star polymer

Abstract

The present invention provides a star polymer which has an arm section derived from an arm polymer obtained by polymerizing a vinyl monomer, and a core section containing a structure derived from a polyfunctional alkenyl compound for cross-linking with the arm section, wherein the arm polymer is contained in an amount equal to 5-25 mol% of the structure derived from the polyfunctional alkenyl compound.

Description

[Technical Field]

[0001] The present disclosure relates to star polymers. [Background technology]

[0002] Acrylic polymers are usually used as adhesives for bonding substrates (Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2019-123885 [Patent Document 2] Special Publication No. 2020-527621 Summary of the Invention [Problem to be solved by the invention]

[0004] Conventional acrylic polymers do not have sufficient film-forming properties for different substrates, such as both metals and fluororesins, and therefore cannot function satisfactorily when used as adhesives.

[0005] An object of the present disclosure is to provide a polymer that has sufficient film-forming properties on heterogeneous substrates. [Means for solving the problem]

[0006] The present disclosure includes the following aspects. [1] An arm portion including a structure derived from an arm polymer, which is a polymer of a vinyl monomer; a core portion including a structure derived from a polyfunctional alkenyl compound that crosslinks the arm portions; The star polymer has the following formula: wherein the structure derived from the arm polymer is 5 to 25 mol % relative to the structure derived from the polyfunctional alkenyl compound. [2] The star polymer according to [1] above, wherein the vinyl monomer is a (meth)acrylic acid ester, a (meth)acrylamide, a styrene, or a vinyl ester. [3] The star polymer according to [1] or [2] above, wherein the arm polymer is a polymer synthesized by living radical polymerization. [4] The arm polymer has the formula (1): R c -(R b ) n -SC(=S)-R a (1) [In formula: R a is alkyl, phenyl, -SR a1 , -OR a2 , -NR a3 2. [ka] and; R a1 , R a2 , R a3 , R a4 , R a5 and R a6 are each independently 1-20 an alkyl group or a phenyl group; R a7 is a hydrogen or halogen atom, R b teeth, -CH2-CR 11 (-COOR 12 )- and R 11 is a hydrogen atom or a methyl group, R 12 is C 1-20 is an alkyl group, R c is R 16 -R 15 - and R 15 may be substituted C 1-6 is an alkylene group, R 16is a carboxyl group, a hydroxyl group, or a phenyl group, n is an integer from 1 to 1,000. The star polymer according to any one of the above [1] to [3], which is a polymer represented by the formula: [5] The arm polymer has the formula (2): R c '-(R b ) n -R a ' (2) [In formula: R a ' is a halogen atom; R b teeth, -CH2-CR 11 (-COOR 12 )- and R 11 is a hydrogen atom or a methyl group, R 12 is C 1-20 is an alkyl group, R c ' is R 18 -R 17 - and R 17 -CR 19 2- and R 19 are each independently a hydrogen atom, C 1-6 an alkyl group, a phenyl group, or a halogen atom; R 18 is R 18a -OCO-, a phenyl group, or a cyano group; R 18a may be substituted C 1-20 is an alkyl group, n is an integer from 1 to 1,000. The star polymer according to any one of the above [1] to [3], which is a polymer represented by the formula: [6] The star polymer according to any one of the above [1] to [5], wherein the polyfunctional alkenyl compound is a dialkenyl compound. [7] The dialkenyl compound has the formula (3): CH2=CR e -R d -CR e =CH2 [In formula: R d is a divalent organic group, R e is a hydrogen atom or a methyl group. The star polymer according to [6] above, which is a compound represented by the formula: [8] R d -R 22 -R 21 -R 23 - and R 21 is C 1-20 an alkylene group, a phenylene group, or —O—(C α H 2α O) β - and α is an integer from 1 to 6, β is an integer from 1 to 10, R 22 is a single bond, C 1-6 an alkylene group or —CO—; R 23 is a single bond, C 1-6 an alkylene group, or -CO-; The star polymer according to [7] above. [9] A resin laminate substrate having an adhesive layer, wherein the resin substrate is coated with the star polymer described in any one of [1] to [8] above, and the coating film has a water contact angle of 80 to 130 degrees.

[10] A coating agent for a laminated substrate having an adhesive layer according to [9] above, wherein the resin substrate has a water contact angle of 60 to 150 degrees.

[11] The coating agent for a laminated substrate having an adhesive layer according to [9] or

[10] above, wherein the resin substrate is a fluororesin substrate.

[12] A coated substrate comprising an adhesive layer in which the star polymer according to any one of the above [1] to [8] covers 80% or more of the surface area of ​​the substrate in solid form.

[13] The coated substrate having an adhesive layer according to

[12] above, wherein the solid content includes a star polymer.

[14] The coated substrate having an adhesive layer according to

[13] above, wherein the substrate is a resin substrate.

[15] The coated substrate having an adhesive layer according to

[14] above, wherein the resin substrate is a fluorine-containing substrate.

[16] A film formed on the coated substrate according to any one of the above

[12] to

[15] .

[17] A fluororesin substrate; An adhesive layer containing the star polymer according to any one of [1] to [8] above; an adherend layer selected from a metal layer, a non-fluorine resin layer, a fluorine resin layer, and an inorganic layer; The fluororesin substrate and the adherend layer are adhered to each other by the adhesive layer. Laminate.

[18] The laminate according to

[17] above, wherein the adherend layer is a metal layer.

[19] The laminate according to

[17] or

[18] above, wherein the fluororesin substrate is a substrate composed of polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkoxyethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, or vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer.

[20] The laminate according to any one of the above

[17] to

[19] , wherein the metal layer is a copper layer.

[21] The laminate according to any one of the above

[17] to

[20] , wherein the metal layer has a surface roughness Rz of 2 μm or less on the side to be bonded.

[22] A circuit board comprising the laminate according to any one of the above items

[17] to

[21] .

[23] The circuit board according to

[22] above, which is a high-frequency circuit board.

[24] A lining material comprising the laminate according to any one of the above

[17] to

[21] .

[25] A laminate tube comprising the laminate according to any one of the above

[17] to

[21] . [Effects of the Invention]

[0007] The star polymer of the present disclosure exhibits high film-forming properties on a variety of substrates, particularly on both metal substrates and resin substrates. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present disclosure provides a star polymer having arm portions including a structure derived from an arm polymer, which is a polymer of a vinyl monomer, and a core portion including a structure derived from a polyfunctional alkenyl compound that crosslinks the arm portions, wherein the arm polymer-derived structure accounts for 5 to 25 mol % of the structure derived from the polyfunctional alkenyl compound.

[0009] The star polymer can be obtained by reacting an arm polymer, which is a polymer of a vinyl monomer, with a polyfunctional alkenyl compound to crosslink the arm polymer.

[0010] [Vinyl Monomer] The vinyl monomer is a monomer having a vinyl group, and examples thereof include (meth)acrylic acid esters, (meth)acrylamides, styrenes, and vinyl esters.

