TW202330651A - Star-shaped polymer - Google Patents

Abstract

The present invention provides a star-shaped polymer having arm portions derived from an arm polymer obtained by polymerizing a vinyl monomer and a core portion containing a structure derived from a polyfunctional alkenyl compound that crosslinks the arm portions, wherein, with respect to the structure derived from the polyfunctional alkenyl compound, the star-shaped polymer has 5 to 25 mol% of the arm polymer.

Description

star polymer

This disclosure relates to a star polymer.

Adhesives for bonding substrates usually use acrylic polymers (Patent Documents 1 and 2).

[Prior Art Literature]

[Patent Document]

Patent Document 1: Japanese PCT Publication No. 2019-123885.

Patent Document 2: Japanese PCT Publication No. 2020-527621.

Conventional acrylic polymers do not have sufficient film-forming properties on different types of substrates, such as metals and fluororesins, and cannot perform sufficient functions when used as adhesives.

The purpose of the present disclosure is to provide a polymer with sufficient film-forming properties on different types of substrates.

This disclosure includes the following aspects.

[1] A star polymer having an arm and a core,

The aforementioned arm portion comprises a structure derived from an arm polymer of a polymer belonging to a vinyl monomer,

The aforementioned core portion comprises a structure derived from a polyfunctional alkenyl compound cross-linked with the aforementioned arm portion,

The aforementioned star polymer has 5 to 25 mol% of the structure derived from the arm polymer relative to the structure derived from the polyfunctional alkenyl compound.

[2] The star-shaped polymer according to the above [1], wherein the vinyl monomer is (meth)acrylate, (meth)acrylamide, styrene, or vinyl ester.

[3] The star polymer according to the above [1] or [2], wherein the arm polymer is a polymer synthesized by living radical polymerization.

[4] The star polymer according to any one of [1] to [3] above, wherein the arm polymer is a compound represented by formula (1).

R ^c -(R ^b ) _n -SC(=S)-R ^a ...(1)

[where:

R ^a is alkyl, phenyl, -SR ^a1 , -OR ^a2 , -NR ^a3 ₂ ,

R ^a1 , R ^a2 , R ^a3 , R ^a4 , R ^a5 and R ^a6 are independently C _1-20 alkyl or phenyl;

R ^a7 is hydrogen or a halogen atom,

R ^b is -CH ₂ -CR ¹¹ (-COOR ¹² )-,

R ¹¹ is a hydrogen atom or a methyl group,

R ¹² is C _1-20 alkyl,

R ^c is R ¹⁶ -R ¹⁵ -,

R ¹⁵ is a C _1-6 alkylene group that may be substituted,

R ¹⁶ is carboxyl, hydroxyl, or phenyl,

n is an integer from 1 to 1,000].

[5] The star polymer according to any one of [1] to [3] above, wherein the aforementioned arm polymer is a compound represented by formula (2).

R ^c '-(R ^b ) _n -R ^a' ... (2)

[where:

R ^a' is a halogen atom;

R ^b is -CH ₂ -CR ¹¹ (-COOR ¹² )-,

R ¹¹ is a hydrogen atom or a methyl group,

R ¹² is C _1-20 alkyl,

R ^c ' is R ¹⁸ -R ¹⁷ -,

R ¹⁷ is -CR ¹⁹ ₂ -,

R ¹⁹ are each independently a hydrogen atom, a C _1-6 alkyl group, a phenyl group, or a halogen atom,

R ¹⁸ is R ^18a -OCO-, phenyl, or cyano,

R ^18a is an optionally substituted C _1-20 alkyl group,

n is an integer from 1 to 1,000].

[6] The star-shaped polymer as described in any one of [1] to [5] above, wherein the aforementioned polyfunctional alkenyl compound is a dienyl compound.

[7] The star-shaped polymer as described in [6] above, wherein the diene-based compound is a compound represented by formula (3).

CH ₂ =CR ^e -R ^d -CR ^e =CH ₂ ... (3)

[where:

R ^d is a divalent organic group,

R ^e is a hydrogen atom or a methyl group].

[8] The star-shaped polymer as described in [7] above, wherein R ^d is -R ²² -R ²¹ -R ²³ -,

R ²¹ is C _1-20 alkylene, phenylene, or -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, C _1-6 alkylene, or -CO-,

R ²³ is a single bond, C _1-6 alkylene, or -CO-.

[9] A resin-laminated substrate with an adhesive layer, comprising: coating the star-shaped polymer described in any one of [1] to [8] above on the resin substrate to form a coating film with a water contact angle of 80 to 130 degrees.

[10] The 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 the above [9] or [10], wherein the resin substrate is a fluororesin substrate.

[12] A coated substrate provided with an adhesive layer, wherein the star-shaped polymer described in any one of [1] to [8] above covers 80% or more of the area of the substrate in solid content.

[13] The coated base material having an adhesive layer according to the above [12], wherein the solid content includes a star polymer.

[14] The coated base material having an adhesive layer according to the above [13], wherein the base material is a resin base material.

[15] The coated base material having an adhesive layer according to the above [14], wherein the resin base material is a fluorine base material.

[16] A film formed on the coated substrate as described in any one of [12] to [15] above.

[17] A laminate comprising:

Fluorine resin substrate;

An adhesive layer comprising the star-shaped polymer described in any one of [1] to [8] above; and

A bonded layer selected from metal layers, non-fluororesin layers, fluororesin layers, and inorganic layers;

The fluororesin substrate and the adhered layer are bonded by the bonding layer.

[18] The laminate according to the above [17], wherein the layer to be adhered is a metal layer.

[19] The laminate according to the above [17] or [18], wherein the fluororesin substrate is composed of polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polychloride Trifluoroethylene, 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 [17] to [19] above, wherein the metal layer is a copper layer.

[21] The laminate according to any one of [17] to [20] above, wherein the surface roughness Rz of the metal layer on the bonding side is 2 μm or less.

[22] A circuit board comprising the laminate described in any one of [17] to [21] above.

[23] The circuit board as described in [22] above, which is a high-frequency circuit board.

