阅读说明：本技术 无规共聚物化合物、末端改性高分子化合物及含有这些化合物的树脂组合物 (Random copolymer compound, terminal-modified polymer compound, and resin composition containing these compounds ) 是由 赤冢泰昌 白井一光 于 2019-11-01 设计创作，主要内容包括：本发明的目的在于提供一种具有优异的薄膜形成能力,并且耐热性及粘合性高且介电常数及介电损耗角正切低的无规共聚物化合物及末端改性高分子化合物。也就是,本发明揭示一种无规共聚物化合物,其为下列(A)及(B)与(C)的无规共聚物化合物：(A)在两末端具有酚性羟基的聚苯醚树脂、(B)在两末端具有醇性羟基的脂肪族高分子、(C)属于结合剂的酰二氯化合物的无规共聚物化合物；且该(A)聚苯醚树脂的摩尔数a、该(B)脂肪族高分子的摩尔数b及该(C)属于结合剂的酰二氯化合物的摩尔数c满足(a+b)＞c的关系。(The purpose of the present invention is to provide a random copolymer compound and a terminal-modified polymer compound that have excellent film-forming ability, high heat resistance and adhesion, and low dielectric constant and dielectric loss tangent. That is, the present invention discloses a random copolymer compound which is a random copolymer compound of the following (A) and (B) and (C): (A) a polyphenylene ether resin having phenolic hydroxyl groups at both ends, (B) an aliphatic polymer having alcoholic hydroxyl groups at both ends, and (C) a random copolymer compound of an acid dichloride compound which is a binder; and the mole number a of the polyphenylene ether resin (A), the mole number B of the aliphatic polymer (B) and the mole number C of the acid dichloride compound (C) belonging to the binder satisfy the relationship of (a + B) > C.)

1. A random copolymer compound which is a random copolymer compound of the following (A), (B) and (C),

(A) a polyphenylene ether resin having phenolic hydroxyl groups at both ends,

(B) An aliphatic polymer having alcoholic hydroxyl groups at both ends, and

(C) an acid dichloride compound belonging to a binder,

and the mole number a of the polyphenylene ether resin (A), the mole number B of the aliphatic polymer (B) and the mole number C of the acid dichloride compound (C) belonging to the binder satisfy the relationship of (a + B) > C.

2. The random copolymer compound according to claim 1, wherein the mole number a and the mole number b satisfy a relationship of a > b.

3. The random copolymer compound according to claim 1, which is represented by the following formula (1);

in the formula (1), RA represents a divalent linking group obtained by removing two hydrogen atoms from phenolic hydroxyl groups at both ends of (A) a polyphenylene ether resin having phenolic hydroxyl groups at both ends, RB represents a divalent linking group obtained by removing two hydrogen atoms from alcoholic hydroxyl groups at both ends of (B) an aliphatic polymer having alcoholic hydroxyl groups at both ends, L represents a divalent linking group represented by the following formula (2),

in the formula (2), RC represents a divalent linking group obtained by removing two acid chloride groups from (C) an acid chloride compound belonging to the binder; d and e are average values of the number of repeating units and each independently represents a real number in the range of 1 to 100.

4. The random copolymer compound according to claim 3, wherein,

RA is a divalent linking group represented by the following formula (3);

in the formula (3), X represents a divalent linking group obtained by removing two phenolic hydroxyl groups from a compound having two phenolic hydroxyl groups, R independently represents a methyl group, an ethyl group, a propyl group, an allyl group or a phenyl group, g and h are average values of the number of repeating units and independently represent real numbers in the range of 1 to 100, and y independently represents an integer of 1 to 4.

5. The random copolymer compound according to claim 4, wherein,

x is a divalent linking group obtained by removing two phenolic hydroxyl groups from bisphenol A, tetramethylbisphenol A, bisphenol F, or 4, 4' -biphenol.

6. The random copolymer compound according to any one of claims 3 to 5, wherein,

RB is a divalent linking group obtained by removing two hydrogen atoms from alcoholic hydroxyl groups at both ends of a polybutadiene rubber having alcoholic hydroxyl groups at both ends.

7. A terminal-modified polymer compound which is a reaction product of the random copolymer compound according to any one of claims 1 to 6 and (D) a compound having a substituent reactive with a hydroxyl group and an unsaturated double bond group.

8. The terminal-modified polymer compound according to claim 7, wherein the compound (D) having a substituent reactive with a hydroxyl group and an unsaturated double bond group is a compound having an acid chloride group and an unsaturated double bond group, a compound having an isocyanate group and an unsaturated double bond group, or a compound having a chlorodimethylsilyl group and an unsaturated double bond group.

