable. The support and the protective film described later may be subjected to surface treatment such as MAD treatment and corona treatment. The release treatment may be performed with a release agent such as a silicone release agent, an alkyd release agent, or a fluororesin release agent.
The thickness of the support film is not particularly limited, but is preferably 10 to 150. Mu.m, more preferably 25 to 50. Mu.m.
A protective film based on the support may be further laminated on the surface of the resin composition layer to which the support is not adhered. The thickness of the protective film is not particularly limited, and is, for example, 1 to 40. Mu.m. By laminating the protective film, adhesion and damage of dirt and the like generated on the surface of the resin composition layer can be prevented. The adhesive film may be wound into a roll for storage.
8. Insulator for printed wiring board
The insulator for a printed wiring board of the present invention is formed from a cured product of any one of the prepreg of the present invention and the adhesive film of the present invention. The method for producing the insulator for a printed wiring board of the present invention is not particularly limited, and examples thereof include a method in which a sheet-like laminate is laminated one by one or a plurality of sheets and then heated and pressed to be molded. The insulator for a printed wiring board of the present invention is suitable as an insulating layer for a single-sided printed board, a double-sided printed board, a multilayer printed board, a flexible printed board, and a build-up board.
9. Laminate with metal foil
The laminate with a metal foil of the present invention includes the layer of the insulator for a printed wiring board of the present invention and the layer of the metal foil. Examples of the metal foil used herein include copper foil and aluminum foil. The thickness is not particularly limited and is in the range of 3 to 200. Mu.m, more preferably 3 to 105. Mu.m.
Examples of the method for producing the laminate with a metal foil of the present invention include the following methods: the sheet-like laminate and the metal foil of the present invention described above are laminated in a layer configuration according to the purpose, and the layers are bonded together under heat and pressure, and heat curing is performed. In the laminate with metal foil of the present invention, the insulator for a printed wiring board and the metal foil are laminated in an arbitrary layer configuration. The metal foil may be used as a surface layer or as an intermediate layer. In addition to the above-described method, lamination and curing may be repeated a plurality of times to achieve multilayering.
In the adhesion to the metal foil, an adhesive may be used. Examples of the adhesive include epoxy, acrylic, phenol, and cyanoacrylate adhesives, but are not particularly limited thereto. The resin composition of the present invention may be used as an adhesive. The lamination molding and curing described above can be performed under the same conditions as those for manufacturing the insulator for a printed wiring board of the present invention.
Industrial applicability
The resin composition containing the polymer of the present invention can be processed into a molding material, sheet or film, and can be used for low dielectric materials, insulating materials, heat-resistant materials, structural materials, etc. which can satisfy characteristics such as low dielectric constant, low water absorption, high heat resistance, etc. in the fields of electric industry, aerospace industry, automobile industry, etc. In particular, it can be used as a single-sided, double-sided, multi-layer printed substrate, flexible printed substrate, build-up substrate, etc. Further, the composition can be applied to a semiconductor-related material or an optical material, a coating material, a photosensitive material, an adhesive, a sewage treatment agent, a heavy metal trapping agent, an ion exchange resin, an antistatic agent, an antioxidant, an antihalation agent, an antirust agent, an anti-stain agent, a bactericide, an insect repellent, a medical material, an agglutinant, a surfactant, a lubricant, a binder for solid fuel, a conductive treatment agent, a resin modified material, an asphalt modified material plasticizer, a sintered binder, and the like.
The polymer of the present invention is a resin having a low dielectric constant and a low dielectric loss tangent, and a high glass transition temperature, showing high solubility in an organic solvent and high compatibility with a thermosetting resin. Therefore, in the fields of the electric and electronic industry, the aerospace industry, the aircraft industry, and the like, as a dielectric material, an insulating material, a heat-resistant material, a structural material, and the like, it is possible to provide a cured molded product free from molding defects such as warpage, in response to the recent strong demand for downsizing and thinning. Further, since the wiring embedding flatness and adhesion to different kinds of materials are excellent, a curable resin composition, a cured product, or a material containing the same excellent in reliability can be realized.
The following examples are given, but the technical scope of the invention of the present application is not limited to the examples.
Examples
(1) Weight average molecular weight (Mw) and dispersity (Mw/Mn)
The weight average molecular weight of the polymer obtained in the examples was measured using the following apparatus and conditions.