[24] An inner lining comprising the laminate according to any one of [17] to [21].

[25] A laminated tube comprising the laminate described in any one of [17] to [21] above.

The star polymers of the present disclosure exhibit high film-forming properties on various substrates, especially on both metal substrates and resin substrates.

The present disclosure provides a star polymer having an arm comprising a structure derived from an arm polymer of a polymer belonging to a vinyl monomer and a core comprising a structure derived from crosslinking the arms For the structure of the polyfunctional alkenyl compound, the aforementioned star polymer has 5 to 25 mol% of the structure derived from the arm polymer relative to the structure derived from the polyfunctional alkenyl compound.

The above-mentioned star polymer is obtained by reacting the arm polymer of a polymer which is a vinyl monomer with a polyfunctional alkenyl compound and cross-linking the arm polymer.

[vinyl monomer]

The aforementioned vinyl monomer refers to a monomer having a vinyl group, such as (meth)acrylate, (meth)acrylamide, styrene, or vinyl ester.

In this specification, "(meth)acrylate" includes "acrylate" and "methacrylate". Likewise, "(meth)acrylamide" includes both "acrylamide" and "methacrylamide".

The above-mentioned (meth)acrylate is preferably an alkyl (meth)acrylate having an alkyl group having 1 to 30 carbon atoms.

The alkyl group in the above-mentioned alkyl (meth)acrylate may be any of linear, branched or cyclic, preferably linear.

The alkyl group in the above-mentioned alkyl (meth)acrylate may be substituted or unsubstituted, preferably unsubstituted.

The alkyl group in the above-mentioned alkyl (meth)acrylate is preferably an alkyl group having 1 to 30 carbons, more preferably an alkyl group having 1 to 24 carbons, such as 1 to 20 or 1 to 18 alkyls.

The aforementioned (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate ,(First base) isobutyl acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, neopentyl (meth)acrylate, octyl (meth)acrylate, (meth)acrylic acid 2 - Alkyl (meth)acrylates such as ethylhexyl, isodecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate and stearyl (meth)acrylate (meth)acrylic acid cyclohexyl ester, (meth)acrylic acid camphenyl ester and (meth)acrylic acid tricyclodecynyl ester and other (meth)acrylic acid cycloalkyl esters; (meth)acrylic acid 2-methyl Oxyethyl ester, dimethylaminoethyl (meth)acrylate, chloroethyl (meth)acrylate, trifluoroethyl (meth)acrylate and tetrahydrofurfuryl (meth)acrylate, (meth) Polypropylene glycol acrylate, glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, Heteroatom-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate.

The aforementioned (meth)acrylamides are preferably compounds represented by the following formulae.

CH ₂ =CX ¹ -CONR ³¹ R ³²

[where,

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. ]

In one aspect, R ³¹ and R ³² are hydrogen atoms.

In other aspects, at least one of R ³¹ and R ³² is an alkyl group which may have a substituent.

The alkyl group in R ³¹ and R ³² above can be any of straight chain, branched chain or cyclic, preferably straight chain.

The alkyl group in ^R31 and ^R32 above is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.

The substituents of the alkyl groups in R ³¹ and R ³² are not particularly limited, and examples thereof include hydroxyl, halogen atoms, alkoxy groups with 1 to 6 carbon atoms, aryl groups, and acyl groups.

The aforementioned (meth)acrylamides include, for example, (meth)acrylamide, N-methacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N,N- Dimethacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N-ethylmethacrylamide, N-methyl-N-ethyl Acrylamide, N-methyl-N-ethylmethacrylamide, N-isopropylacrylamide, N-n-propylacrylamide, N-isopropylmethacrylamide, N- N-propylmethacrylamide, N-methyl-N-n-propylacrylamide, N-methyl-N-isopropylacrylamide, N,N'-methylenebisacrylamide, N,N'-methylenebismethacrylamide, N-butyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-octyl(meth)acrylamide Amide, N-dodecyl (meth)acrylamide, N-octadecyl (meth)acrylamide, N-benzyl (meth)acrylamide, diacetone acrylamide, diacetone acrylamide, Acetone methacrylamide, N-methylol methacrylamide, N-methylol methacrylamide, etc.

The above-mentioned styrene is preferably a compound represented by the following formula.

[where:

^X2 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. ]

In one aspect, R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , and R ³⁹ are hydrogen atoms.

In other aspects, at least one of R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , and R ³⁹ is an alkyl group.

The alkyl groups in R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , and R ³⁹ above may be linear, branched, or cyclic.

The alkyl group in R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , and R ³⁹ is preferably an alkyl group with 1 to 10 carbons, more preferably an alkyl group with 1 to 6 carbons, and even more preferably an alkane with 1 to 4 carbons. base.

The alkyl groups in R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , and R ³⁹ above may be substituted. The substituent of the alkyl group is not particularly limited, and examples thereof include a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an aryl group.

The aforementioned halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom or a chlorine atom.

The above-mentioned styrenes include, for example, styrene, o-, m-, or p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene Methylstyrene, 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-methylstyrene 2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethylstyrene, o-, m- or p-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, ortho, meta or p-tert-butylstyrene, ortho, M-or p-methoxystyrene, ortho-, m-or-p-chloromethylstyrene, ortho-, m-or-p-bromomethylstyrene, silicon-substituted styrene derivatives, etc.

The aforementioned vinyl ester is preferably a compound represented by the following formula.

CH ₂ =CX ³ -OCO-R ⁴¹

[where:

^X3 is a hydrogen atom or a methyl group,

R ⁴¹ is an alkyl group or an aryl group. ]

The alkyl group in the above-mentioned R ⁴¹ may be any of linear, branched or cyclic.

The alkyl group in R ⁴¹ above is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.

The aryl group in the above R ⁴¹ is preferably phenyl.

The alkyl and aryl groups in the above R ⁴¹ may be substituted. The substituents of the alkyl and aryl groups are not particularly limited, and examples thereof include halogen atoms, alkoxy groups having 1 to 6 carbon atoms, and aryl groups.