9. The terminal-modified polymer compound according to claim 8, which is a compound represented by the following formula (4);

in the formula (4), RA, RB, L, d and e are the same as those in the formula (1) described in claim 3; z independently represents a substituent represented by the following formula (5-1), (5-2) or (5-3);

in the formula (5-1), RD represents a residue obtained by removing an acid chloride group from a compound having an acid chloride group and an unsaturated double bond in one molecule; in the formula (5-2), RE represents a residue obtained by removing an isocyanate group from a compound having an isocyanate group and an unsaturated double bond group in one molecule; in the formula (5-3), RF represents a residue obtained by removing a chlorodimethylsilyl group from a compound having a chlorodimethylsilyl group and an unsaturated double bond in one molecule.

10. A resin composition comprising: a random copolymer compound according to any one of claims 1 to 6 or a terminal-modified polymer compound according to any one of claims 7 to 9, and a radical initiator.

11. A film-like adhesive comprising the resin composition according to claim 10.

12. A cured product of the resin composition according to claim 10 or the film-like adhesive according to claim 11.

Technical Field

The present invention relates to a random copolymer compound which can be easily formed into a film shape by a method of casting a solution onto a substrate, can be cured by using a radical initiator in combination, and has excellent flexibility, heat resistance, water resistance, dielectric characteristics, and adhesiveness, a terminal-modified polymer compound, and a resin composition containing the same.

Background

The phenoxy resin is a polymer compound having a very large molecular weight obtained by polymerizing a bifunctional epoxy resin and a bifunctional phenol compound. Since a general epoxy resin composition or radical polymerizable composition can be formed into a film shape by adding the phenoxy resin, the phenoxy resin can be used as an important component of a film-like adhesive in a wide range of fields. In particular, the copper foil is used in the electrical and electronic fields as an interlayer insulating layer of a printed circuit board, a resin-coated copper foil, or the like. However, a cured product of a resin composition containing a phenoxy resin has low heat resistance, and has a high dielectric constant/dielectric loss tangent (a dielectric constant of 3.5 at a frequency of 1GHz and a dielectric loss tangent of about 0.03.), although it is excellent in adhesiveness, and therefore, it is practically unusable for electronic equipment applications in which a signal response speed has been increased in recent years. As a resin having excellent dielectric characteristics such as low dielectric constant and low dielectric loss tangent, a polymer fluorine compound such as Polytetrafluoroethylene (PTFE) (patent document 1) or a liquid crystal polymer (patent document 2) is generally known, but these resins have a problem of extremely low compatibility with other resins and low adhesiveness.

Patent document 3 describes a method of mixing a rubber component to impart flexibility to a polyphenylene ether resin, but since only a polyphenylene ether resin or a rubber component is poor in adhesion, an epoxy resin has to be added. Epoxy resins have a problem that, although they have excellent adhesion, they generate alcoholic hydroxyl groups having high polarity during the reaction, and thus they deteriorate dielectric properties as in the case of the phenoxy resins.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent application laid-open No. 2005-001274

[ patent document 2] Japanese patent application laid-open No. 2014-060449

[ patent document 3] Japanese patent application laid-open No. 2010-222408.

Disclosure of Invention

[ problems to be solved by the invention ]

The present invention has been made in view of the above problems, and an object of the present invention is to provide a random copolymer compound having excellent film formability, high heat resistance and adhesiveness, and low dielectric constant and dielectric loss tangent, a terminal-modified polymer compound, and a resin composition containing the same.

[ means for solving the problems ]

As a result of extensive studies, the present inventors have found that a random copolymer compound comprising a polyphenylene ether resin having a relatively low molecular weight and phenolic hydroxyl groups at both ends, an aliphatic polymer having alcoholic hydroxyl groups at both ends, and a binder, and a terminal-modified polymer compound obtained by modifying the terminals of the random copolymer compound with a compound having an unsaturated double bond satisfy the above-mentioned requirements, and have completed the present invention.

That is, the present invention pertains to:

(1) a random copolymer compound which is a random copolymer compound of the following (A), (B) and (C),

(A) a polyphenylene ether resin having phenolic hydroxyl groups at both ends,

(B) An aliphatic polymer having alcoholic hydroxyl groups at both ends, and

(C) an acid dichloride compound belonging to a binder,

and the mole number a of the polyphenylene ether resin (A), the mole number B of the aliphatic polymer (B) and the mole number C of the acid dichloride compound (C) belonging to the binder satisfy the relationship of (a + B) > C.

(2) The random copolymer compound according to the above (1), wherein the molar number a and the molar number b satisfy a relationship of a > b.

(3) The random copolymer compound according to the above item (1), which is represented by the following formula (1);

in the formula (1), RA represents a divalent linking group obtained by removing two hydrogen atoms from the phenolic hydroxyl groups at both ends of (a) the polyphenylene ether resin having phenolic hydroxyl groups at both ends, and RB represents a divalent linking group obtained by removing two hydrogen atoms from the alcoholic hydroxyl groups at both ends of (B) the aliphatic polymer having alcoholic hydroxyl groups at both ends; l represents a divalent linking group represented by the following formula (2),

in the formula (2), RC represents a divalent linking group obtained by removing two acid chloride groups from (C) an acid chloride compound belonging to the binder; d and e are average values of the number of repeating units and each independently represents a real number in the range of 1 to 100.

