CN112789320A - Dispersion liquid and method for producing metal foil with resin - Google Patents
Dispersion liquid and method for producing metal foil with resin Download PDFInfo
- Publication number
- CN112789320A CN112789320A CN201980065447.8A CN201980065447A CN112789320A CN 112789320 A CN112789320 A CN 112789320A CN 201980065447 A CN201980065447 A CN 201980065447A CN 112789320 A CN112789320 A CN 112789320A
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- Prior art keywords
- polymer
- meth
- acrylate
- dispersion
- layer
- Prior art date
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- 239000006185 dispersion Substances 0.000 title claims abstract description 112
- 239000007788 liquid Substances 0.000 title claims abstract description 95
- 239000011347 resin Substances 0.000 title claims abstract description 76
- 229920005989 resin Polymers 0.000 title claims abstract description 76
- 239000011888 foil Substances 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 50
- 239000002184 metal Substances 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 206
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000000843 powder Substances 0.000 claims abstract description 62
- 239000002612 dispersion medium Substances 0.000 claims abstract description 34
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 21
- 230000009477 glass transition Effects 0.000 claims abstract description 15
- 239000010410 layer Substances 0.000 claims description 119
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 51
- 239000011247 coating layer Substances 0.000 claims description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 239000002609 medium Substances 0.000 claims description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000003566 oxetanyl group Chemical group 0.000 claims description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 238000010410 dusting Methods 0.000 abstract description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 31
- 239000011889 copper foil Substances 0.000 description 30
- 238000000034 method Methods 0.000 description 20
- 230000000704 physical effect Effects 0.000 description 18
- 239000007789 gas Substances 0.000 description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 description 15
- -1 Polytetrafluoroethylene Polymers 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 11
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 238000009832 plasma treatment Methods 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 230000001186 cumulative effect Effects 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229910000679 solder Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 5
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical group 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
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- 239000000758 substrate Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
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- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
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- 238000005227 gel permeation chromatography Methods 0.000 description 1
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- 125000005067 haloformyl group Chemical group 0.000 description 1
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- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
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- 238000010348 incorporation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000007760 metering rod coating Methods 0.000 description 1
- MKIJJIMOAABWGF-UHFFFAOYSA-N methyl 2-sulfanylacetate Chemical compound COC(=O)CS MKIJJIMOAABWGF-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
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- 239000003973 paint Substances 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Provided are a dispersion liquid which suppresses dusting at the time of forming a layer (resin layer) and can form a layer (resin layer) having excellent layer (resin layer) properties such as electrical properties, and a method for producing a resin-attached metal foil. The dispersion liquid of the present invention comprises a powder of a tetrafluoroethylene polymer, a (meth) acrylate polymer having a glass transition temperature of 0 to 120 ℃, and a liquid dispersion medium in which the tetrafluoroethylene polymer is dispersed. The dispersion liquid contains 0.1 to 10 parts by mass of the (meth) acrylic acid ester polymer per 100 parts by mass of the tetrafluoroethylene polymer.
Description
Technical Field
The present invention relates to a dispersion liquid which suppresses dusting during layer (resin layer) formation and enables formation of a layer (resin layer) having excellent physical properties of various layers (resin layers), and a method for producing a metal foil with resin.
Background
Tetrafluoroethylene polymers such as Polytetrafluoroethylene (PTFE) are excellent in chemical resistance, water-and oil-repellency, heat resistance, electrical characteristics and other physical properties, and various applications and various forms of use such as powders and films are known. Patent document 1 describes an aqueous dispersion containing a tetrafluoroethylene polymer powder, a depolymerizable acrylic polymer powder, and an aqueous medium.
In recent years, as a material for a printed circuit board corresponding to a frequency in a high frequency band, a tetrafluoroethylene polymer excellent in heat resistance such as low dielectric constant, low dielectric loss tangent and the like and solder reflow resistance has attracted attention.
Patent document 2 describes a resin-attached metal foil having a PTFE layer formed from a dispersion liquid in which PTFE powder is dispersed in a nonaqueous medium, and a method for forming a transmission line on the metal foil to produce a printed circuit board. Patent document 3 describes a nonaqueous dispersion of PTFE-containing powder as the dispersion.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2003/011991
Patent document 2: japanese patent laid-open publication No. 2015-509113
Patent document 3: international publication No. 2016/159102
Disclosure of Invention
Technical problem to be solved by the invention
The layer (resin layer) of the tetrafluoroethylene polymer formed from the dispersion is formed by: the dispersion liquid is applied to the surface of a substrate, the liquid dispersion medium is volatilized to form a filler layer of the powder on the surface of the substrate, and the powder is further melted or fired. However, the tetrafluoroethylene polymer is essentially non-adhesive, and the powder lacks inter-particle interactions. Therefore, the powder is easily broken (chipped) when the filling layer is formed.