The aforementioned vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, trimethylvinyl acetate, vinyl caproate, n-octanoic vinyl ester, 2-ethylhexanoic acid Vinyl, Vinyl Laurate, Vinyl Myristate, Vinyl Palmitate, Vinyl Stearate, Vinyl Trimethyl Acetate, Vinyl Diethyl Acetate, Vinyl Chloroacetate, Vinyl Dichloroacetate, Methoxyvinyl acetate, Butoxyvinyl acetate, Vinyl phenylacetate, Vinyl acetoacetate, Vinyl beta-phenylbutyrate, Vinyl benzoate, Vinyl salicylate, Vinyl chlorobenzoate , vinyl tetrachlorobenzoate, vinyl naphthoate, etc.

[Arm polymer]

The above-mentioned arm polymer can be obtained by polymerizing the above-mentioned vinyl monomer.

In a preferred aspect, the aforementioned arm polymer is a polymer synthesized by living radical polymerization of vinyl monomers.

In a more preferred aspect, the above-mentioned arm polymer is polymerized by reversible addition-fragmentation chain transfer (RAFT), atom transfer radical polymerization (ATRP), nitroxide mediated radical polymerization (NMP), reversible transfer catalyst Polymers synthesized by polymerization (RTCP), reversible coordination-mediated polymerization (RCMP), and organic tellurium-mediated living radical polymerization (TERP).

In yet a more preferable aspect, the above-mentioned arm polymer is a polymer represented by formula (1).

R ^c -(R ^b ) _n -SC(=S)-R ^a ...(1)

[where:

R ^a is alkyl, phenyl, -SR ^a1 , -OR ^a2 , -NR ^a3 ₂ ,

R ^a1 , R ^a2 , R ^a3 , R ^a4 , R ^a5 and R ^a6 are independently C _1-20 alkyl or phenyl;

R ^a7 is hydrogen or a halogen atom,

R ^b is -CH ₂ -CR ¹¹ (-COOR ¹² )-,

R ¹¹ is a hydrogen atom or a methyl group,

R ¹² is C _1-20 alkyl,

R ^c is R ¹⁶ -R ¹⁵ -,

R ¹⁵ is a C _1-6 alkylene group that may be substituted,

R ¹⁶ is carboxyl, hydroxyl, or phenyl,

n is an integer of 1 to 1,000. ]

In the above formula, R ^a is alkyl, phenyl, -SR ^a1 , -OR ^a2 , -NR ^a3 ₂ ,

^Ra can be part of a RAFT agent.

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.

The aforementioned R ^a1 is preferably a C _1-20 alkyl group, more preferably a C _3-18 alkyl group, and even more preferably a C _4-12 alkyl group.

The above R ^a2 is preferably phenyl or C _1-20 alkyl. The C _1-20 alkyl group is preferably a C _1-10 alkyl group, more preferably a C _1-6 alkyl group, and even more preferably a C _1-3 alkyl group.

The aforementioned R ^a3 is preferably a C _1-20 alkyl group, more preferably a C _1-10 alkyl group, more preferably a C _1-6 alkyl group, and even more preferably a C _1-3 alkyl group.

The aforementioned R ^a4 is preferably a C _1-6 alkyl group, more preferably a C _1-3 alkyl group, and even more preferably a methyl group.

The above-mentioned R ^a5 is preferably a C _1-6 alkyl group, more preferably a C _1-3 alkyl group, and even more preferably a methyl group.

The above-mentioned R ^a6 is preferably a C _1-6 alkyl group, more preferably a C _1-3 alkyl group, and even more preferably a methyl group.

The aforementioned R ^a7 is hydrogen or a halogen atom (such as fluorine, chlorine, bromine or iodine, preferably chlorine).

In one aspect, R ^a is -SR ^a1 or -OR ^a2 .

In the above formula, R ^b is a group represented by -CH ₂ -CR ¹¹ (-COOR ¹² )-.

[where:

R ¹¹ is a hydrogen atom or a methyl group,

R ¹² is C _1-20 alkyl. ]

The aforementioned R ¹² may be any of straight chain, branched chain or cyclic.

The aforementioned R ¹² is preferably a C _1-18 alkyl group, more preferably a C _1-6 alkyl group.

The aforementioned R ^c is R ¹⁶ -R ¹⁵ -, R ¹⁵ is a C _1-6 alkylene group that may be substituted, and R ¹⁶ is carboxyl, hydroxyl, or phenyl.

The above-mentioned C _1-6 alkylene group of R ¹⁵ may be a straight chain or a branched chain.

In one aspect, the above R ¹⁵ is an unsubstituted C _1-6 alkylene group.

In one aspect, the above R ¹⁵ is a substituted C _1-6 alkylene group. The substituent of the C _1-6 alkylene group is not particularly limited, and examples thereof include a halogen atom, a cyano group, a hydroxyl group, and an aryl group.

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

The number average molecular weight of the aforementioned arm polymer is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000. The number average molecular weight is a value measured by GPC measurement (polystyrene conversion).

The molecular weight distribution (PDI (Poly Dispersity Index)) of the arm polymer of the present disclosure is preferably not less than 1.0 and not more than 3.0, more preferably not less than 1.1 and not more than 2.0.

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

In other preferred aspects, the above-mentioned arm polymer is a polymer represented by formula (2).

R ^c '-(R ^b ) _n -R ^a' ... (2)

[where:

R ^a' is a halogen atom;

R ^b is -CH ₂ -CR ¹¹ (-COOR ¹² )-,

R ¹¹ is a hydrogen atom or a methyl group,

R ¹² is C _1-20 alkyl,

R ^c ' is R ¹⁸ -R ¹⁷ -,

R ¹⁷ is -CR ¹⁹ ₂ -,

R ¹⁹ are each independently a hydrogen atom, a C _1-6 alkyl group, a phenyl group, or a halogen atom,

R ¹⁸ is R ^18a -OCO-, phenyl, or cyano,

R ^18a is an optionally substituted C _1-20 alkyl group,

n is an integer of 1 to 1,000. ]

The aforementioned R ^a' is a halogen atom, more preferably chlorine or bromine, still more preferably bromine.

