US-12624220-B2 - Composition and cured product thereof

US12624220B2US 12624220 B2US12624220 B2US 12624220B2US-12624220-B2

Abstract

A varnish having low viscosity and a cured product thereof having a high degree of cross-linking, exhibiting excellent low dielectric properties and mechanical properties at high temperature, and a low coefficient of linear thermal expansion are provided. A varnish comprising an olefin-aromatic vinyl compound-aromatic polyene copolymerized oligomer satisfying specific conditions, one or more selected from the following (a) to (c), and (d) a solvent: (a) a curing agent; (b) one or a plurality of resins selected from a hydrocarbon-based elastomer, a polyphenylene ether-based resin, an olefin-aromatic vinyl compound-aromatic polyene copolymer, and an aromatic polyene-based resin; and (c) a polar monomer; and a cured product of the varnish.

Inventors

Toru Arai

Assignees

DENKA COMPANY LIMITED

Dates

Publication Date: 20260512
Application Date: 20210713
Priority Date: 20200715

Claims (20)

1 . A varnish, comprising: an olefin-aromatic vinyl compound-aromatic polyene copolymerized oligomer; one or more selected from the group consisting of the following (a) to (c): (a) a curing agent, (b) one or a plurality of resins selected from the group consisting of a hydrocarbon-based elastomer, a polyphenylene ether-based resin, an olefin-aromatic vinyl compound-aromatic polyene copolymer, and an aromatic polyene-based resin, and (c) a polar monomer; and a solvent, wherein the olefin-aromatic vinyl compound-aromatic polyene copolymerized oligomer satisfies all of the following conditions (1) to (4): (1) a number average molecular weight of the copolymerized oligomer is 500 or more and less than 12000; (2) the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 or more and 20 or less carbon atoms, and a content of a unit of the aromatic vinyl compound monomer is 0 mass % or more and 90 mass % or less; (3) the aromatic polyene is one or more selected from the group consisting of polyenes having 5 or more and 20 or less carbon atoms, and an average number of the vinyl groups and/or the vinylene groups derived from a unit of the aromatic polyene is 1.5 or more and less than 10 per oligomer, wherein the average number is determined using the number average molecular weight; and (4) the olefin is one or more selected from olefins having 2 or more and 20 or less carbon atoms, and a total of units of the olefin monomer, the aromatic vinyl compound, and the aromatic polyene monomer is 100 mass %, and wherein a cured product of the olefin-aromatic vinyl compound-aromatic polyene copolymerized oligomer alone has a storage elastic modulus at 300° C. of 1×10 6 Pa or more.
2 . The varnish according to claim 1 , wherein the varnish has at least a resin concentration of 33 mass % or more and a viscosity measured at 25° C. and 1 sec −1 of 2000 mPa·s or less.
3 . A cured product of the varnish according to claim 1 .
4 . A molded product, comprising: an olefin-aromatic vinyl compound-aromatic polyene copolymerized oligomer satisfying all of the following conditions (1) to (4): (1) a number average molecular weight of the copolymerized oligomer is 500 or more and less than 12000; (2) the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 or more and 20 or less carbon atoms, and a content of a unit of the aromatic vinyl compound monomer is 0 mass % or more and 90 mass % or less; (3) the aromatic polyene is one or more selected from polyenes having 5 or more and 20 or less carbon atoms and having a plurality of vinyl groups and/or vinylene groups in the molecule, and an average number of the vinyl groups and/or the vinylene groups derived from a unit of the aromatic polyene is 1.5 or more and less than 10 per oligomer, wherein the average number is determined using the number average molecular weight; and (4) the olefin is one or more selected from olefins having 2 or more and 20 or less carbon atoms, and a total of units of the olefin monomer, the aromatic vinyl compound, and the aromatic polyene monomer is 100 mass %, and wherein a cured product of the olefin-aromatic vinyl compound-aromatic polyene copolymerized oligomer alone has a storage elastic modulus at 300° C. of 1×10 6 Pa or more.
5 . The molded product according to claim 4 , further comprising one or more selected from the group consisting of the following (a) to (c): (a) a curing agent; (b) one or a plurality of resins selected from the group consisting of a hydrocarbon-based elastomer, a polyphenylene ether-based resin, an olefin-aromatic vinyl compound-aromatic polyene copolymer, and an aromatic polyene-based resin; and (c) a polar monomer.