[0011] As used herein, "(meth)acrylic acid ester" encompasses "acrylic acid ester" and "methacrylic acid ester." Similarly, "(meth)acrylamide" encompasses "acrylamide" and "methacrylamide."

[0012] The (meth)acrylic acid ester is preferably a (meth)acrylic acid alkyl ester in which the alkyl group has 1 to 30 carbon atoms.

[0013] The alkyl group in the alkyl (meth)acrylate may be straight-chain, branched-chain, or cyclic, but is preferably straight-chain.

[0014] The alkyl group in the above alkyl (meth)acrylate ester may be substituted or unsubstituted, but is preferably unsubstituted.

[0015] The alkyl group in the alkyl (meth)acrylate is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 24 carbon atoms, for example, 1 to 20 or 1 to 18 carbon atoms.

[0016] Examples of the (meth)acrylic acid esters include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, neopentyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, and stearyl (meth)acrylate; and alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and tricyclodecyl (meth)acrylate. Examples of heteroatom-containing (meth)acrylic acid esters include alicyclic alkyl acrylates, 2-methoxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, chloroethyl (meth)acrylate, trifluoroethyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate, polypropylene glycol (meth)acrylate, glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0017] The (meth)acrylamides are preferably represented by the following formula: CH2=CX 1 -CONR 31 R 32 [In the formula, X 1 is a hydrogen atom or a methyl group, R 31 and R 32 are each independently a hydrogen atom or an alkyl group which may have a substituent. It is a compound represented by the formula:

[0018] In one embodiment, R 31 and R 32 is a hydrogen atom.

[0019] In another embodiment, R 31 and R 32 At least one of the groups is an alkyl group which may have a substituent.

[0020] Above R 31 and R 32 The alkyl group in may be straight-chain, branched-chain or cyclic, but is preferably straight-chain.

[0021] Above R 31 and R 32 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

[0022] Above R 31 and R 32 The substituent of the alkyl group in the formula (I) is not particularly limited, but examples thereof include a hydroxyl group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an aryl group, and an acyl group.

[0023] Examples of the (meth)acrylamides include (meth)acrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N-ethylmethacrylamide, N-methyl-N-ethylacrylamide, N-methyl-N-ethylmethacrylamide, N-isopropylacrylamide, Nn-propylacrylamide, N-isopropylmethacrylamide, Nn-propylmethacrylamide, N-methyl-Nn -propylacrylamide, N-methyl-N-isopropylacrylamide, N,N'-methylenebisacrylamide, N,N'-methylenebismethacrylamide, N-butyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-octyl(meth)acrylamide, N-dodecyl(meth)acrylamide, N-octadecyl(meth)acrylamide, N-benzyl(meth)acrylamide, diacetone acrylamide, diacetone methacrylamide, N-methylolacrylamide, and N-methylol methacrylamide.

[0024] The styrenes preferably have the following formula: [ka] [In formula: X 2 is a hydrogen atom or a methyl group, R 35 , R 36 , R 37 , R 38 , and R 39 are each independently a hydrogen atom, a halogen atom, an alkoxy group, or an alkyl group. It is a compound represented by the formula:

[0025] In one embodiment, R 35 , R 36 , R 37 , R 38 , and R 39 is a hydrogen atom.

[0026] In another embodiment, R 35 , R 36 , R 37 , R 38 , and R 39 At least one of the groups is an alkyl group.

[0027] Above R 35 , R 36 , R 37 , R 38 , and R 39 The alkyl group in may be straight-chain, branched-chain or cyclic.

[0028] Above R 35 , R 36 , R 37 , R 38 , and R 39 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

[0029] Above R 35 , R 36 , R 37 , R 38 , and R 39 The alkyl group in the formula (I) may be substituted. The substituent of the alkyl group is not particularly limited, but examples thereof include a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an aryl group.

[0030] The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom or a chlorine atom.

[0031] Examples of the styrenes include styrene, o-, m-, or p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethylstyrene, o-, m-, or p-methylstyrene. o-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro-m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o-, m-, or pt-butylstyrene, o-, m-, or p-methoxystyrene, o-, m-, or p-chloromethylstyrene, o-, m-, or p-bromomethylstyrene, and styrene derivatives substituted with a silyl group.

[0032] The vinyl ester preferably has the formula: CH2=CX 3 -OCO-R 41 [In formula: X 3 is a hydrogen atom or a methyl group, R 41 is an alkyl group or an aryl group. It is a compound represented by the formula:

[0033] Above R 41 The alkyl group in may be straight-chain, branched-chain or cyclic.

[0034] Above R 41The alkyl group in the formula (I) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

[0035] Above R 41 The aryl group in is preferably a phenyl group.

[0036] Above R 41 The alkyl group and aryl group in the formula (I) may be substituted. The substituents on the alkyl group and aryl group are not particularly limited, but examples thereof include a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an aryl group.

[0037] Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl hexanoate, vinyl n-octanoate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.

[0038] [Arm Polymer] The arm polymer can be obtained by polymerizing the above-mentioned vinyl monomer.

[0039] In a preferred embodiment, the arm polymer is a polymer synthesized by living radical polymerization of vinyl monomers.

[0040] In a more preferred embodiment, the arm polymer is a polymer synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization, atom transfer radical polymerization (ATRP), nitroxide-mediated radical polymerization (NMP), reversible transfer catalyzed polymerization (RTCP), reversible coordination-mediated polymerization (RCMP), or organotellurium-mediated living radical polymerization (TERP).

[0041] In a further preferred embodiment, the arm polymer has the formula (1): R c -(R b ) n -SC(=S)-R a [In formula: R a is alkyl, phenyl, -SR a1 , -OR a2 , -NR a3 2. [ka] and; R a1 , R a2 , R a3 , R a4 , R a5 and R a6 are each independently 1-20 an alkyl group or a phenyl group; R a7 is a hydrogen or halogen atom, R b teeth, -CH2-CR 11 (-COOR 12 )- and R 11 is a hydrogen atom or a methyl group, R 12 is C 1-20 is an alkyl group, R c is R 16 -R 15 - and R 15 may be substituted C 1-6 is an alkylene group, R 16 is a carboxyl group, a hydroxyl group, or a phenyl group, n is an integer from 1 to 1,000. It is a polymer represented by the formula:

[0042] In the above formula, R a is alkyl, phenyl, -SR a1 , -OR a2 , -NR a3 2. [ka] R a can be part of a so-called RAFT agent.

[0043] In the above formula, R a1 , R a2 , R a3 , R a4 , R a5 and R a6 are each independently an alkyl group or a phenyl group.

[0044] Above R a1 is preferably C 1-20 Alkyl groups, more preferably C 3-18 alkyl group, more preferably C 4-12 It is an alkyl group.

[0045] Above R a2 is preferably a phenyl group or C 1-20 It is an alkyl group. 1-20 The alkyl group is preferably C 1-10 Alkyl groups, more preferably C 1-6 alkyl group, more preferably C 1-3 It is an alkyl group.