The above-mentioned R ^b has the same meaning as described in the polymer represented by the above-mentioned formula (1).

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

The above R ^c ' is R ¹⁸ -R ¹⁷ -, R ¹⁷ is -CR ¹⁹ ₂ -, R ¹⁹ is independently hydrogen atom, C _1-6 alkyl, phenyl, or halogen atom, R ¹⁸ is R ^18a - OCO-, phenyl, or cyano, R ^18a is a hydrogen atom, or a C _1-20 alkyl group that may be substituted, preferably a C _1-20 alkyl group that may be substituted.

The aforementioned R ¹⁸ is preferably R ^18a -OCO-.

The above-mentioned C _1-20 alkyl group of R ^18a may be linear or branched.

In one aspect, the above R ^18a is an unsubstituted C _1-20 alkyl group.

In one aspect, the above R ^18a is a substituted C _1-20 alkyl group. The substituent of the C _1-20 alkyl group is not particularly limited, and examples thereof include hydroxyl, vinyl, propargyl, trialkylsilyl, trialkoxysilyl, and the like.

The C _1-20 alkyl group of R ^18a is preferably a C _1-10 alkyl group, more preferably a C _1-6 alkyl group, and more preferably a methyl group or an ethyl group.

The above-mentioned C _1-6 alkyl group of R ¹⁹ may be linear or branched.

The above-mentioned R ¹⁹ is preferably a C _1-3 alkyl group, more preferably a methyl group.

The polymer represented by the above formula (2) can be synthesized by, for example, the so-called ATRP (Atom transfer Radical polymerization) method.

[Polyfunctional alkenyl compound]

The above polyfunctional alkenyl compound refers to a compound having a plurality of double bonds.

The number of the above-mentioned double bonds is preferably 2 to 6, more preferably 2 to 4, still more preferably 2 or 3, particularly preferably 2. This double bond is preferably present at the terminal of the molecule. That is, the double bond exists as a CH ₂ =CR ^e - group (wherein, R ^e represents a hydrogen atom, a chlorine atom, a fluorine atom or an alkyl group having 1 to 10 carbons).

In one aspect, the polyfunctional alkenyl compound is a dienyl compound.

In a preferred aspect, the above-mentioned dienyl compound is a compound represented by formula (3).

CH ₂ =CR ^e -R ^d -CR ^e =CH ₂ ... (3)

[where:

R ^d is a divalent organic group,

R ^e is a hydrogen atom or a methyl group. ]

The aforementioned R ^d is preferably a group represented by -R ²² -R ²¹ -R ²³ -.

[where:

R ²¹ is C _1-20 alkylene, phenylene, or -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, C _1-6 alkylene, or -CO-,

R ²³ is a single bond, C _1-6 alkylene, or -CO-. ]

The alkylene group in R ²¹ , R ²² , and R ²³ above is preferably any one of straight chain, branched chain or cyclic, and may be substituted or unsubstituted.

The C _1-20 alkylene in the above R ²¹ is preferably a C _2-16 alkylene, more preferably a C _4-10 alkylene.

The above-mentioned α is preferably 2 to 4, more preferably 2.

The aforementioned β is preferably 2-10, more preferably 2-6.

The aforementioned R ²² and R ²³ are preferably CO.

In one aspect, R ^e is a hydrogen atom.

In one aspect, Re ^is methyl.

The polyfunctional alkenyl compound mentioned above can be, for example, divinylbenzene; (meth)acrylates at both ends of diols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, and cyclohexanedimethanol; polyester polyols (meth)acrylates; (meth)acrylates of polyols such as trimethylolpropane or neopentylthritol; make epoxy in monomers with acid groups and monomers with epoxypropyl groups Reacting propyl groups with acid groups; reacting monomers with hydroxyl groups with monomers with isocyanate, etc.

The star-shaped polymer of the present disclosure has an arm portion comprising a structure of an arm polymer derived from a polymer belonging to a vinyl monomer, and a core portion comprising a multifunctional structure derived from cross-linking the arm portion. For the structure of the alkenyl compound, the aforementioned star polymer has 5 to 25 mol% of the structure derived from the arm polymer relative to the structure derived from the polyfunctional alkenyl compound.

The cross-linked polymer of the present disclosure can be obtained by reacting the arm polymer with a polyfunctional alkenyl compound, and cross-linking the arm polymer with the polyfunctional alkenyl compound.

For example, when the arm polymer shown in formula (1) or (2) is reacted with the dienyl compound shown in formula (3), the growth terminal of the arm polymer shown in formula (1) (R ^c -(R ^b ) _n - terminal, or R ^c '-(R ^b ) _n - terminal) reacts with -CH=CH ₂ on one side of the dienyl compound shown in formula (3), and polymerizes the block of the dienyl compound in the arm polymer. The -CR ^e =CH ₂ derived from the diene compound in the obtained block polymer reacts with the growing end of another block polymer, whereby the arm polymer can be cross-linked by the diene compound.

The above-mentioned core part is formed by making the end of the arm polymer and the polyfunctional alkenyl compound form a microgel. For example, the star-shaped polymer is obtained by reacting the arm polymer shown in formula (1) or (2) with the diene compound shown in formula (3). In the star-shaped polymer, the arm polymer shown in formula (1) The -SC(=S)-R ^a part or the R ^a ' part of the arm polymer represented by formula (2) and the part derived from the dienyl compound represented by formula (3) will constitute the core part.

The arm portion is a polymer chain branched from the core portion. The arm portion is typically composed of the polymer portion of the arm polymer. For example, in the case of the arm polymer shown in formula (1), the R ^c -(R ^b ) _n -part will constitute the arm, and in the case of the arm polymer shown in formula (2), R ^c '-(R ^b ) _{The n} -section will form the arm.

The aforementioned arm polymer is preferably obtainable by living radical polymerization. Synthesizing the arm polymer by living radical polymerization can reduce the molecular weight distribution (PDI) of the arm polymer, and further reduce the molecular weight distribution of the star polymer.