(4) The random copolymer compound according to the above item (3), wherein RA is a divalent linking group represented by the following formula (3);

in the formula (3), X represents a divalent linking group obtained by removing two phenolic hydroxyl groups from a compound having two phenolic hydroxyl groups, R independently represents a methyl group, an ethyl group, a propyl group, an allyl group or a phenyl group, g and h are average values of the number of repeating units and independently represent real numbers in the range of 1 to 100, and y independently represents an integer of 1 to 4.

(5) The random copolymer compound according to the above (4), wherein X is a divalent linking group obtained by removing two phenolic hydroxyl groups from bisphenol A, tetramethylbisphenol A, bisphenol F or 4, 4' -biphenol.

(6) The random copolymer compound according to any one of the above (3) to (5), wherein RB is a divalent linking group obtained by removing two hydrogen atoms from alcoholic hydroxyl groups at both ends of a polybutadiene rubber having alcoholic hydroxyl groups at both ends.

(7) A terminal-modified polymer compound which is a reactant of the random copolymer compound described in any one of the above (1) to (6) and (D) a compound having a substituent reactive with a hydroxyl group and an unsaturated double bond group.

(8) The terminal-modified polymer compound according to the above item (7), wherein the compound (D) having a substituent reactive with a hydroxyl group and an unsaturated double bond group is a compound having an acid chloride group and an unsaturated double bond group, a compound having an isocyanate group and an unsaturated double bond group, or a compound having a chlorodimethylsilyl group and an unsaturated double bond group.

(9) The terminal-modified polymer compound according to the above (8), which is a compound represented by the following formula (4);

in formula (4), RA, RB, L, d, and e have the same meanings as RA, RB, L, d, and e in formula (1) described in the preceding item (3). Z independently represents a substituent represented by the following formula (5-1), (5-2) or (5-3);

in the formula (5-1), RD represents a residue obtained by removing an acid chloride group from a compound having an acid chloride group and an unsaturated double bond in one molecule; in the formula (5-2), RE represents a residue obtained by removing an isocyanate group from a compound having an isocyanate group and an unsaturated double bond group in one molecule; in the formula (5-3), RF represents a residue obtained by removing a chlorodimethylsilyl group from a compound having a chlorodimethylsilyl group and an unsaturated double bond in one molecule.

(10) A resin composition comprising the random copolymer compound according to any one of the above (1) to (6) or the terminal-modified polymer compound according to any one of the above (7) to (9), and a radical initiator.

(11) A film-like adhesive comprising the resin composition as recited in the aforementioned item (10).

(12) A cured product of the resin composition according to item (10) above or the film-like adhesive according to item (11) above.

[ Effect of the invention ]

According to the present invention, a random copolymer compound which can be easily formed into a thin film shape by a casting method and can be formed into a cured product by a resin composition using a radical initiator in combination, and a terminal-modified polymer compound which are excellent in properties such as flexibility, heat resistance, water resistance, dielectric properties, and adhesiveness can be provided.

Detailed Description

Embodiments of the present invention are described below.

< random copolymer Compound >

The polyphenylene ether resin (hereinafter, also referred to simply as "component a") having phenolic hydroxyl groups at both ends, which is (a) a raw material of the random copolymer compound of the present invention, may generally have a structure represented by the following formula (8).

In the formula (8), X represents a divalent linking group obtained by removing two phenolic hydroxyl groups from a compound having two phenolic hydroxyl groups. Specific examples of the compound having two phenolic hydroxyl groups include bisphenol a, tetramethylbisphenol a, bisphenol F, 4' -biphenol, and the like.

In the formula (8), R represents a methyl group, an ethyl group, a propyl group, an allyl group or a phenyl group.

In formula (8), y represents an integer of 1 to 4.

In formula (8), g and h are average values of the number of repeating units, and each independently represents a real number in the range of 1 to 100.

(A) While commercially available products having a number average molecular weight of several thousand to several hundred thousand are generally available as the component (b), the random copolymer compound of the present invention is preferably a product having a number average molecular weight of ten thousand or less as a raw material. (A) Specific examples of the component (A) in the market products include, but are not limited to, NORYL SA90 (number average molecular weight: 1,700) manufactured by SABIC contract Co., Ltd.

The molecular weight in the present specification refers to a value obtained in terms of polystyrene from the measurement result of Gel Permeation Chromatography (GPC).