[0046] Above R a3 is preferably C 1-20 Alkyl groups, more preferably C 1-10 alkyl group, more preferably C 1-6 alkyl groups, even more preferably C 1-3It is an alkyl group.

[0047] Above R a4 is preferably C 1-6 Alkyl groups, more preferably C 1-3 It is preferably an alkyl group, more preferably a methyl group.

[0048] Above R a5 is preferably C 1-6 Alkyl groups, more preferably C 1-3 It is preferably an alkyl group, more preferably a methyl group.

[0049] Above R a6 is preferably C 1-6 Alkyl groups, more preferably C 1-3 It is preferably an alkyl group, more preferably a methyl group.

[0050] Above R a7 is a hydrogen or halogen atom (for example, fluorine, chlorine, bromine or iodine, preferably chlorine).

[0051] In one embodiment, R a -SR a1 -OR a2 is.

[0052] In the above formula, R b teeth, -CH2-CR 11 (-COOR 12 )- [In formula: R 11 is a hydrogen atom or a methyl group, R 12 is C 1-20 is an alkyl group. It is a group represented by the formula:

[0053] Above R 12 may be straight chain, branched chain or cyclic.

[0054] Above R 12 is preferably C 1-18Alkyl groups, more preferably C 1-6 It is an alkyl group.

[0055] Above R c is R 16 -R 15 - and R 15 may be substituted C 1-6 is an alkylene group, and R 16 is a carboxyl group, a hydroxyl group, or a phenyl group.

[0056] Above R 15 C 1-6 The alkylene group may be a straight chain or a branched chain.

[0057] In one embodiment, the R 15 is the unsubstituted C 1-6 It is an alkylene group.

[0058] In one embodiment, the R 15 is a substitution C 1-6 It is an alkylene group. 1-6 The substituent of the alkylene group is not particularly limited, but examples thereof include a halogen atom, a cyano group, a hydroxyl group, and an aryl group.

[0059] n is an integer of 1 to 1,000, preferably an integer of 1 to 500.

[0060] The number average molecular weight of the arm polymer is preferably 3,000 to 100,000, and more preferably 5,000 to 50,000. The number average molecular weight is a value measured by GPC measurement (polystyrene equivalent).

[0061] The molecular weight distribution (PDI (PolyDispersity Index)) of the arm polymer of the present disclosure is preferably 1.0 or more and 3.0 or less, more preferably 1.1 or more and 2.0 or less.

[0062] The polymer represented by the above formula (1) can be synthesized, for example, by utilizing so-called RAFT (Reversible addition-fragmentation chain transfer) type radical polymerization.

[0063] In another preferred embodiment, the arm polymer has the formula (2): R c '-(R b ) n -R a ' (2) [In formula: R a ' is a halogen atom; R b teeth, -CH2-CR 11 (-COOR 12 )- and R 11 is a hydrogen atom or a methyl group, R 12 is C 1-20 is an alkyl group, R c ' is R 18 -R 17 - and R 17 -CR 19 2- and R 19 are each independently a hydrogen atom, C 1-6 an alkyl group, a phenyl group, or a halogen atom; R 18 is R 18a -OCO-, a phenyl group, or a cyano group; R 18a may be substituted C 1-20 is an alkyl group, n is an integer from 1 to 1,000. It is a polymer represented by the formula:

[0064] Above R a ' is a halogen atom, more preferably chlorine or bromine, even more preferably bromine.

[0065] Above R b has the same meaning as in the polymer represented by formula (1) above.

[0066] The above n has the same meaning as in the polymer represented by the above formula (1).

[0067] Above R c ' is R 18 -R 17 - and R 17 -CR 19 2- and R 19 are each independently a hydrogen atom, C 1-6 alkyl group, phenyl group, or halogen atom, and R 18 is R 18a -OCO-, a phenyl group, or a cyano group; R 18a is a hydrogen atom or an optionally substituted C 1-20 Alkyl, preferably optionally substituted C 1-20 It is an alkyl group.

[0068] Above R 18 is preferably R 18a -OCO-.

[0069] Above R 18a C 1-20 The alkyl group may be straight-chain or branched.

[0070] In one embodiment, the R 18a is unsubstituted C 1-20 It is an alkyl group.

[0071] In one embodiment, the R 18a is a substitution C 1-20 It is an alkyl group. 1-20 The substituent on the alkyl group is not particularly limited, but examples thereof include a hydroxy group, a vinyl group, a propargyl group, a trialkylsilyl group, and a trialkoxysilyl group.

[0072] Above R 18a C 1-20The alkyl group is preferably C 1-10 Alkyl groups, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group or an ethyl group.

[0073] Above R 19 C 1-6 The alkyl group may be straight-chain or branched.

[0074] Above R 19 is preferably C 1-3 It is an alkyl group, more preferably methyl.

[0075] The polymer represented by the above formula (2) can be synthesized, for example, by utilizing the so-called ATRP (atom transfer radical polymerization) method.

[0076] [Polyfunctional alkenyl compounds] The polyfunctional alkenyl compound is a compound having a plurality of double bonds.

[0077] The number of double bonds is preferably 2 to 6, more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. Such double bonds are preferably present at the terminals of the molecule. That is, such double bonds are preferably CH2=CR e - group (in the formula, R e represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms).

[0078] In one embodiment, the polyfunctional alkenyl compound is a dialkenyl compound.

[0079] In a preferred embodiment, the dialkenyl compound has the formula (3): CH2=CR e -R d -CR e =CH2 [In formula: R d is a divalent organic group, Re is a hydrogen atom or a methyl group. It is a compound represented by the formula:

[0080] Above R d is preferably -R 22 -R 21 -R 23 - [In formula: R 21 is C 1-20 an alkylene group, a phenylene group, or —O—(C α H 2α O) β - and α is an integer from 1 to 6, β is an integer from 1 to 10, R 22 is a single bond, C 1-6 an alkylene group or —CO—; R 23 is a single bond, C 1-6 an alkylene group, or —CO—.] It is a group represented by the formula:

[0081] Above R 21 , R 22 , and R 23 The alkylene group in may be preferably straight-chain, branched-chain or cyclic, and may be substituted or unsubstituted.

[0082] Above R 21 C in 1-20 The alkylene group is preferably C 2-16 Alkylene groups, more preferably C 4-10 It is an alkylene group.

[0083] The above α is preferably 2 to 4, and more preferably 2.

[0084] The above β is preferably 2-10, more preferably 2-6.

[0085] Above R 22 and R 23is preferably CO.

[0086] In one embodiment, R e is a hydrogen atom.

[0087] In one embodiment, R e is a methyl group.