6 . The molded product according to claim 3 , further comprising one or more selected from the group consisting of the following (e) to (g): (e) a filler; (f) a flame retardant; and (g) a surface modifier.
7 . The molded product according to claim 4 , further comprising one or more selected from the group consisting of the following (e) to (g): (e) a filler; (f) a flame retardant; and (g) a surface modifier.
8 . The cured product according to claim 3 , being an electrically insulating material.
9 . The cured product of the molded product according to claim 4 .
10 . The cured product according to claim 9 , being an electrically insulating material.
11 . The cured product according to claim 3 , wherein the product does not contain solvent.
12 . The cured product according to claim 9 , wherein the product does not contain solvent.
13 . An electrically insulating material, comprising the cured product according to claim 3 .
14 . An electrically insulating material, comprising the cured product according to claim 9 .
15 . A CCL circuit board, an FCCL circuit board, an interlayer insulating layer or an interlayer adhesive layer, comprising the cured product according to claim 3 .
16 . A CCL circuit board, an FCCL circuit board, an interlayer insulating layer or an interlayer adhesive layer, comprising the cured product according to claim 9 .
17 . A cured product, comprising: an olefin-aromatic vinyl compound-aromatic polyene copolymerized oligomer, as a product of a reaction using a single-site-coordinated polymerization catalyst composed of a transition metal compound represented by the following general formula (1) and a co-catalyst: wherein M is zirconium or hafnium; Cp1 and Cp2 are cyclopentadienyl groups having no substituent, or cyclopentadienyl groups having one or two alkyl substituents having no cyclic structure; the Cp1 and Cp2 are the same or different from each other; one of the Cp1 and Cp2 groups is optionally an indenyl group having no substituent, or an indenyl group having one or two alkyl substituents having no cyclic structure; Y is carbon, silicon, germanium or boron having a bond with Cp1 and Cp2 and having a hydrogen atom or a substituent; the substituents are different from each other or the same, and optionally have a cyclic structure; X is selected from the group consisting of hydrogen, halogens, alkyl groups and aryl groups, or two X are bonded to each other to form a diene group, and wherein a cured product of the olefin-aromatic vinyl compound-aromatic polyene copolymerized oligomer alone has a storage elastic modulus at 300° C. of 1×10 6 Pascals (Pa) or more.
18 . A method for manufacturing a varnish, the method comprising the steps of: obtaining an olefin-aromatic vinyl compound-aromatic polyene copolymerized oligomer, as a product of a reaction using a single-site-coordinated polymerization catalyst composed of a transition metal compound represented by the following general formula (1) and a co-catalyst: wherein M is zirconium or hafnium; Cp1 and Cp2 are cyclopentadienyl groups having no substituent, or cyclopentadienyl groups having one or two alkyl substituents having no cyclic structure; the Cp1 and Cp2 are the same or different from each other; one of the Cp1 and Cp2 groups is optionally an indenyl group having no substituent, or an indenyl group having one or two alkyl substituents having no cyclic structure; Y is carbon, silicon, germanium or boron having a bond with Cp1 and Cp2 and having a hydrogen atom or a substituent; the substituents are different from each other or the same, and optionally have a cyclic structure; X is selected from the group consisting of hydrogen, halogens, alkyl groups and aryl groups, or two X are bonded to each other to form a diene group; and adding a solvent to the olefin-aromatic vinyl compound-aromatic polyene copolymerized oligomer to prepare a varnish, and wherein a cured product of the olefin-aromatic vinyl compound-aromatic polyene copolymerized oligomer alone has a storage elastic modulus at 300° C. of 1×10 6 Pascals (Pa) or more.
19 . A method for manufacturing a cured product of the varnish obtained by the method according to claim 18 , the method comprising the steps of: adding a peroxide to the varnish; and curing the varnish.
20 . The method according to claim 19 , further comprising: removing the solvent from the varnish.