Examples of the aliphatic polymer (B) having alcoholic hydroxyl groups at both ends (hereinafter, also simply referred to as "component (B)") which is a raw material of the random copolymer compound of the present invention include a butadiene copolymer having alcoholic hydroxyl groups at both ends, a hydrogenated butadiene copolymer having alcoholic hydroxyl groups at both ends, and the like. The number average molecular weight of these (B) components is usually 500 to 10,000, more preferably 750 to 7,000.

The amount of the component (a) and the component (B) used in the production of the random copolymer compound of the present invention is not particularly limited, but the component (B) may be used in an excess molar amount with respect to the component (a), the component (a) may be used in an excess molar amount with respect to the component (B), or the component (a) and the component (B) may be used in an excess molar amount with respect to the component (B), but the component (a) is preferably used in an excess molar amount with respect to the component (B), that is, the molar amount a of the component (a) and the molar amount B of the component (B) satisfy a > B relationship. When the amounts of the components (A) and (B) used satisfy the above-described preferable relationship, a random copolymer compound excellent in heat resistance and solvent solubility can be obtained.

The acid dichloride compound (hereinafter, also referred to simply as "component (C)") which is a binder as the raw material of the random copolymer compound of the present invention is not particularly limited as long as it is an acid dichloride compound, but specific examples thereof include phthaloyl dichloride, glutaryl chloride, isophthaloyl dichloride, terephthaloyl dichloride, oxalyl chloride, malonyl chloride, adipoyl chloride, azelaioyl chloride, sebacoyl chloride, azobenzene-4, 4 ' -dicarbonyl dichloride, 4 ' -biphenyldicarbonyl chloride, methylenesuccinyl chloride, hexahydroterephthaloyl dichloride, 2, 6-naphthalenedicarboxylic acid chloride, 4 ' -oxydibenzoyl chloride, 2, 5-furandicarbonyl dichloride, and dihydroxyacetyl chloride.

The random copolymer compound of the present invention has a structure in which the component (a) and the component (B) are randomly copolymerized with the component (C) interposed therebetween. Copolymerization is caused between the components (A) and (B) with the component (C) interposed therebetween, and between the components (A) and (B). The resulting copolymer has a structure in which these components are bonded by ester bonds.

The random copolymer compound of the present invention is a compound having a phenolic hydroxyl group and/or an alcoholic hydroxyl group at both ends, that is, a copolymer of components (a), (B) and (C) in which the number of moles a of component (a), the number of moles B of component (B) and the number of moles C of component (C) satisfy the relationship of (a + B) > C. The random copolymer compound can be a terminal-modified polymer compound of the present invention in which the structure of the terminal is further modified by using a compound having a phenolic hydroxyl group and/or an alcoholic hydroxyl group at both terminals and having a substituent reactive with the hydroxyl group (D) described later and an unsaturated double bond group by utilizing these terminal hydroxyl groups.

The random copolymer compound of the present invention is preferably a compound represented by the following formula (1).

In formula (1), RA represents a divalent linking group obtained by removing two hydrogen atoms from phenolic hydroxyl groups at both ends of (a) a polyphenylene ether resin having phenolic hydroxyl groups at both ends, RB represents a divalent linking group obtained by removing two hydrogen atoms from alcoholic hydroxyl groups at both ends of (B) an aliphatic polymer having alcoholic hydroxyl groups at both ends, L represents a divalent linking group represented by formula (2) below, and d and e are average values of the number of repeating units and independently represent real numbers in the range of 1 to 100, respectively.

In the formula (2), RC represents a divalent linking group obtained by removing two acid chloride groups (-COCl groups) from (C) an acid dichloride compound which is a binder.

The random copolymer compound of the present invention is more preferably a compound in which RA in the formula (1) is a divalent linking group represented by the following formula (3).

In formula (3), X represents a divalent linking group obtained by removing two phenolic hydroxyl groups from a compound having two phenolic hydroxyl groups, R each independently represents a methyl group, an ethyl group, a propyl group, an allyl group, or a phenyl group, g and h are average values of the number of repeating units and each independently represent a real number in a range of 1 to 100, and y each independently represents an integer of 1 to 4.

Further, the random copolymer compound of the present invention is more preferably a compound in which X in the formula (3) is a divalent linking group obtained by removing two hydroxyl groups from bisphenol a, tetramethylbisphenol a, bisphenol F, or 4, 4' -biphenol.

Further, the random copolymer compound of the present invention is more preferably a compound in which RB in the above formula (1) is a divalent linking group obtained by removing two hydrogen atoms from alcoholic hydroxyl groups at both ends of a polybutadiene rubber having alcoholic hydroxyl groups at both ends.

< end-modified Polymer Compound >

The terminal-modified polymer compound of the present invention is a compound obtained by modifying a phenolic hydroxyl group and/or an alcoholic hydroxyl group at a terminal of the random copolymer compound of the present invention with (D) a compound having a substituent reactive with a hydroxyl group and an unsaturated double bond group (hereinafter, also referred to simply as a "(D) component"). The modification is caused by the reaction of a hydroxyl group at the terminal of the random copolymer compound and a substituent reactive with the hydroxyl group of the component (D), and both terminals of the random copolymer compound may be modified or only one terminal may be modified.