In the above reaction, the concentration of the polyfunctional alkenyl compound is preferably 150 to 500 mM. By using the polyfunctional alkenyl compound at this concentration, high wettability and high adhesion to substrates, especially fluororesin substrates can be obtained.

Relative to the structure derived from the multifunctional alkenyl compound, the star polymer of the present disclosure has 5 to 25 mol% of the structure derived from the arm polymer, preferably 5 to 22 mol%, more preferably 5 to 20 mol%. That is, the star polymer of the present disclosure is obtained by reacting a polyfunctional alkenyl compound with 5 to 25 mol % of an arm polymer relative to the polyfunctional alkenyl compound.

The number average molecular weight of the star polymer disclosed herein is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 800,000, and still more preferably from 15,000 to 600,000. This number average molecular weight is a value measured by GPC measurement (polystyrene conversion).

The molecular weight distribution (PDI) of the star polymer disclosed herein is preferably not less than 1.0 and not more than 10.0, more preferably not less than 1.1 and not more than 7.0, and more preferably not less than 1.1 and not more than 5.0.

The present disclosure provides a composition comprising the star polymer of the present disclosure.

In one aspect, the above composition is a coating agent.

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

The above-mentioned solvents include chlorine-containing solvents such as chloroform, dichloromethane, dichloroethane, and carbon tetrachloride; aprotic polar solvents such as dimethylformamide and dimethylsulfoxide; hexane, cyclohexane, and the like; Hydrocarbon solvents such as alkanes, cellothane solvents such as methyl cellothreon, ethyl cellothreonate, methyl cellothreon acetate, ethyl cellothreoacetate, etc.; diethyl oxalate, ethyl pyruvate Ethyl 2-Hydroxybutyrate, Ethyl Acetate, Ethyl Acetate, Butyl Acetate, Amyl Acetate, Ethyl Butyrate, Butyl Butyrate, Methyl Lactate, Ethyl Lactate, 3-Methoxy Ester solvents such as methyl propionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; 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, dipropylene glycol dimethyl ether and other propylene glycol solvents; acetone, methyl ethyl ketone , methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylamino ketone, 2-heptanone and other ketone solvents; methanol, ethanol, propanol, isopropanol, butanol, diacetone alcohol and other alcohols Solvents; aromatic hydrocarbons such as toluene and xylene, etc. These solvents can be used individually or in mixture of 2 or more types.

The concentration of the star polymer in the composition disclosed herein is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, and more preferably 3 to 20% by mass.

The 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 still more preferably 90 to 120 degrees.

In this specification, the water contact angle is the static contact angle when the measurement object is placed horizontally and 2 μL of water is dropped on the surface.

The coating agents of the present disclosure can be applied to substrates.

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

The aforementioned substrate is preferably a resin substrate, more preferably a fluororesin substrate. That is to say, the coating agent disclosed herein can be used for resin substrates, preferably for fluororesin substrates.

The above-mentioned fluororesin is not particularly limited, and examples thereof include polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene/tetrafluoroethylene copolymer, vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene Fluoroethylene copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/perfluoroalkoxyethylene copolymer, ethylene/chlorotrifluoroethylene copolymer, vinylidene fluoride/hexafluoropropylene copolymer, or Difluoroethylene/tetrafluoroethylene/hexafluoropropylene copolymer, etc.

From the viewpoint of bonding strength between fluororesin and metal, fluororesin may be surface-treated.

Surface treatment can be, for example, etching treatment, plasma treatment, corona treatment, photochemical treatment, etc., preferably plasma treatment or corona treatment. The conditions of the surface treatment can be appropriately set according to the composition of the fluororesin and the like.

The coating agent of the present disclosure has excellent film-forming properties. For example, drop more than 0.5mL of the coating agent of the present disclosure on a substrate with a water contact angle of 30mm×30mm and a water contact angle of 60 to 150 degrees to cover the entire substrate, spin coating at 300rpm for 3 seconds, and then spin coating at 2500rpm At 27 seconds, the solid content can cover more than 80% of the substrate area, more preferably more than 90%.

The coating agent disclosed herein can also be used as an adhesive.

The present disclosure provides a laminate comprising a fluororesin substrate, an adhesive layer containing the star-shaped polymer of the present disclosure, and an adhesive layer selected from a metal layer, a non-fluororesin layer, a fluororesin layer, and an inorganic The next layer in the layer. In this laminate, the fluororesin substrate and the adhered layer are bonded by the bonding layer.

In the laminate of the present disclosure, a layer containing the star-shaped polymer of the present disclosure that exhibits good adhesion and wettability to the base material and the layer to be bonded is used as an adhesive layer, so that the layers can be firmly bonded.

The above-mentioned adhered layer is a layer adhered to the substrate by an adhesive layer, and is selected from a metal layer, a non-fluororesin layer, a fluororesin layer, and an inorganic layer.

In one aspect, the above-mentioned adhered layer is a metal layer.

The surface roughness Rz of the bonding side of the metal layer is preferably 2 μm or less. Thereby, the transmission loss between the base material and the metal layer in the laminate can be improved.

The surface roughness Rz is more preferably at most 1.8 μm, more preferably at most 1.5 μm, more preferably at least 0.3 μm, and more preferably at least 0.5 μm.

In addition, the surface roughness Rz is a value calculated by the method of JIS C 6515-1998 (maximum height roughness).

The metal constituting the above-mentioned metal layer is preferably at least one selected from the group consisting of copper, gold, silver, stainless steel, aluminum, iron, ruthenium, and these alloys, more preferably selected from copper, gold, silver , stainless steel, ruthenium, and at least one of the group consisting of aluminum, and more preferably copper.

Examples of the above-mentioned stainless steel include Worthian iron-based stainless steel, Matian iron-based stainless steel, fertilizer iron-based stainless steel, and the like.

In a preferable aspect, the above-mentioned laminate is a circuit board, a lining material, or a laminate tube.