[0088] Examples of the polyfunctional alkenyl compound include divinylbenzene; (meth)acrylates at both ends of diols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, and cyclohexanedimethanol; (meth)acrylates of polyester polyols; (meth)acrylates of polyhydroxyl compounds such as trimethylolpropane and pentaerythritol; products in which the glycidyl group and the acid group of a monomer having an acid group are reacted with each other; and products in which a monomer having a hydroxyl group is reacted with a monomer having an isocyanate.

[0089] The star polymer of the present disclosure is a star polymer having arm portions containing a structure derived from an arm polymer, which is a polymer of a vinyl monomer, and a core portion containing a structure derived from a polyfunctional alkenyl compound that crosslinks the arm portions, and the arm polymer-derived structure accounts for 5 to 25 mol % of the structure derived from the polyfunctional alkenyl compound.

[0090] The crosslinkable polymer of the present disclosure can be obtained by reacting an arm polymer with a polyfunctional alkenyl compound to crosslink the arm polymer with the polyfunctional alkenyl compound.

[0091] For example, when an arm polymer represented by formula (1) or (2) is reacted with a dialkenyl compound represented by formula (3), the growing end (R c -(R b ) n -End or R c’ -(R b ) nThe -CR group derived from the dialkenyl compound in the resulting block polymer reacts with one of the -CH=CH2 groups of the dialkenyl compound represented by formula (3), resulting in block polymerization of the dialkenyl compound. e The =CH2 reacts with the growing end of another block polymer, thereby crosslinking the arm polymer with the dialkenyl compound.

[0092] The core is formed by the formation of a microgel between the terminal of the arm polymer and the polyfunctional alkenyl compound. For example, a star polymer obtained by reacting an arm polymer represented by formula (1) or (2) with a dialkenyl compound represented by formula (3) has a structure similar to that of the arm polymer represented by formula (1), where the -SC(=S)-R a R of the arm polymer represented by formula (2) a’ The moiety and the moiety derived from the dialkenyl compound represented by formula (3) constitute the core.

[0093] The arm portion is a polymer chain extending in a branched manner from the core portion. The arm portion is typically composed of a polymer portion of an arm polymer. For example, in the case of an arm polymer represented by formula (1), R c -(R b ) n In the case where the - moiety constitutes the arm portion and the arm polymer is represented by formula (2), R c’ -(R b ) n -The part forms the arm.

[0094] The arm polymer can be preferably obtained by living radical polymerization. By synthesizing the arm polymer by living radical polymerization, the molecular weight distribution (PDI) of the arm polymer becomes small, and therefore the molecular weight distribution of the star polymer also becomes small.

[0095] In the above reaction, the concentration of the polyfunctional alkenyl compound is preferably 150 to 500 mM. By using a polyfunctional alkenyl compound at such a concentration, high wettability and high adhesion to substrates, particularly fluororesin substrates, can be obtained.

[0096] The star polymer of the present disclosure has 5 to 25 mol %, preferably 5 to 22 mol %, and more preferably 5 to 20 mol % of arm polymer-derived structures relative to the structure derived from the polyfunctional alkenyl compound. That is, the star polymer of the present disclosure can be obtained by reacting a polyfunctional alkenyl compound with 5 to 25 mol % of arm polymers relative to the polyfunctional alkenyl compound.

[0097] The number average molecular weight of the star polymer of the present disclosure is preferably 5,000 to 1,000,000, more preferably 10,000 to 800,000, and even more preferably 15,000 to 600,000. The number average molecular weight is a value measured by GPC measurement (polystyrene equivalent).

[0098] The molecular weight distribution (PDI) of the star polymer of the present disclosure is preferably 1.0 or more and 10.0 or less, more preferably 1.1 or more and 7.0 or less, and even more preferably 1.1 or more and 5.0 or less.

[0099] The present disclosure provides compositions comprising the star polymers of the present disclosure.

[0100] In one embodiment, the composition is a coating agent.

[0101] The composition of the present disclosure may be a solution in which the star polymer of the present disclosure is dissolved as a solid in a solvent, or may be solvent-free.

[0102] Examples of the solvent include chlorine-containing solvents such as chloroform, dichloromethane, dichloroethane, and carbon tetrachloride; aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide; hydrocarbon solvents such as hexane and cyclohexane; cellosolve-based solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate; ester-based solvents such as diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, ethyl acetate, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate; Examples of suitable solvents include propylene glycol solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylaminoketone, and 2-heptanone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, and diacetone alcohol; and aromatic hydrocarbons such as toluene and xylene. These solvents can be used alone or in combination.

[0103] The concentration of the star polymer in the composition of the present disclosure is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, and even more preferably 3 to 20% by mass.

[0104] A film obtained from the composition of the present disclosure preferably has a water contact angle of 80 to 130 degrees, more preferably 85 to 125 degrees, and even more preferably 90 to 120 degrees.

[0105] In this specification, the water contact angle is a static contact angle when the measurement object is placed horizontally and 2 μL of water is dropped onto the surface.

[0106] The coating of the present disclosure is applied to a substrate.

[0107] The substrate preferably has a water contact angle of 60 to 150 degrees, more preferably 70 to 130 degrees, and even more preferably 80 to 120 degrees.

[0108] The substrate is preferably a resin substrate, more preferably a fluororesin substrate. That is, the coating agent of the present disclosure can be used for a resin substrate, preferably a fluororesin substrate.

[0109] The fluororesin is not particularly limited, but examples thereof include polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkoxyethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, and vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer.

[0110] From the viewpoint of the bonding strength between the fluororesin and the metal, the fluororesin may be subjected to a surface treatment.

[0111] Examples of the surface treatment include etching, plasma, corona, and photochemical treatments, with plasma and corona treatments being preferred. The conditions for the surface treatment can be appropriately set depending on the composition of the fluororesin, etc.

[0112] The coating agent of the present disclosure has excellent film-forming properties. For example, when 0.5 mL or more of the coating agent of the present disclosure is dropped onto a 30 mm × 30 mm substrate having a water contact angle of 60 to 150 degrees so as to cover the entire substrate, and the substrate is spin-coated at 300 rpm for 3 seconds and then at 2500 rpm for 27 seconds, the solid content can cover 80% or more, and more preferably 90% or more, of the substrate area.

[0113] The coating agent of the present disclosure can also be used as an adhesive.

[0114] The present disclosure provides a laminate comprising a fluororesin substrate, an adhesive layer comprising the star polymer of the present disclosure, and an adherend layer selected from a metal layer, a non-fluororesin layer, a fluororesin layer, and an inorganic layer, wherein the fluororesin substrate and the adherend layer are adhered to each other by the adhesive layer.

[0115] In the laminate of the present disclosure, the adhesive layer uses a layer containing the star polymer of the present disclosure, which exhibits good adhesion and wettability to the substrate and the adherend layer, and therefore the layers are firmly bonded together.

[0116] The adherend layer is a layer that is adhered to the substrate by the adhesive layer, and is selected from a metal layer, a non-fluorine resin layer, a fluorine resin layer, and an inorganic layer.

[0117] In one embodiment, the adherend layer is a metal layer.