The component (D) used for the terminal modification of the random copolymer compound is not particularly limited as long as it is a compound having a substituent reactive with a hydroxyl group and an unsaturated double bond group in one molecule, but is preferably a compound having an acid chloride group and an unsaturated double bond group in one molecule, a compound having an isocyanate group and an unsaturated double bond group in one molecule, or a compound having a chlorodimethylsilyl group and an unsaturated double bond group in one molecule.

The "unsaturated double bond group" in the present specification is not particularly limited as long as it is a substituent group having a carbon-carbon double bond, and examples thereof include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclohexenyl group, and a heptenyl group, and a vinyl group or an allyl group is preferable.

Specific examples of the compound having an acid chloride group and an unsaturated double bond group in one molecule include methacryloyl chloride and acryloyl chloride.

Specific examples of the compound having an isocyanate group and an unsaturated double bond group in one molecule include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 2- [ (3, 5-dimethylpyrazolyl) carbonylamino ] ethyl methacrylate, 1- (bisacryloxymethyl) ethyl isocyanate, vinylbenzyl chloride, and 3-isopropenyl- α, α -dimethylbenzyl isocyanate.

Specific examples of the compound having a chlorodimethylsilyl group and an unsaturated double bond group in one molecule include vinyldimethylchlorosilane and allyldimethylchlorosilane.

The terminal-modified polymer compound of the present invention is preferably a compound represented by the following formula (4).

In formula (4), RA, RB, L, d and e are as defined in formula (1). Z independently represents a substituent represented by the following formula (5-1), (5-2) or (5-3).

In the formula (5-1), RD is a residue obtained by removing an acid chloride group from a compound having an acid chloride group and an unsaturated double bond in one molecule. In the formula (5-2), RE represents a residue obtained by removing an isocyanate group from a compound having an isocyanate group and an unsaturated double bond group in one molecule. In the formula (5-3), RF represents a residue obtained by removing a chlorodimethylsilyl group from a compound having a chlorodimethylsilyl group and an unsaturated double bond in one molecule.

< method for producing random copolymer compound and terminal-modified Polymer Compound >

Next, the methods for producing the random copolymer compound and the terminal-modified polymer compound of the present invention will be described.

The random copolymer compound of the present invention can be obtained by uniformly dissolving the components (a) and (B) in a solvent, and then adding the component (C) to the mixture to react the mixture under heating. More preferably, the number of moles of the component (A) is larger than the number of moles of the component (B). The terminal-modified polymer compound of the present invention can be obtained by adding component (D) to the random copolymer compound of the present invention obtained as described above and reacting the mixture under heating. Examples of the solvent include toluene, xylene, Methyl isobutyl ketone, cyclopentanone, cyclohexanone, N-methylpyrrolidone (Methyl pyrrolidone), dimethylformamide, and dimethylacetamide, and a mixed solvent thereof is also acceptable, and particularly, toluene having a low boiling point and being easily dried is preferable. In the reaction in which the component (C) is added and the reaction in which the component (D) is added, the reaction temperature is usually 50 to 150 ℃ and preferably 60 to 140 ℃. The reaction time is more preferably 5 to 60 hours.

In order to promote the reaction, a catalyst may be used in combination. The catalyst is preferably an organic basic compound such as triethylamine, triallylamine or pyridine. When an organic base catalyst is used, hydrochloric acid generated by the reaction forms a salt with an organic base, so that the hydrochloric acid does not corrode a reaction apparatus and the reaction can be carried out safely. The salt formed can be easily removed by filtration after the reaction is completed. The organic base catalyst is used not only as a catalyst when the component (D) is an acid chloride compound but also as a catalyst when an isocyanate compound or a dimethylchlorosilane compound is used as the component (D). The amount of the catalyst used is generally 0.1 to 200% by mass, and more preferably 0.5 to 100% by mass, based on the total amount of the reactants.

In order to prevent the polymerization reaction between double bonds in the molecule during the reaction, it is preferable to add a polymerization inhibitor in advance before the reaction. Specific examples of the polymerization inhibitor include p-methoxyphenol and methylhydroquinone.

The molecular weight ranges of the random copolymer compound and the terminal-modified polymer compound of the present invention obtained in this manner are preferably 10,000 to 200,000, more preferably 15,000 to 150,000, in terms of weight average molecular weight in terms of polystyrene in GPC. When the molecular weight is smaller than the above range, the film forming ability may be insufficient, and when the molecular weight is larger, the viscosity may be high and the coating may be difficult.