The above-mentioned circuit board is preferably a printed wiring board. In addition, the above-mentioned circuit board is preferably a high-frequency circuit board.

The star-shaped polymers, compositions and laminates of the present disclosure are described above in detail, but the present invention is not limited thereto.

(Example)

The following examples illustrate the star-shaped polymer and the laminate of the present disclosure, but the present disclosure is not limited to the following examples.

(Synthesis example 1) Arm polymer: Synthesis of polymethyl acrylate (pMA)

Add 1,4-dioxane (41mL), methyl acrylate (8.61g), 4-cyano-4-(dodecylmercaptothiocarbonyl)mercaptopentanoic acid into a nitrogen-substituted reaction vessel (0.404g) and 2,2'-azobis(isobutyronitrile) (16.4mg), reacted at 60°C for 24 hours. The polymerization solution was dried under reduced pressure to obtain the arm polymer pMA. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 6,700 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.36.

(Synthesis Example 2) Arm polymer: Synthesis of polybutyl acrylate (pBA)

Add 1,4-dioxane (14.3mL), butyl acrylate (5.12g), 4-cyano-4-(dodecylhydrogenthiocarbonyl)hydromercaptan to a nitrogen-substituted reaction vessel Acid (0.162g), and 2,2'-azobis(isobutyronitrile) (6.6mg), react at 60°C for 24 hours, drop the polymerization solution into methanol/water mixed solvent (volume ratio 9:1) , to obtain the arm polymer pBA. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 8,000 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.12.

(Synthesis Example 3) Arm polymer: Synthesis of polyoctyl acrylate (pOA)

Add 1,4-dioxane (17.5mL), octyl acrylate (11.1g), 4-cyano-4-(dodecylhydrogenthiocarbonyl)hydromercaptan to a nitrogen-substituted reaction vessel acid (0.242g), and 2,2'-azobis(isobutyronitrile) (9.9mg), react at 80°C for 6 hours, drop the polymerization solution into methanol, and obtain arm polymerization Object pOA. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 8,900 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.34.

(Synthesis Example 4) Arm polymer: Synthesis of polydodecyl acrylate (pDA)

Add 1,4-dioxane (4.54mL), dodecyl acrylate (4.80g), 4-cyano-4-(dodecylhydrogenthiocarbonyl) hydrogen sulfide into a nitrogen-substituted reaction vessel Gvaleric acid (80.8 mg) and 2,2'-azobis(isobutyronitrile) (3.3 mg) were reacted at 60° C. for 24 hours, and the polymerization solution was dropped into methanol to obtain the arm polymer pDA. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 14,000 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.23.

(Synthesis example 5) Arm polymer: Synthesis of polystearyl acrylate (pSA)

Add 1,4-dioxane (10mL), stearyl acrylate (6.50g), 4-cyano-4-(dodecylhydrogenthiocarbonyl)hydromercaptan to a nitrogen-substituted reaction vessel acid (80.9mg), and 2,2'-azobis(isobutyronitrile) (3.3mg), reacted at 60°C for 24 hours, dripped the polymerization solution into methanol and precipitated it, and added 1,4-dioxane By washing, the arm polymer pSA was obtained. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 13,000 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.22.

(Synthesis Example 6) Arm polymer: Synthesis of hydroxyl-terminated polybutylacrylate (pBA)

Add 1,4-dioxane (14.3mL), butyl acrylate (5.13g), 4-cyano-4-[(dodecylhydrogenthiocarbonyl)hydrogenthio to a nitrogen-substituted reaction vessel ]amyl alcohol (0.156g), and 2,2'-azobis(isobutyronitrile) (6.6mg), reacted at 60°C for 24 hours, and dripped the polymerization solution into methanol/water mixed solvent (volume ratio of 9: 1), to obtain the arm polymer pBA. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 10,300 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.15.

(Synthesis Example 7) Arm polymer: synthesis of benzyl-terminated polybutylacrylate (pBA)

Add 1,4-dioxane (14.3mL), butyl acrylate (5.10g), benzyl dodecyl trithiocarbonate (0.148g), and 2,2'-isocyanate into a nitrogen-substituted reaction vessel Nitrobis(isobutyronitrile) (6.6 mg) was reacted at 60° C. for 24 hours, and the polymerization solution was dropped into a mixed solvent of methanol/water (9:1 by volume) to obtain the arm polymer pBA. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 12,000 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.19.

(Synthesis example 8) Synthesis of pMA arm star polymer, crosslinking agent concentration 200mM

Add 1,4-dioxane (9.5 mL), pMA (2.0 g) obtained in Synthesis Example 1, and polyethylene glycol diacrylate [number average molecular weight 250] (0.50 g) into a nitrogen-substituted reaction vessel, and 2,2'-azobis(isobutyronitrile) (3.3 mg), and reacted at 60° C. for 24 hours. The polymerization solution was dropped into a mixed solvent of methanol/water (4:1 by volume) to obtain a star-shaped polymer. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 30,200 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.52.

(Synthesis example 9) Synthesis of pBA arm star polymer, cross-linking agent concentration 400mM

1,4-dioxane (6.35 mL), pBA obtained in Synthesis Example 2 (1.88 g), polyethylene glycol diacrylate [number average molecular weight 250] (0.70 g), and 2,2'-Azobis(isobutyronitrile) (2.3 mg), reacted at 60°C for 24 hours. The polymerization solution was dropped into methanol to obtain a star-shaped polymer. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 54,600 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.91.

(Synthesis example 10) Synthesis of pOA arm star polymer, crosslinking agent concentration 400mM

1,4-dioxane (9.0 mL), pOA (4.02 g) obtained in Synthesis Example 3, polyethylene glycol diacrylate [number average molecular weight of 250] (1.0 g), and 2,2'-Azobis(isobutyronitrile) (3.3 mg), reacted at 80°C for 20 hours. The polymerization solution was dropped into methanol and precipitated, followed by re-precipitating in cooled acetone, thereby obtaining a star-shaped polymer. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 252,000 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.49.