[0118] The metal layer preferably has a surface roughness Rz of 2 μm or less on the side to be bonded, which improves the transmission loss between the substrate and the metal layer in the laminate.

[0119] The surface roughness Rz is more preferably 1.8 μm or less, even more preferably 1.5 μm or less, and is more preferably 0.3 μm or more, even more preferably 0.5 μm or more. The surface roughness Rz is a value (maximum height roughness) calculated by the method of JIS C 6515-1998.

[0120] The metal constituting the metal layer is preferably at least one selected from the group consisting of copper, gold, silver, stainless steel, aluminum, iron, ruthenium, and alloys thereof, more preferably at least one selected from the group consisting of copper, gold, silver, stainless steel, ruthenium, and aluminum, and even more preferably copper.

[0121] Examples of the stainless steel include austenitic stainless steel, martensitic stainless steel, and ferritic stainless steel.

[0122] In a preferred embodiment, the laminate is a circuit board, a lining material, or a laminate tube.

[0123] The circuit board is preferably a printed wiring board and is also preferably a high-frequency circuit board.

[0124] Although the star polymer, composition, and laminate of the present disclosure have been described in detail above, the present invention is not limited thereto.

[0125] Example The star polymer and laminate of the present disclosure will be described below in examples, but the present disclosure is not limited to the following examples.

[0126] Synthesis Example 1: Arm polymer: Synthesis of polymethyl acrylate (pMA) A nitrogen-purged reaction vessel was charged with 1,4-dioxane (41 mL), methyl acrylate (8.61 g), 4-cyano-4-(dodecylsulfanylthiocarbonyl)sulfanylpentanoic acid (0.404 g), and 2,2'-azobis(isobutyronitrile) (16.4 mg), and the mixture was allowed to react at 60°C for 24 hours. The polymer solution was dried under reduced pressure to obtain arm polymer pMA. GPC analysis using chloroform as the eluent revealed that the number-average molecular weight (Mn) of this polymer was 6,700 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.36.

[0127] Synthesis Example 2: Arm polymer: Synthesis of polybutyl acrylate (pBA) A nitrogen-purged reactor was charged with 1,4-dioxane (14.3 mL), butyl acrylate (5.12 g), 4-cyano-4-(dodecylsulfanylthiocarbonyl)sulfanylpentanoic acid (0.162 g), and 2,2'-azobis(isobutyronitrile) (6.6 mg). The reaction was allowed to proceed at 60 °C for 24 hours. The polymer solution was then added dropwise to a methanol / water mixture (9:1 by volume) to obtain arm polymer pBA. GPC analysis using chloroform as the eluent revealed that the number-average molecular weight (Mn) of this polymer was 8,000 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.12.

[0128] Synthesis Example 3: Arm polymer: Synthesis of poly(octyl acrylate) (pOA) In a nitrogen-purged reaction vessel, 1,4-dioxane (17.5 mL), octyl acrylate (11.1 g), 4-cyano-4-(dodecylsulfanylthiocarbonyl)sulfanylpentanoic acid (0.242 g), and 2,2'-azobis(isobutyronitrile) (9.9 mg) were added and reacted at 80 °C for 6 hours. The polymerization solution was added dropwise to methanol to obtain arm polymer pOA. GPC analysis using chloroform as the eluent revealed that the number-average molecular weight (Mn) of this polymer was 8,900 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.34.

[0129] Synthesis Example 4: Arm polymer: Synthesis of poly(dodecyl acrylate) (pDA) In a nitrogen-purged reaction vessel, 1,4-dioxane (4.54 mL), dodecyl acrylate (4.80 g), 4-cyano-4-(dodecylsulfanylthiocarbonyl)sulfanylpentanoic acid (80.8 mg), and 2,2'-azobis(isobutyronitrile) (3.3 mg) were added and reacted at 60 °C for 24 hours. The polymerization solution was added dropwise to methanol to obtain arm polymer pDA. GPC analysis using chloroform as the eluent revealed that the number-average molecular weight (Mn) of this polymer was 14,000 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.23.

[0130] Synthesis Example 5: Arm polymer: Synthesis of polystearyl acrylate (pSA) A nitrogen-purged reaction vessel was charged with 1,4-dioxane (10 mL), stearyl acrylate (6.50 g), 4-cyano-4-(dodecylsulfanylthiocarbonyl)sulfanylpentanoic acid (80.9 mg), and 2,2'-azobis(isobutyronitrile) (3.3 mg). The reaction was allowed to proceed at 60 °C for 24 hours. The polymer solution was precipitated by adding it dropwise to methanol and washed with 1,4-dioxane to obtain arm polymer pSA. GPC analysis using chloroform as the eluent revealed that the number-average molecular weight (Mn) of this polymer was 13,000 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.22.

[0131] Synthesis Example 6: Arm polymer: Synthesis of hydroxy-terminated polybutyl acrylate (pBA) A nitrogen-purged reactor was charged with 1,4-dioxane (14.3 mL), butyl acrylate (5.13 g), 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanol (0.156 g), and 2,2'-azobis(isobutyronitrile) (6.6 mg). The mixture was allowed to react at 60 °C for 24 hours. The polymer solution was then added dropwise to a methanol / water mixture (9:1 by volume) to obtain arm polymer pBA. GPC analysis using chloroform as the eluent revealed that the number-average molecular weight (Mn) of this polymer was 10,300 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.15.

[0132] Synthesis Example 7: Arm polymer: Synthesis of benzyl-terminated polybutyl acrylate (pBA) A nitrogen-purged reaction vessel was charged with 1,4-dioxane (14.3 mL), butyl acrylate (5.10 g), benzyldodecyl trithiocarbonate (0.148 g), and 2,2'-azobis(isobutyronitrile) (6.6 mg) and reacted at 60°C for 24 hours. The polymerized solution was added dropwise to a methanol / water mixed solvent (volume ratio 9:1) to obtain arm polymer pBA. GPC analysis using chloroform as the eluent revealed that the number-average molecular weight (Mn) of this polymer was 12,000 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.19.

[0133] Synthesis Example 8: Synthesis of pMA-arm star polymer, crosslinker concentration 200 mM In a nitrogen-purged reaction vessel, 1,4-dioxane (9.5 mL), pMA (2.0 g) obtained in Synthesis Example 1, polyethylene glycol diacrylate [number average molecular weight 250] (0.50 g), and 2,2'-azobis(isobutyronitrile) (3.3 mg) were added and reacted at 60°C for 24 hours. The polymerization solution was added dropwise to a methanol / water mixed solvent (volume ratio 4:1) to obtain a star polymer. GPC measurement using chloroform as the eluent revealed that the number average molecular weight (Mn) of this polymer was 30,200 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.52.