< resin composition >

The resin composition of the present invention comprises: a mixture of either or both of the random copolymer compound and the terminal-modified polymer compound of the present invention and a radical initiator. The amount of the radical initiator used in the resin composition of the present invention is 0.1 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, based on 100 parts by mass of the total of the resin components. Representative examples of the radical initiator include benzoyl peroxide, cumyl hydroperoxide, 2, 5-dimethylhexane-2, 5-dihydroperoxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, di-t-butylperoxide, t-butylcumyl peroxide, α -bis (t-butylperoxy-m-isopropyl) benzene, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, diisopropylphenyl peroxide, di-t-butylperoxy isophthalate, t-butylperoxy benzoate, 2-bis (t-butylperoxy) butane, 2-bis (t-butylperoxy) octane, 2, 5-dimethyl-2, peroxides such as 5-bis (benzoylperoxy) hexane, bis (trimethylsilyl) peroxide, and trimethylsilyltriphenylsilyl peroxide.

An organic solvent may be used in combination with the resin composition of the present invention. Specific examples of the organic solvent include aromatic solvents such as toluene and xylene, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether monoacetate, and propylene glycol monobutyl ether, ketone solvents such as Methyl ethyl ketone, Methyl isobutyl ketone, cyclopentanone, and cyclohexanone, lactones such as γ -butyrolactone and γ -valerolactone, amide solvents such as N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide, and N, N-dimethylimidazolidinone, and sulfones such as tetramethylene sulfone. The content of the organic solvent in the resin composition of the present invention is usually 90% by mass or less, and preferably 30 to 80% by mass in the resin composition.

The storage stability is improved, and the resin composition of the present invention may be used in combination with a polymerization inhibitor. As the polymerization inhibitor, generally known polymerization inhibitors can be used, and examples thereof include quinones such as hydroquinone, methylhydroquinone, p-benzoquinone, Chloranil (Chloranil), and trimethylquinone, aromatic diols, and di-t-butylhydroxytoluene.

The resin composition of the present invention may contain a radically polymerizable compound for the purpose of improving heat resistance and the like. Specifically, it is selected from the group consisting of triallyl isocyanurate, triallyl cyanurate, divinylbenzene, divinyl isophthalate, N-phenyl-maleimide, N-phenyl-methylmaleimide, N-phenyl-chloromaleimide, N-p-chlorophenyl-maleimide, N-p-methoxyphenyl-maleimide, N-p-methylphenyl-maleimide, N-p-nitrophenyl-maleimide, N-p-phenoxyphenyl-maleimide, N-p-phenylaminophenyl-maleimide, N-p-phenoxycarbonylphenyl-maleimide, 1-maleimide-4-acetoxysuccinimide-benzene, and mixtures thereof, 4-maleimide-4 '-acetoxysuccinimide-diphenylmethane, 4-maleimide-4' -acetoxysuccinimide-diphenyl ether, 4-maleimide-4 '-acetamide-diphenyl ether, 2-maleimide-6-acetamide-pyridine, 4-maleimide-4' -acetamide-diphenylmethane and N-p-phenylcarbonylphenyl-maleimide N-ethylmaleimide, N-2.6-ditolylmaleimide, N-cyclohexylmaleimide, N-2, 3-ditolymaleimide, 2, 6-ditolymaleimide, N-phenylmaleimide, 4, 4' -bismaleimide diphenylmethane and combinations thereof.

The resin composition of the present invention can be used by blending fillers or additives in an amount within a range not impairing the original properties thereof, depending on the purpose of imparting desired properties to the resin composition for use. The filler may be in the form of a fiber or a powder, and examples thereof include silica, carbon black, alumina, talc, mica, glass beads, and glass hollow spheres.

The resin composition of the present invention may also contain a flame retardant compound, an additive, and the like. These are not particularly limited as long as they are flame retardant compounds, additives, and the like which are generally used. Examples of the flame retardant compound include bromine compounds such as 4, 4-dibromobiphenyl, phosphate esters, melamine phosphate, phosphorus-containing epoxy resins, nitrogen compounds such as melamine and benzoguanamine, Oxazine (Oxazine) ring-containing compounds, and silicon-based compounds. The additives may be used by appropriately combining an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent brightener, a photosensitizer, a dye, a pigment, a thickener, a lubricant, an antifoaming agent, a dispersant, a leveling agent, a gloss agent, and the like as needed.

The resin composition of the present invention can be used by coating or impregnating various substrates. For example, a film-like adhesive obtained by applying a resin composition containing an organic solvent to a PET film and then removing the organic solvent can be used as an interlayer insulating layer of a multilayer printed board. In addition, a polyimide film having a film-like adhesive provided on the surface thereof by the same method as described above was used as the cover layer, and a copper foil having a film-like adhesive provided on the surface thereof by the same method as described above was used as the resin-coated copper foil. The prepreg can be used as a printed circuit board or a prepreg of CFRP by impregnating glass cloth, cellophane, carbon fiber, various nonwoven fabrics, and the like.