(Synthesis example 11) Synthesis of pDA arm star polymer, cross-linking agent concentration 400mM

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) (2.0mg), react at 60°C for 24 hours. The polymerization solution was dropped into methanol to form a precipitate, and the precipitate was dissolved in toluene, and methanol was added thereto, thereby obtaining a star-shaped polymer as a precipitate. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 291,000 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.94.

(Synthesis example 12) Synthesis of pSA arm star polymer, cross-linking agent concentration 400mM

1,4-dioxane (4.60 mL), pSA obtained in Synthesis Example 5 (3.40 g), polyethylene glycol diacrylate [number average molecular weight 250] (0.50 g), and 2,2'-Azobis(isobutyronitrile) (1.6 mg), reacted at 60°C for 24 hours. The polymerization solution was dropped into methanol to form a precipitate, and the precipitate was dissolved in toluene, and methanol was added thereto, thereby obtaining a star-shaped polymer as a precipitate. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 111,000 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.72.

(Synthesis example 13) Synthesis of pBA arm star polymer, crosslinking agent concentration 300mM

Except having changed the quantity of polyethylene glycol diacrylate [the number average molecular weight is 250] into 0.53 g, it carried out similar operation to the synthesis example 9, and obtained the star polymer. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 54,700 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.66.

(Synthesis example 14) Synthesis of pBA arm star polymer, crosslinking agent concentration 200mM

Except having changed the quantity of polyethylene glycol diacrylate [the number average molecular weight is 250] into 0.35 g, it carried out similar operation to the synthesis example 9, and obtained the star polymer. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 31,200 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.24.

(Synthesis example 15) Synthesis of pBA arm star polymer, crosslinking agent concentration 100mM

Except having changed the quantity of polyethylene glycol diacrylate [the number average molecular weight is 250] into 0.18g, it carried out similar operation to the synthesis example 9, and obtained the star polymer. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 28,000 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.28.

(Synthesis example 16) Synthesis of pDA arm star polymer, cross-linking agent concentration 300mM

Except having changed the quantity of polyethylene glycol diacrylate [the number average molecular weight is 250] into 0.45 g, it carried out similar operation to the synthesis example 11, and obtained the star polymer. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 25,500 (in terms of polystyrene), and the molecular weight distribution (PDI) was 2.85.

(Synthesis example 17) Synthesis of pDA arm star polymer, crosslinking agent concentration 200mM

Except having changed the quantity of polyethylene glycol diacrylate [the number average molecular weight is 250] into 0.30 g, it carried out similar operation to the synthesis example 11, and obtained the star polymer. eluting with chloroform When measured by GPC of the liquid, the number average molecular weight (Mn) of the polymer was 19,600 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.82.

(Synthesis Example 18) Synthesis of hydroxyl-terminated pBA arm star polymer, cross-linking agent concentration 300mM

1,4-dioxane (6.50 mL), pBA (1.89 g) obtained in Synthesis Example 6, polyethylene glycol diacrylate [number average molecular weight of 250] (0.53 g), and 2,2'-Azobis(isobutyronitrile) (2.3 mg), reacted at 60°C for 24 hours. The polymerization solution was dropped into methanol to obtain a star-shaped polymer. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 129,000 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.39.

(Synthesis Example 19) Synthesis of benzyl-terminated pBA arm star polymer, cross-linking agent concentration 400mM

1,4-dioxane (3.65 mL), pBA (1.07 g) obtained in Synthesis Example 7, polyethylene glycol diacrylate [number average molecular weight of 250] (0.40 g), and 2,2'-Azobis(isobutyronitrile) (3.3 mg), reacted at 60°C for 144 hours. The polymerization solution was dropped into methanol to obtain a star-shaped polymer. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 166,000 (in terms of polystyrene), and the molecular weight distribution (PDI) was 3.13.

(Synthesis Example 20) Arm polymer: Synthesis of polybutyl acrylate (pBA)

Add anisole (8.8mL), copper (II) bromide (1.8mg), 2,2'-azobis(isobutyronitrile) (13.1mg), three [2-( Dimethylamino)ethyl]amine (Me ₆ TREN) in 50mM DMF solution (0.8mL), butyl acrylate (5.11g), ethyl 2-bromoisobutyrate (77.8mg), react at 70°C for 24 Hours, the polymerization solution was dropped into a methanol/water mixed solvent to obtain the arm polymer pBA. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 8,200 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.25.

(Synthesis example 21) Synthesis of pBA arm star polymer, cross-linking agent concentration 400mM

Add anisole (6.35mL), copper(II) bromide (5.2mg), 2,2'-azobis(isobutyronitrile) (7.7mg), tris[2-( Dimethylamino) ethyl] amine (Me ₆ TREN) 50mM DMF solution (0.47mL), pBA (1.93g) obtained in Synthesis Example 20, polyethylene glycol diacrylate [the number average molecular weight is 250] (0.70 g) react at 70° C. for 24 hours, drop the polymerization solution into methanol, and obtain a star-shaped polymer. When GPC measurement was performed using chloroform as an eluent, the number average molecular weight (Mn) of the polymer was 65,000 (in terms of polystyrene), and the molecular weight distribution (PDI) was 1.30.

Evaluation of Film Formability on Substrates

Add 0.5 mL or more of the 5% by mass chloroform solution of the linear polymers obtained in Synthesis Examples 1 to 7 and 20 and the star-shaped polymers obtained in Synthesis Examples 8 to 19 and 21 into a 30 mm × 30 mm polystyrene in such a way as to cover the entire surface of the substrate. Vinyl fluoride (PTFE) substrate (manufactured by NICHIAS), tetrafluoroethylene/perfluoroalkoxyethylene copolymer resin (PFA) substrate (manufactured by Daikin Industries), or copper foil (surface roughness Rz: 0.85 μm, Fukuda Metal Foil Co., Ltd.), spin coating at 300 rpm for 3 seconds, and then spin coating at 2500 rpm for 27 seconds to form a film (Examples 1 to 12, Comparative Examples 1 to 9).

Film-forming properties were evaluated visually. The evaluation criteria are as follows.

1: The coverage rate of the substrate surface of the coating film is more than 80%.