[0134] Synthesis Example 9: Synthesis of pBA-arm star polymer, crosslinker concentration 400 mM In a nitrogen-purged reaction vessel, 1,4-dioxane (6.35 mL), pBA (1.88 g) obtained in Synthesis Example 2, polyethylene glycol diacrylate [number average molecular weight 250] (0.70 g), and 2,2'-azobis(isobutyronitrile) (2.3 mg) were added and reacted at 60°C for 24 hours. The polymerization solution was added dropwise to methanol to obtain a star polymer. GPC measurement using chloroform as the eluent revealed that the number average molecular weight (Mn) of this polymer was 54,600 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.91.

[0135] Synthesis Example 10: Synthesis of pOA-arm star polymer, crosslinker concentration 400 mM In a nitrogen-purged reaction vessel, 1,4-dioxane (9.0 mL), pOA (4.02 g) obtained in Synthesis Example 3, polyethylene glycol diacrylate [number average molecular weight 250] (1.0 g), and 2,2'-azobis(isobutyronitrile) (3.3 mg) were added and reacted at 80 °C for 20 hours. The polymerization solution was precipitated by adding it dropwise to methanol, followed by reprecipitation with cooled acetone to obtain a star polymer. GPC analysis using chloroform as the eluent revealed that the number average molecular weight (Mn) of this polymer was 252,000 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.49.

[0136] Synthesis Example 11: Synthesis of pDA arm star polymer, crosslinker concentration 400 mM In a nitrogen-purged reaction vessel, 1,4-dioxane (5.50 mL), pDA (2.90 g) obtained in Synthesis Example 4, polyethylene glycol diacrylate [number average molecular weight 250] (0.60 g), and 2,2'-azobis(isobutyronitrile) (2.0 mg) were added and reacted at 60°C for 24 hours. The polymerization solution was added dropwise to methanol, and the resulting precipitate was dissolved in toluene. Methanol was then added to the solution, yielding a star polymer as a precipitate. GPC analysis using chloroform as the eluent revealed that the number average molecular weight (Mn) of this polymer was 291,000 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.94.

[0137] Synthesis Example 12: Synthesis of pSA-arm star polymer, crosslinker concentration 400 mM In a nitrogen-purged reaction vessel, 1,4-dioxane (4.60 mL), pSA (3.40 g) obtained in Synthesis Example 5, polyethylene glycol diacrylate [number average molecular weight 250] (0.50 g), and 2,2'-azobis(isobutyronitrile) (1.6 mg) were added and reacted at 60°C for 24 hours. The polymerization solution was added dropwise to methanol, and the resulting precipitate was dissolved in toluene. Methanol was then added to the solution, yielding a star polymer as a precipitate. GPC analysis using chloroform as the eluent revealed that the number average molecular weight (Mn) of this polymer was 111,000 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.72.

[0138] Synthesis Example 13: Synthesis of pBA-arm star polymer, crosslinker concentration 300 mM A star polymer was obtained by the same procedure as in Synthesis Example 9, except that the amount of polyethylene glycol diacrylate [number average molecular weight 250] was changed to 0.53 g. GPC measurement using chloroform as an eluent revealed that the number average molecular weight (Mn) of this polymer was 54,700 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.66.

[0139] Synthesis Example 14: Synthesis of pBA-arm star polymer, crosslinker concentration 200 mM A star polymer was obtained by the same procedure as in Synthesis Example 9, except that the amount of polyethylene glycol diacrylate [number average molecular weight 250] was changed to 0.35 g. GPC measurement using chloroform as an eluent revealed that the number average molecular weight (Mn) of this polymer was 31,200 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.24.

[0140] Synthesis Example 15: Synthesis of pBA-arm star polymer, crosslinker concentration 100 mM A star polymer was obtained by the same procedure as in Synthesis Example 9, except that the amount of polyethylene glycol diacrylate [number average molecular weight 250] was changed to 0.18 g. GPC measurement using chloroform as an eluent revealed that the number average molecular weight (Mn) of this polymer was 28,000 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.28.

[0141] Synthesis Example 16: Synthesis of pDA arm star polymer, crosslinker concentration 300 mM A star polymer was obtained by the same procedure as in Synthesis Example 11, except that the amount of polyethylene glycol diacrylate [number average molecular weight 250] was changed to 0.45 g. GPC measurement using chloroform as an eluent revealed that the number average molecular weight (Mn) of this polymer was 25,500 (polystyrene equivalent) and the molecular weight distribution (PDI) was 2.85.

[0142] Synthesis Example 17: Synthesis of pDA arm star polymer, crosslinker concentration 200 mM A star polymer was obtained by the same procedure as in Synthesis Example 11, except that the amount of polyethylene glycol diacrylate [number average molecular weight 250] was changed to 0.30 g. GPC measurement using chloroform as an eluent revealed that the number average molecular weight (Mn) of this polymer was 19,600 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.82.

[0143] Synthesis Example 18: Synthesis of Hydroxy-Terminated pBA Arm Star Polymer, Crosslinker Concentration 300 mM In a nitrogen-purged reaction vessel, 1,4-dioxane (6.50 mL), pBA (1.89 g) obtained in Synthesis Example 6, polyethylene glycol diacrylate [number average molecular weight 250] (0.53 g), and 2,2'-azobis(isobutyronitrile) (2.3 mg) were added and reacted at 60°C for 24 hours. The polymerization solution was added dropwise to methanol to obtain a star polymer. GPC measurement using chloroform as the eluent revealed that the number average molecular weight (Mn) of this polymer was 129,000 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.39.

[0144] Synthesis Example 19: Synthesis of benzyl-terminated pBA arm star polymer, crosslinker concentration 400 mM 1,4-Dioxane (3.65 mL), pBA (1.07 g) obtained in Synthesis Example 7, polyethylene glycol diacrylate [number average molecular weight 250] (0.40 g), and 2,2'-azobis(isobutyronitrile) (3.3 mg) were added to a nitrogen-purged reaction vessel and reacted at 60°C for 144 hours. The polymerization solution was added dropwise to methanol to obtain a star polymer. GPC measurement using chloroform as the eluent revealed that the number average molecular weight (Mn) of this polymer was 166,000 (polystyrene equivalent) and the molecular weight distribution (PDI) was 3.13.

[0145] Synthesis Example 20: Arm polymer: Synthesis of polybutyl acrylate (pBA) Anisole (8.8 mL), copper(II) bromide (1.8 mg), 2,2'-azobis(isobutyronitrile) (13.1 mg), a 50 mM DMF solution of tris[2-(dimethylamino)ethyl]amine (Me6TREN) (0.8 mL), butyl acrylate (5.11 g), and ethyl 2-bromoisobutyrate (77.8 mg) were added to a nitrogen-purged reaction vessel and reacted at 70 °C for 24 h. The polymer solution was then added dropwise to a methanol / water mixture to obtain arm polymer pBA. GPC analysis using chloroform as the eluent revealed that the number-average molecular weight (Mn) of this polymer was 8,200 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.25.