These interlayer insulating layers, cover layers, resin-coated copper foils, prepregs, and the like can be molded by heating and pressing with a hot press or the like to form a cured product.

[ examples ]

The present invention will be described in more detail below with reference to examples and comparative examples. The present invention is not limited to these examples.

Example 1 (Synthesis of random copolymer Compound 1 of the present invention)

In a flask equipped with a thermometer, a cooling tube and a stirrer, 24 parts (0.0141 mol) of polyphenylene ether resin (average molecular weight 1,700, manufactured by SA-90, SABIC Corp.) having phenolic hydroxyl groups at both ends, 16 parts (0.0053 mol) of polybutadiene resin (average molecular weight 3,000, manufactured by G-3000 Nippon Kazada corporation) having alcoholic hydroxyl groups at both ends, 50 parts of toluene and 0.2 part of methoxyphenol were charged, and after stirring and dissolving, 5 parts of triethylamine as a catalyst was added. The solution obtained above was heated to 105 ℃ and 3.29 parts (0.0162 mol) of terephthaloyl dichloride dissolved in 30 parts of toluene was added dropwise over 10 minutes, followed by reaction at 105 ℃ for 2 hours. Thereafter, triethylamine hydrochloride produced by the reaction was removed by filtration, the obtained filtrate was concentrated under reduced pressure and remaining triethylamine was distilled off together with toluene, and 120 parts of a 35% toluene solution of the random copolymer compound 1 of the present invention was obtained by adjusting the amount of toluene. The resulting random copolymer compound 1 had a weight average molecular weight of 83,000 and a number average molecular weight of 10,000. The weight average molecular weight and the number average molecular weight are values obtained in terms of polystyrene as a result of measurement by Gel Permeation Chromatography (GPC).

Example 2 (Synthesis of terminal-modified Polymer Compound 1 of the present invention)

In a flask equipped with a thermometer, a cooling tube and a stirrer, 24 parts (0.0141 mol) of polyphenylene ether resin (average molecular weight 1,700, manufactured by SA-90, SABIC Corp.) having phenolic hydroxyl groups at both ends, 16 parts (0.0053 mol) of polybutadiene resin (average molecular weight 3,000, manufactured by G-3000 Nippon Kazada corporation) having alcoholic hydroxyl groups at both ends, 50 parts of toluene and 0.2 part of methoxyphenol were charged, and after stirring and dissolving, 5 parts of triethylamine as a catalyst was added. The solution obtained above was heated to 105 ℃ and 3.29 parts (0.0162 mol) of terephthaloyl dichloride dissolved in 30 parts of toluene was added dropwise over 10 minutes, followed by reaction at 105 ℃ for 2 hours. After the temperature in the system was decreased to 80 ℃, 0.678 part (0.0064 mol) of methacryloyl chloride was added to the reaction solution, and the reaction was further carried out at 80 ℃ for 2 hours. Thereafter, triethylamine hydrochloride produced by the reaction was removed by filtration, the obtained filtrate was concentrated under reduced pressure, and remaining triethylamine was distilled off together with toluene, and the amount of toluene was adjusted to obtain 123 parts of a 35% toluene solution of the terminal-modified polymer compound 1 of the present invention. The weight-average molecular weight of the resulting terminal-modified polymer compound 1 was 85,000, and the number-average molecular weight was 11,000.

Example 3 (Synthesis of terminal-modified Polymer Compound 2 of the present invention)

In a flask equipped with a thermometer, a cooling tube and a stirrer, 24 parts (0.0141 mol) of polyphenylene ether resin (average molecular weight 1,700, manufactured by SA-90, SABIC Corp.) having phenolic hydroxyl groups at both ends, 16 parts (0.0053 mol) of polybutadiene resin (average molecular weight 3,000, manufactured by G-3000 Nippon Kazada corporation) having alcoholic hydroxyl groups at both ends, 50 parts of toluene and 0.2 part of methoxyphenol were charged, and after stirring and dissolving, 5 parts of triethylamine was added as a catalyst. The solution obtained above was heated to 105 ℃ and 3.29 parts (0.0162 mol) of terephthaloyl dichloride dissolved in 30 parts of toluene was added dropwise over 10 minutes, and further reacted at 105 ℃ for 2 hours. After the temperature in the system was decreased to 80 ℃, 1.005 parts (0.0064 mol) of 2-isocyanatoethyl methacrylate was added and the reaction was further carried out at 80 ℃ for 2 hours. Thereafter, triethylamine hydrochloride produced by the reaction was removed by filtration, the obtained filtrate was concentrated under reduced pressure, and remaining triethylamine was distilled off together with toluene, and the amount of toluene was adjusted to obtain 123 parts of a 35% toluene solution of the terminal-modified polymer compound 2 of the present invention. The weight-average molecular weight of the resulting terminal-modified polymer compound 2 was 84,500, and the number-average molecular weight was 12,000.