[ device ]
Sample injection device: waters 2695Alliance
Separation column: shodexKF-G, 805L, 804L
A detector: waters 2414 differential Refractive (RI) detector
2998 photodiode array (PDA) detector
Column incubator: column incubator manufactured by Waters company
[ Condition ]
Column oven temperature: 40 DEG C
RI detector temperature: 40 DEG C
Mobile phase: tetrahydrofuran (THF)
Flow rate: 1.0mL/mIn
Standard injection amount: 200 mu L
PDA detector extraction wavelength: 254.0nm
Quantitative calculation: converted according to standard polymethyl methacrylate
(2) Glass transition temperature
Using 10mg of polyacrylamide as a sample, the temperature was raised at a temperature rise rate of 10℃per minute using a DSC (differential scanning calorimeter) apparatus (Q2000 manufactured by TA Instruments Co., ltd.) to obtain an intermediate value of 2 inflection points temperatures derived from glass transition in the temperature rise curve as a glass transition temperature.
(3) Relative permittivity and dielectric loss tangent
The measurement was performed under the following conditions using polyacrylamide powder and using a resonance method.
The device comprises: AET Inc. cylindrical cavity resonator
Frequency 1GHz
Measuring temperature: 23 DEG C
(4) Solubility of
To 50 parts by weight of polyacrylamide, 50 parts by weight of an organic solvent was added, and the mixture was stirred at room temperature for 2 hours. The state of the resin solution after standing for 1 day was evaluated according to the following criteria. As the organic solvent, MEK, toluene, and cyclohexanone were used.
And (2) the following steps: the resin solution has fluidity and is transparent.
Delta: the resin solution had fluidity but produced cloudiness.
X: the resin solution had no fluidity and the resin was not completely dissolved.
Example 1
Synthesis of N, N-bis (4- (tert-butyl) phenyl) acrylamide
[ chemical formula 26]
Into a nitrogen-substituted 1L four-necked flask were charged bis (4-t-butylphenyl) amine (100 g,0.355 mol), N-dimethylaniline (64.59 g,0.53 mol), and 400mL of ultra-dehydrated toluene, and stirred until dissolved uniformly. Next, the reaction solution was cooled to 0℃or lower in an ice/ethanol bath, and acryloyl chloride (38.59 g,0.426 mol) was slowly added dropwise thereto, followed by stirring for 30 minutes. Then, the reaction solution was warmed to room temperature and reacted for 24 hours. After the completion of the reaction, the reaction mixture was washed with 1N aqueous hydrochloric acid, saturated aqueous sodium bicarbonate and brine. The organic layer was dehydrated with magnesium sulfate, and then the filtrate was distilled off by an evaporator. The obtained crude product was purified by recrystallization from hexane, whereby N, N-bis (4- (t-butyl) phenyl) acrylamide (92.90 g, yield 79%) was obtained.
Example 2
Polyacrylamide A; preparation of Poly [ N, N-bis (4- (t-butyl) phenyl) acrylamide ]
Into a 300mL four-necked flask, 50g of N, N-bis (4- (t-butyl) phenyl) acrylamide and 0.15g of AIBN were charged, and dissolved in 75g of toluene. Degassing was performed by applying a reduced pressure operation, and stirring was performed under heating at 65℃for 24 hours under a nitrogen atmosphere. Then, 0.10g of AIBN was added thereto and stirred at 80℃for 2 hours. The heating and stirring were stopped, and the reaction solution was sampled and subjected to gel permeation chromatography. The reaction liquid was added dropwise to methanol 1L, whereby powdering was performed. The precipitate was separated by filtration, and dried at 60℃under reduced pressure using a vacuum dryer.
Yield 46.2g, mw=58,000, mw/mn=2.40
Comparative example 1
Synthesis of N, N-bis (4- (N-butyl) phenyl) acrylamide
[ chemical formula 27]
Into a 300mL four-necked flask replaced with nitrogen, bis (4-N-butylphenyl) amine (25.4 g,0.090 mol), N-dimethylaniline (21.09 g,0.174 mol), and 100mL of ultra-dehydrated toluene were charged and stirred until they were uniformly dissolved. Next, the reaction solution was cooled to 0℃or lower in an ice/ethanol bath, and acryloyl chloride (9.46 g,0.105 mol) was slowly added dropwise thereto and stirred for 30 minutes. Then, the reaction solution was warmed to room temperature and reacted for 24 hours. After the completion of the reaction, the reaction mixture was washed with 1N aqueous hydrochloric acid, saturated aqueous sodium bicarbonate and distilled water. The organic layer was dehydrated with magnesium sulfate, and then the filtrate was distilled off by an evaporator. The obtained crude product was isolated and purified by silica gel column chromatography using hexane/ethyl acetate=4:1 (v/v) as a solvent, whereby N, N-bis (4- (N-butyl) phenyl) acrylamide (20.80 g, yield 69%) was obtained.