2: The coverage rate of the substrate surface of the coating film is less than 80%.

Determination of the water contact angle of the coating film

The water contact angle of the star-shaped polymer coating film fabricated on PTFE substrate and PFA substrate was measured. The drop volume is 2 μL. In addition, in the evaluation of film-forming property, the polymer-coated surface of the base material was small in two cases, and the contact angle measurement could not be performed.

[Table 1]

From the above results, it was confirmed that the star polymer of the present disclosure has high film-forming properties even on PTFE substrates and PFA substrates.

(Availability of industry)

The disclosed star polymers are suitable for use as adhesives.

Claims (25)

A star polymer having an arm and a core, The aforementioned arm portion comprises a structure derived from an arm polymer of a polymer belonging to a vinyl monomer, The aforementioned core portion comprises a structure derived from a polyfunctional alkenyl compound cross-linked with the aforementioned arm portion, The aforementioned star polymer has 5 to 25 mol% of the structure derived from the arm polymer relative to the structure derived from the polyfunctional alkenyl compound. The star-shaped polymer according to claim 1, wherein the aforementioned vinyl monomer is (meth)acrylate, (meth)acrylamide, styrene, or vinyl ester. The star polymer according to claim 1 or 2, wherein the aforementioned arm polymer is a polymer synthesized by living radical polymerization. The star-shaped polymer according to any one of claims 1 to 3, wherein the aforementioned arm polymer is a polymer represented by formula (1), R ^c -(R ^b ) _n -SC(=S)-R ^a ...(1) [where: R ^a is alkyl, phenyl, -SR ^a1 , -OR ^a2 , -NR ^a3 ₂ ,

R ^a1 , R ^a2 , R ^a3 , R ^a4 , R ^a5 and R ^a6 are independently C _1-20 alkyl or phenyl; R ^a7 is hydrogen or a halogen atom, R ^b is -CH ₂ -CR ¹¹ (-COOR ¹² )-, R ¹¹ is a hydrogen atom or a methyl group, R ¹² is C _1-20 alkyl, R ^c is R ¹⁶ -R ¹⁵ -, R ¹⁵ is a C _1-6 alkylene group that may be substituted, R ¹⁶ is carboxyl, hydroxyl, or phenyl, n is an integer from 1 to 1,000]. The star polymer as described in any one of claims 1 to 3, wherein the aforementioned arm polymer is a polymer represented by formula (2), R ^c '-(R ^b ) _n -R ^a' ...(2) [where: R ^a' is a halogen atom; R ^b is -CH ₂ -CR ¹¹ (-COOR ¹² )-, R ¹¹ is a hydrogen atom or a methyl group, R ¹² is C _1-20 alkyl, R ^c ' is R ¹⁸ -R ¹⁷ -, R ¹⁷ is -CR ¹⁹ ₂ -, R ¹⁹ are independently hydrogen atom, C _1-6 alkyl, phenyl, or halogen atom, R ¹⁸ is R ^18a -OCO-, phenyl, or cyano, R ^18a is an optionally substituted C _1-20 alkyl group, n is an integer from 1 to 1,000]. The star-shaped polymer according to any one of claims 1 to 5, wherein the aforementioned polyfunctional alkenyl compound is a dienyl compound. The star-shaped polymer as claimed in item 6, wherein the aforementioned diene-based compound is a compound shown in formula (3), CH ₂ =CR ^e -R ^d -CR ^e =CH ₂ ... (3) [where: R ^d is a divalent organic group, R ^e is a hydrogen atom or a methyl group]. The star polymer as claimed in item 7, wherein R ^d is -R ²² -R ²¹ -R ²³ -, R ²¹ is C _1-20 alkylene, phenylene, or -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, C _1-6 alkylene, or -CO-, R ²³ is a single bond, C _1-6 alkylene, or -CO-. A coating agent for a resin laminated base material with an adhesive layer, which is: the coating film formed by coating the resin base material with the star-shaped polymer described in any one of claims 1 to 8 has a water contact angle of 80 to 130 degrees. The coating agent for a laminated substrate having an adhesive layer according to claim 9, wherein the resin substrate has a water contact angle of 60 to 150 degrees. The coating agent for a laminated substrate having an adhesive layer according to claim 9 or 10, wherein the resin substrate is a fluororesin substrate. A coated substrate with an adhesive layer, which is a star-shaped polymer as described in any one of Claims 1 to 8 covering more than 80% of the area of the substrate with solid content. The coated substrate with an adhesive layer according to claim 12, wherein the aforementioned solid content includes a star polymer. The coated substrate with an adhesive layer according to claim 13, wherein the aforementioned substrate is a resin substrate. The coated substrate with an adhesive layer as described in claim 14, wherein the aforementioned resin substrate is a fluorine substrate. A film formed on the coated substrate according to any one of claims 12 to 15. A laminate comprising: Fluorine resin substrate; An adhesive layer comprising a star polymer according to any one of claims 1 to 8; and A bonded layer selected from metal layers, non-fluororesin layers, fluororesin layers, and inorganic layers; The fluororesin substrate and the adhered layer are bonded by the bonding layer. The laminated body according to claim 17, wherein the layer to be adhered is a metal layer. The laminate according to claim 17 or 18, wherein the fluororesin substrate is made of the following: polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene/tetrafluoroethylene Vinyl fluoride copolymer, vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/perfluoroalkoxyethylene copolymer, ethylene/chlorotrifluoroethylene copolymer compound, vinylidene fluoride/hexafluoropropylene copolymer, or vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene copolymer. The laminate according to any one of claims 17 to 19, wherein the metal layer is a copper layer. The laminate according to any one of claims 17 to 20, wherein the surface roughness Rz of the metal layer on the bonding side is 2 μm or less. A circuit substrate comprising the laminate according to any one of Claims 17 to 21. The circuit substrate according to claim 22, which is a high-frequency circuit substrate. An inner lining material comprising the laminate according to any one of Claims 17 to 21. A laminated pipe comprising the laminate according to any one of Claims 17 to 21.