[0146] Synthesis Example 21: Synthesis of pBA-arm star polymer, crosslinker concentration 400 mM Anisole (6.35 mL), copper(II) bromide (5.2 mg), 2,2'-azobis(isobutyronitrile) (7.7 mg), a 50 mM DMF solution of tris[2-(dimethylamino)ethyl]amine (Me6TREN) (0.47 mL), pBA (1.93 g) from Synthesis Example 20, and polyethylene glycol diacrylate (number average molecular weight 250) (0.70 g) were added to a nitrogen-purged reaction vessel and reacted at 70 °C for 24 hours. The polymerization solution was added dropwise to methanol to obtain a star polymer. GPC analysis using chloroform as the eluent revealed that the number average molecular weight (Mn) of this polymer was 65,000 (polystyrene equivalent) and the molecular weight distribution (PDI) was 1.30.

[0147] Evaluation of film formation on substrate A 5% by mass chloroform solution of the linear polymers obtained in Synthesis Examples 1 to 7 and 20 and the star polymers obtained in Synthesis Examples 8 to 19 and 21 was dropped onto a 30 mm × 30 mm polytetrafluoroethylene (PTFE) substrate (manufactured by Nichias Corporation), a tetrafluoroethylene-perfluoroalkoxyethylene copolymer resin (PFA) substrate (manufactured by Daikin Industries, Ltd.), or a copper foil (surface roughness Rz: 0.85 μm, manufactured by Fukuda Metal Foil & Powder Co., Ltd.) in an amount of 0.5 mL or more so that the entire substrate surface was covered, and the substrate was spin-coated at 300 rpm for 3 seconds and then at 2500 rpm for 27 seconds to form a film (Examples 1 to 12, Comparative Examples 1 to 9).

[0148] The film-forming properties were evaluated visually according to the following criteria: 1: The coating film coverage of the substrate surface was 80% or more. 2: The coating film coverage of the substrate surface was less than 80%.

[0149] Measurement of water contact angle of coating film The water contact angle of the star-shaped polymer coating film formed on the PTFE substrate and PFA substrate was measured. The drop volume was 2 μL. Note that for the film-forming evaluation 2, the surface area of ​​the substrate coated with the polymer was small, so the contact angle could not be measured.

[0150] [Table 1]

[0151] The above results confirmed that the star polymer of the present disclosure has high film-forming properties even on PTFE and PFA substrates. [Industrial Applicability]

[0152] The star polymers of the present disclosure are suitable for use as adhesives.

Claims

1. an arm portion including a structure derived from an arm polymer that is a polymer of a vinyl monomer; a core portion including a structure derived from a polyfunctional alkenyl compound that crosslinks the arm portions; A star polymer having 5 to 25 mol % of a structure derived from an arm polymer relative to a structure derived from a polyfunctional alkenyl compound, The arm polymer is Formula (1): R ｃ -(R ｂ ) ｎ -S-C(=S)-R ａ (1) [In the formula: R ａ is alkyl, phenyl, -SR ａ１ , -OR ａ２ , -NR ａ３ ２ , 【Chemistry 1】 and R ａ１ , R ａ２ , R ａ３ , R ａ４ , R ａ５ and R ａ６ are each independently C １－２０ is an alkyl group or a phenyl group; R ａ７ is a hydrogen or halogen atom, R ｂ teeth, -CH ２ -CR １１ (-COOR １２ )- and R １１ is a hydrogen atom or a methyl group, R １２ is C １－２０ is an alkyl group, R ｃ is R １６ -R １５ - and R １５ is an optionally substituted C １－６ is an alkylene group, R １６ is a carboxyl group, a hydroxyl group, or a phenyl group, n is an integer from 1 to 1,000. or a polymer represented by Formula (2): R ｃ ’-(R ｂ ) ｎ -R ａ ’ (2) [In the formula: R ａ ' is a halogen atom; R ｂ teeth, -CH ２ -CR １１ (-COOR １２ )- and R １１ is a hydrogen atom or a methyl group, R １２ is C １－２０ is an alkyl group, R ｃ ' is R １８ -R １７ - and R １７ is -CR １９ ２ - and R １９ are each independently a hydrogen atom, C １－６ an alkyl group, a phenyl group, or a halogen atom; R １８ is R １８ａ -OCO-, a phenyl group, or a cyano group; R １８ａ is an optionally substituted C １－２０ is an alkyl group, n is an integer from 1 to 1,000. is a polymer represented by the polyfunctional alkenyl compound is a dialkenyl compound, The dialkenyl compound has the formula (3): CH ２ =CR ｅ -R ｄ -CR ｅ =CH ２ [In the formula: R ｄ is -R ２２ -R ２１ -R ２３ - and R ２１ is -O-(C α H ２α O) β - and α is an integer from 1 to 6, β is an integer from 1 to 10, R ２２ is a single bond, C １－６ an alkylene group or —CO—; R ２３ is a single bond, C １－６ an alkylene group or —CO—; R ｅ is a hydrogen atom or a methyl group. is a compound represented by Star polymers.

2. 2. The star polymer of claim 1, wherein the vinyl monomer is a (meth)acrylic acid ester, a (meth)acrylamide, a styrene, or a vinyl ester.

3. 3. The star polymer according to claim 1, wherein the arm polymer is a polymer synthesized by living radical polymerization.

4. The arm polymer has the formula (1): R ｃ -(R ｂ ) ｎ -S-C(=S)-R ａ (1) [In the formula: R ａ is alkyl, phenyl, -SR ａ１ , -OR ａ２ , -NR ａ３ ２ , 【Chemistry 2】 and R ａ１ , R ａ２ , R ａ３ , R ａ４ , R ａ５ and R ａ６ are each independently C １－２０ is an alkyl group or a phenyl group; R ａ７ is a hydrogen or halogen atom, R ｂ teeth, -CH ２ -CR １１ (-COOR １２ )- and R １１ is a hydrogen atom or a methyl group, R １２ is C １－２０ is an alkyl group, R ｃ is R １６ -R １５ - and R １５ is an optionally substituted C １－６ is an alkylene group, R １６ is a carboxyl group, a hydroxyl group, or a phenyl group, n is an integer from 1 to 1,000. The star polymer according to any one of claims 1 to 3, which is a polymer represented by the formula:

5. The arm polymer has the formula (2): R ｃ ’-(R ｂ ) ｎ -R ａ ’ (2) [In the formula: R ａ ' is a halogen atom; R ｂ teeth, -CH ２ -CR １１ (-COOR １２ )- and R １１ is a hydrogen atom or a methyl group, R １２ is C １－２０ is an alkyl group, R ｃ ' is R １８ -R １７ - and R １７ is -CR １９ ２ - and R １９ are each independently a hydrogen atom, C １－６ an alkyl group, a phenyl group, or a halogen atom; R １８ is R １８ａ -OCO-, a phenyl group, or a cyano group; R １８ａ is an optionally substituted C １－２０ is an alkyl group, n is an integer from 1 to 1,000. The star polymer according to any one of claims 1 to 3, which is a polymer represented by the formula:

6. A coating agent for a resin laminated substrate having an adhesive layer, wherein the coating film formed by coating a resin substrate with a star polymer has a water contact angle of 80 to 130 degrees, The star polymer is an arm portion including a structure derived from an arm polymer that is a polymer of a vinyl monomer; a core portion including a structure derived from a polyfunctional alkenyl compound that crosslinks the arm portions; and has 5 to 25 mol % of a structure derived from an arm polymer relative to the structure derived from a polyfunctional alkenyl compound, The number average molecular weight of the star polymer is 15,000 or more. A coating agent for a resin laminated substrate having an adhesive layer, The arm polymer is Formula (1): R c -(R b ) n -S-C(=S)-R a (1) [In the formula: R a is alkyl, phenyl, —SR a1 , —OR a2 , —NR a3 2 , 【Transformation 3】 and R a1 , R a2 , R a3 , R a4 , R a5 and R a6 each independently represent a C 1-20 alkyl group or a phenyl group; R a7 is a hydrogen or halogen atom; R b is -CH 2 -CR 11 (-COOR 12 )- and R 11 is a hydrogen atom or a methyl group; R 12 is a C 1-20 alkyl group; R c is R 16 -R 15 -; R 15 is an optionally substituted C 1-6 alkylene group; R 16 is a carboxyl group, a hydroxyl group, or a phenyl group; n is an integer from 1 to 1,000. or a polymer represented by Formula (2): R c' - (R b ) n - R a ' (2) [In the formula: R a ' is a halogen atom; R b is -CH 2 -CR 11 (-COOR 12 )- and R 11 is a hydrogen atom or a methyl group; R 12 is a C 1-20 alkyl group; R c ′ is R 18 -R 17 —; R 17 is —CR 19 2 —; R 19 is independently a hydrogen atom, a C 1-6 alkyl group, a phenyl group, or a halogen atom; R 18 is R 18a —OCO—, a phenyl group, or a cyano group; R 18a is an optionally substituted C 1-20 alkyl group; n is an integer from 1 to 1,000. is a polymer represented by the polyfunctional alkenyl compound is a dialkenyl compound, The dialkenyl compound has the formula (3): CH 2 =CR e -R d -CR e =CH 2 [In the formula: R d is —R 22 —R 21 —R 23 —; R 21 is —O—(C α H 2α O) β —; α is an integer from 1 to 6, β is an integer from 1 to 10, R 22 is a single bond, a C 1-6 alkylene group, or —CO—; R 23 is a single bond, a C 1-6 alkylene group, or —CO—; R e is a hydrogen atom or a methyl group. A coating agent for resin laminated substrates, which is a compound represented by the formula:

7. 7. The coating agent for laminated substrates having an adhesive layer according to claim 6, wherein the resin substrate has a water contact angle of 60 to 150 degrees.

8. The coating agent for laminated substrates having an adhesive layer according to claim 6 or 7, wherein the resin substrate is a fluororesin substrate.

9. A coated substrate having an adhesive layer that covers 80% or more of the area of ​​the substrate with solid content, the adhesive layer comprises a star polymer; The star polymer is an arm portion including a structure derived from an arm polymer that is a polymer of a vinyl monomer; a core portion including a structure derived from a polyfunctional alkenyl compound that crosslinks the arm portions; and has 5 to 25 mol % of a structure derived from an arm polymer relative to the structure derived from a polyfunctional alkenyl compound, The number average molecular weight of the star polymer is 15,000 or more. A coated substrate having an adhesive layer, The arm polymer is Formula (1): R c -(R b ) n -S-C(=S)-R a (1) [In the formula: R a is alkyl, phenyl, —SR a1 , —OR a2 , —NR a3 2 , 【Chemistry 4】 and R a1 , R a2 , R a3 , R a4 , R a5 and R a6 each independently represent a C 1-20 alkyl group or a phenyl group; R a7 is a hydrogen or halogen atom; R b is -CH 2 -CR 11 (-COOR 12 )- and R 11 is a hydrogen atom or a methyl group; R 12 is a C 1-20 alkyl group; R c is R 16 -R 15 -; R 15 is an optionally substituted C 1-6 alkylene group; R 16 is a carboxyl group, a hydroxyl group, or a phenyl group; n is an integer from 1 to 1,000. or a polymer represented by Formula (2): R c' - (R b ) n - R a ' (2) [In the formula: R a ' is a halogen atom; R b is -CH 2 -CR 11 (-COOR 12 )- and R 11 is a hydrogen atom or a methyl group; R 12 is a C 1-20 alkyl group; R c ′ is R 18 -R 17 —; R 17 is —CR 19 2 —; R 19 is independently a hydrogen atom, a C 1-6 alkyl group, a phenyl group, or a halogen atom; R 18 is R 18a —OCO—, a phenyl group, or a cyano group; R 18a is an optionally substituted C 1-20 alkyl group; n is an integer from 1 to 1,000. is a polymer represented by the polyfunctional alkenyl compound is a dialkenyl compound, The dialkenyl compound has the formula (3): CH 2 =CR e -R d -CR e =CH 2 [In the formula: R d is —R 22 —R 21 —R 23 —; R 21 is —O—(C α H 2α O) β —; α is an integer from 1 to 6, β is an integer from 1 to 10, R 22 is a single bond, a C 1-6 alkylene group, or —CO—; R 23 is a single bond, a C 1-6 alkylene group, or —CO—; R e is a hydrogen atom or a methyl group. A coated substrate having an adhesive layer, the adhesive layer being a compound represented by the formula:

10. The coated substrate with an adhesive layer according to claim 9 , wherein the solid content comprises a star polymer.

11. The coated substrate provided with an adhesive layer according to claim 10 , wherein the substrate is a resin substrate.

12. The coated substrate provided with an adhesive layer according to claim 11 , wherein the resin substrate is a fluorine-based substrate.

13. A film formed on the coated substrate according to any one of claims 9 to 12.

14. a fluororesin substrate; An adhesive layer comprising the star polymer of any one of claims 1 to 5; an adherend layer selected from a metal layer, a non-fluorine resin layer, a fluorine resin layer, and an inorganic layer; The fluororesin substrate and the adherend layer are adhered to each other by the adhesive layer. Laminate.

15. The laminate according to claim 14 , wherein the adherend layer is a metal layer.

16. The laminate according to claim 14 or 15, wherein the fluororesin substrate is a substrate composed of polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkoxyethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, or vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer.

17. The laminate according to any one of claims 14 to 16, wherein the metal layer is a copper layer.

18. The laminate according to any one of claims 14 to 17, wherein the metal layer has a surface roughness Rz of 2 µm or less on the side to be bonded.

19. A circuit board comprising the laminate according to any one of claims 14 to 18.

20. 20. The circuit board of claim 19, which is a high frequency circuit board.

21. A lining material comprising the laminate according to any one of claims 14 to 18.

22. A laminate tube comprising the laminate according to any one of claims 14 to 18.

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