Comparative example 2
Polyacrylamide B: preparation of Poly [ N, N-bis (4- (N-butyl) phenyl) acrylamide ]
To a 100mL double-necked flask, 20g of N, N-bis (4- (N-butyl) phenyl) acrylamide and 0.06g of AIBN were charged and dissolved in 22.5g of toluene. Degassing was performed by applying a reduced pressure operation, and stirring was performed under nitrogen at 60℃for 24 hours. Then, 0.10g of AIBN was added thereto and stirred at 60℃for 24 hours. The heating and stirring were stopped, and the reaction solution was sampled and subjected to gel permeation chromatography. The reaction liquid was added dropwise to methanol 1L, whereby powdering was performed. The precipitate was separated by filtration, and dried at 60℃under reduced pressure using a vacuum dryer. Yield 18.1g, mw=76,000, mw/mn=2.89
TABLE 1
From the test results, it is found that the polyacrylamide of the present invention has excellent heat resistance and dielectric characteristics, can be dissolved in an organic solvent at a high concentration, and has excellent compatibility with other thermoplastic resins and thermosetting resins.
Example 3, comparative example 3
The reagents were added to toluene in the compositions (parts by weight) shown in table 2 so that the solid content concentration became 50% by weight, and mixed. Then, toluene was removed from the obtained liquid by an evaporator, thereby obtaining a resin composition in a powder form. The resin composition was thermally pressurized at 200℃for 90 minutes, thereby curing it. The physical properties of the obtained cured product were measured in the following items, and the results are shown in table 2.
< glass transition temperature (Tg) >)
A DSC (differential scanning calorimeter) device (Q2000 manufactured by TA Instruments) was used to raise the temperature at a temperature-raising rate of 10 ℃/min, and the intermediate value of the 2 inflection point temperatures derived from the glass transition in the temperature-raising curve was used as the glass transition temperature.
< dielectric constant test (Dk) & dielectric loss tangent test (Df) >)
Measurement was performed at 10GHz using a cylindrical cavity resonator (TE mode resonator) manufactured by AET inc.
TABLE 2
NC3000: biphenyl type epoxy resin manufactured by Japanese chemical medicine Co
HPC-8000-65T: reactive ester resin produced by DIC Co
DMAP: dimethylaminopyridine
Example 4, comparative example 4
The reagents were added to toluene in the compositions (parts by weight) shown in table 3 so that the solid content concentration became 50% by weight, and mixed. Then, toluene was removed from the obtained liquid by an evaporator, thereby obtaining a resin composition in a powder form. The resin composition was thermally pressurized at 200℃for 120 minutes, thereby curing it. The physical properties of the obtained cured product were measured in the following items, and the results are shown in table 3.
< glass transition temperature (Tg) >)
A DSC (differential scanning calorimeter) device (Q2000 manufactured by TA Instruments) was used to raise the temperature at a temperature-raising rate of 10 ℃/min, and the intermediate value of the 2 inflection point temperatures derived from the glass transition in the temperature-raising curve was used as the glass transition temperature.
< dielectric constant test (Dk) & dielectric loss tangent test (Df) >)
Measurement was performed at 10GHz using a cylindrical cavity resonator (TE mode resonator) manufactured by AET inc.
TABLE 3
SA9000: SABIC Innovative Plastics Co., ltd. Preparation of methacryloyl modified polyphenylene ether Compound
PERBUTYL (registered trademark) P: alpha, alpha' -di (t-butylperoxy) diisopropylbenzene manufactured by Nikko Co.