Description

TECHNICAL FIELD The present invention relates to a composition and a cured product thereof. BACKGROUND ART Due to the shift of communication frequency to gigahertz bands and frequency bands higher than those, needs for insulating materials having low dielectric properties have increased. Polyolefins such as polyethylene and aromatic vinyl compound polymers such as polystyrene are known as materials exhibiting excellent low dielectric constant and low dielectric tangent due to having no polar groups in molecular structures. However, due to dependence of the heat resistance on the melting point of crystals or the glass transition temperature, they have a problem in the heat resistance as electric insulator, and due to being thermoplastic resins, they have a problem in a film forming process (Patent Literature 1). Although fluorine-based resins such as perfluoroethylene have characteristics excellent in low dielectric constant, low dielectric loss and heat resistance, device suitability is low due to difficulty in moldability and film formability. In addition, there is a problem in the adhesive strength with a copper foil of wiring. Meanwhile, although substrates and insulating materials using post-curable resins such as epoxy resins, unsaturated polyester resins, polyimide resins, and phenol resins have been widely used due to the heat resistance and easy handling, improvement is required as insulating materials for high frequencies due to relatively high dielectric constants and dielectric losses (Patent Literature 2). An electrically insulating material including graft or block copolymer including olefin-based and styrene-based polymer segments has been proposed (Patent Literature 3). The material focuses on the low dielectric constant and low dielectric loss essential to olefin-based or styrene-based hydrocarbon polymers. The production method includes general graft polymerization of commercially available polyethylene and polypropylene with a styrene monomer or a divinylbenzene monomer in the presence of a radical polymerization initiator. Such a method has problems of poor graft efficiency and insufficient uniformity of the polymer. Further, the resulting polymer contains a gel, so that there exist problems of poor processability and filling property. In addition, the material is a thermoplastic resin having insufficient heat resistance, so that an addition of a heat-resistant resin such as 4-methyl-1-pentene is required. Further, it is difficult to use the material in a molding method including applying the material to a predetermined place or filling a predetermined place with the material and then curing the material. In Patent Literature 4, an insulating layer including a crosslinked structure containing a hydrocarbon compound having a plurality of aromatic vinyl groups as a cross-linking component is described. The cured product of the cross-linking component specifically described in examples is rigid, so that it is presumed that filling with a large amount of filler is difficult. In Patent Literature 5, a cured product obtained from a specific polymerization catalyst, including an ethylene-olefin (aromatic vinyl compound)-polyene copolymer having specific composition and formulation and a non-polar vinyl compound copolymer, is shown. Although the cured product specifically described in examples of Patent Literature 5 has characteristics including low dielectric constant and low dielectric tangent, it is extremely soft, so that improvement in mechanical strength such as elastic modulus at normal temperature and high temperature is required. For use as thin film insulating materials such as interlayer insulating materials of FPC (flexible printed circuit board) and FCCL (flexible copper clad laminate) and coverlay applications, it is preferable to improve stability in dimensions such as thickness during a mounting process or during use after mounting. In Patent Literature 6, a cured product obtained from the similar specific polymerization catalyst, including an ethylene-olefin (aromatic vinyl compound)-polyene copolymer having specific composition and formulation and a non-polar vinyl compound copolymer is shown. A cured product of a composition containing a similar copolymer is also shown in Patent Literature 7. However, the ethylene-olefin (aromatic vinyl compound)-polyene copolymers described in Patent Literature 5 to 7, have a high molecular weight, so that the viscosity is high when dissolved in a solvent or monomer. Accordingly, when used as a varnish, improvement in the coatability and impregnation may be required. Further, in Patent Literature 5 to 7, no cured product of the ethylene-olefin (aromatic vinyl compound)-polyene copolymer alone or as a main component is described. Further, in Patent Literature 8, although a production method of an ethylene-styrene copolymer oligomer having a low molecular weight is disclosed, description on the production of an ethylene-styrene-divinylbenzene co