Example 4 (Synthesis of terminal-modified Polymer Compound 3 of the present invention)

In a flask equipped with a thermometer, a cooling tube and a stirrer, 24 parts (0.0141 mol) of polyphenylene ether resin (average molecular weight 1,700, manufactured by SA-90, SABIC Corp.) having phenolic hydroxyl groups at both ends, 16 parts (0.0053 mol) of polybutadiene resin (average molecular weight 3,000, manufactured by G-3000 Nippon Kazada corporation) having alcoholic hydroxyl groups at both ends, 50 parts of toluene and 0.2 part of methoxyphenol were charged, and after stirring and dissolving, 5 parts of triethylamine as a catalyst was added. The solution obtained above was heated to 105 ℃ and 3.29 parts (0.0162 mol) of terephthaloyl dichloride dissolved in 30 parts of toluene was added dropwise over 10 minutes, followed by reaction at 105 ℃ for 2 hours. After the temperature in the system was decreased to 80 ℃, 0.768 parts (0.0064 mol) of vinyldimethyldichlorosilane was added and the reaction mixture was further reacted at 80 ℃ for 2 hours. Thereafter, triethylamine hydrochloride produced by the reaction was removed by filtration, the obtained filtrate was concentrated under reduced pressure, and remaining triethylamine was distilled off together with toluene, and the amount of toluene was adjusted to obtain 123 parts of a 35% toluene solution of the terminal-modified polymer compound 3 of the present invention. The resulting terminal-modified polymer compound 3 had a weight-average molecular weight of 87,000 and a number-average molecular weight of 13,000.

Examples 5 to 8

To 10 parts each of the solutions of the random copolymer compound 1 and the terminal-modified polymer compounds 1 to 3 obtained in examples 1 to 4, 0.06 part of diisopropylphenyl peroxide as a radical initiator was added and uniformly mixed, whereby resin compositions 1 to 4 of the present invention were obtained. The resin compositions 1 to 4 of the present invention obtained as described above were coated on a polyimide film with a thickness of 200 μm using an APPLICATOR (application), heated at 90 ℃ for 10 minutes to dry the solvent, and then further heated in a vacuum oven at 180 ℃ for 1 hour, whereby hardened products of the resin compositions 1 to 4 of the present invention were obtained. The thickness of the cured product obtained was 75 μm, and the cured product had sufficient flexibility and strength.

(measurement of tensile Strength, modulus of elasticity, glass transition temperature and dielectric Properties)

The cured products of the resin compositions 1 to 4 of the present invention obtained in examples 5 to 8 were measured for tensile strength and modulus of elasticity using Autograph AGX-50 (manufactured by shimadzu corporation), for glass transition temperature using dynamic viscoelasticity measuring apparatus EXSTAR6000 (manufactured by SEIKO EPSON corporation), and for dielectric constant and dielectric loss tangent at 1GHz using a network analyzer 8719ET (manufactured by AGILENT techlogy) by a cavity resonance method. The results are shown in table 1.

(measurement of adhesive Strength)

The resin compositions 1 to 4 of the present invention obtained in examples 5 to 8 were applied to the surface of a high-frequency low-roughness copper foil (CF-T4X-SV, manufactured by Futian Metal foil powder Co., Ltd.) having a thickness of 12 μm by an applicator to a thickness of 50 μm, and the coated surface was heated at 90 ℃ for 10 minutes to dry the solvent, thereby obtaining copper foils each having a film-like adhesive composed of the resin composition of the present invention. On the adhesive surface of the copper foil obtained above, the same copper foil as described above was laminated on the gasket surface thereof, and cured in a vacuum press at a temperature of 180 ℃ under a pressure of 3MPa for 1 hour, and then the 90 ° peel strength (adhesive strength) between the copper foil and the cured product of the resin composition was measured using AUTOGRAPH AGX-50 (manufactured by Shimadzu corporation). The results are shown in table 1.

[ Table 1]

TABLE 1 evaluation results of resin compositions

	Example 5	Example 6	Example 7	Example 8
						Resin composition 1	Resin composition 2	Resin composition 3	Resin composition 4
Random copolymer compound	1
					Terminal-modified polymer compound		1	2	3
Tensile Strength (MPa)	30.4	36.6	35.4	38
					Modulus of elasticity (GPa)	1	1.2	1.1	1.3
Glass transition temperature (. degree. C.)	184	188	188	186
					Dielectric constant (1GHz)	2.53	2.64	2.67	2.63
Dielectric loss tangent (1GHz)	0.0027	0.0023	0.0023	0.0022
					Adhesive Strength (N/mm)	0.7	0.82	0.83	0.8

As described above, the resin composition and cured product thereof containing the random copolymer compound or the terminal-modified polymer compound of the present invention have high flexibility and exhibit excellent heat resistance, dielectric properties, and adhesion.