Claims (20)

1. A polymer having at least 1 of repeating units derived from a polymerizable compound represented by formula (I),
[ chemical formula 1]
In the formula (I), X 1 、X 2 Each independently represents a C3-C6 branched alkyl group, a C3-C6 cyclic alkyl group, a C3-C6 branched alkoxy group, or a C3-C6 cyclic alkoxy group, n represents 0 or 1, Z 1 、Z 2 Each independently represents a single bond or a C1-C3 alkylene group, each R independently represents an organic group or a halogenated group, each of m1 and m2 independently represents an integer of 0 to 4, and Y represents a polymerizable functional group.
2. The polymer of claim 1, wherein Y is an acryl or methacryl group.
3. A resin composition comprising the polymer according to claim 1.
4. The resin composition according to claim 3, further comprising a resin other than the polymer according to claim 1.
5. The resin composition according to claim 4, wherein the resin other than the polymer according to claim 1 is a thermosetting resin.
6. The resin composition according to claim 5, wherein the thermosetting resin is an epoxy resin.
7. The resin composition according to claim 6, further comprising an active ester compound as a curing agent.
8. The resin composition according to claim 5, wherein the thermosetting resin is at least 1 or more selected from the group consisting of:
maleimide compounds having more than one maleimide group,
a polyphenylene ether compound which comprises a polyphenylene ether compound,
polybutadiene with a molar ratio of 1,2 bond structure to 1,4 bond structure of 80:20-100:0,
styrene-butadiene-styrene block copolymer (SBS) having a molar ratio of 1,2 bond structure to 1,4 bond structure in the butadiene block of 80:20 to 100:0, and
a polymer having a repeating unit represented by the formula (V) in the molecule,
[ chemical formula 2]
In the formula (V), Z 3 Represents a C6-C12 arylene group, R 2 ～R 7 Each independently represents a hydrogen atom or a C1-C6 alkyl group.
9. The resin composition according to claim 8, wherein the polyphenylene ether compound is a polyphenylene ether compound obtained by terminal-modifying a group represented by the formula (VI), an acryl group or a methacryl group,
[ chemical formula 3]
In formula (VI), p represents an integer of 0 to 10, Z 4 Represents a C6-C12 arylene group, R 8 ～R 10 Each independently represents a hydrogen atom or a C1-C6 alkyl group.
10. A molded article comprising the cured product of the resin composition according to claim 3.
11. The resin composition according to any one of claims 3 to 9, which is a resin composition for an insulating layer of a printed wiring board.
12. A resin varnish comprising the resin composition according to any one of claims 3 to 9.
13. A prepreg obtained by impregnating the resin composition according to any one of claims 3 to 9 with a base material.
14. An adhesive film comprising a support film and a resin composition layer comprising the resin composition according to any one of claims 3 to 9.
15. An insulator for a printed wiring board, which is formed from the cured product of the prepreg according to claim 13.
16. An insulator for a printed wiring board, which is formed from the cured product of the adhesive film according to claim 14.
17. A laminate with a metal foil comprising a layer formed of the insulator for a printed wiring board according to claim 15 and a layer formed of a metal foil.
18. A laminate with a metal foil comprising a layer formed of the insulator for a printed wiring board according to claim 16 and a layer formed of a metal foil.
19. A compound represented by the formula (III),
[ chemical formula 4]
In the formula (III), X 1 、X 2 Each independently represents a C3-C6 branched alkyl group, a C3-C6 cyclic alkyl group, a C3-C6 branched alkoxy group, or a C3-C6 cyclic alkoxy group, n represents 0 or 1, Z 1 、Z 2 Each independently represents a single bond or a C1-C3 alkylene group, each R independently represents an organic group or a halogenated group, each of m1 and m2 independently represents an integer of 0 to 4, and Y represents a polymerizable functional group.
20. The compound according to claim 19, wherein the compound represented by the formula (III) is a compound represented by the formula (IV),
[ chemical formula 5]
In the formula (IV), R 1 Represents a hydrogen atom or a methyl group.
CN202280047695.1A 2021-07-14 2022-07-08 Novel polymer, resin composition containing the same, and molded article thereof Pending CN117597371A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2021-116330 2021-07-14
JP2022-090373 2022-06-02
JP2022090373 2022-06-02
PCT/JP2022/027125 WO2023286713A1 (en) 2021-07-14 2022-07-08 Novel polymer, resin composition including same, and molded body thereof

Publications (1)

Publication Number Publication Date
CN117597371A true CN117597371A (en) 2024-02-23

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Country Link
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