The falling powder of the powder not only deteriorates the physical properties of the layer (resin layer), but also contaminates the article itself or the manufacturing apparatus, and lowers the productivity thereof. Therefore, there is a demand for a dispersion that can form a layer (resin layer) having excellent electrical properties (electrical properties such as dielectric constant and electrostatic loss tangent) and surface properties (heat resistance, chemical resistance, smoothness, gloss, etc.) while suppressing dusting.
The present inventors have assiduously studied and found that a dispersion containing a powder of a predetermined (meth) acrylate polymer and a tetrafluoroethylene polymer at a predetermined ratio can form a layer (resin layer) having excellent electrical properties and surface properties while suppressing dusting.
Technical scheme for solving technical problem
The present invention has the following technical contents.
[1] A dispersion liquid which comprises a powder of a tetrafluoroethylene polymer, a (meth) acrylate polymer having a glass transition temperature of 0 to 120 ℃, and a liquid dispersion medium in which the tetrafluoroethylene polymer is dispersed, wherein the (meth) acrylate polymer is contained in an amount of 0.1 to 10 parts by mass per 100 parts by mass of the tetrafluoroethylene polymer.
[2] The dispersion liquid according to [1], wherein the (meth) acrylate polymer is contained in an amount of 0.1 or more and less than 5 parts by mass per 100 parts by mass of the tetrafluoroethylene polymer.
[3] The dispersion liquid according to [1] or [2], wherein the liquid dispersion medium is a nonaqueous medium.
[4] The dispersion liquid according to any one of [1] to [3], wherein the liquid dispersion medium is an ester or an amide.
[5] The dispersion liquid according to any one of [1] to [4], wherein the tetrafluoroethylene-based polymer has at least 1 kind of functional group selected from a carbonyl group-containing group, a hydroxyl group, an epoxy group, an oxetanyl group, an amino group, a nitro group and an isocyanate group.
[6] The dispersion liquid according to any one of [1] to [5], wherein the (meth) acrylate polymer has a hydroxyl group.
[7] The dispersion liquid according to any one of [1] to [6], wherein the (meth) acrylate-based polymer comprises units based on at least 1 kind of (meth) acrylate selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobornyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth) acrylate.
[8] The dispersion liquid according to any one of [1] to [7], wherein the (meth) acrylate polymer is a methacrylate polymer.
[9] The dispersion liquid according to any one of [1] to [8], wherein the (meth) acrylate polymer has a weight average molecular weight of 10000 to 150000.
[10] The dispersion liquid according to any one of [1] to [9], further comprising a fluorine-based dispersant.
[11] The dispersion liquid according to any one of [1] to [10], further comprising at least 1 fluorine-based dispersant selected from the group consisting of fluoroalcohols, fluorosilicones, and fluoropolyethers.
[12] A method for producing a resin-equipped metal foil having a metal foil and a resin layer containing a tetrafluoroethylene polymer and provided in contact with the surface of the metal foil,
applying the dispersion liquid described in any one of [1] to [11] to the surface, forming a coating layer from the dispersion liquid, and further heating to remove the liquid dispersion medium, thereby melting or firing the tetrafluoroethylene polymer to form the resin layer.
[13] The production method according to [12], wherein the formation of the coating layer is performed at a temperature equal to or higher than a glass transition temperature of the (meth) acrylate polymer.
[14] The production method according to [12] or [13], wherein the formation of the resin layer is performed at 250 to 400 ℃.
[15] The production method according to any one of [12] to [14], wherein a thickness of the resin layer is less than 20 μm.
Effects of the invention
The present invention provides a dispersion containing a tetrafluoroethylene polymer, which can form a layer (resin layer) having excellent electrical properties (dielectric constant, electrostatic loss tangent, etc.) and surface physical properties (heat resistance, chemical resistance, smoothness, gloss, etc.) while suppressing dusting of powder particles.
Detailed Description
The following terms have the following meanings.
"D50 of the powder" means a particle size distribution of the powder measured by a laser diffraction scattering method, and a cumulative curve obtained by taking the total volume of the powder particle group as 100%, and a point on the cumulative curve where the cumulative volume reaches 50% (volume-based cumulative 50% diameter).
"D90 of the powder" means a particle size distribution of the powder measured by a laser diffraction scattering method, and a cumulative curve obtained by taking the total volume of the powder particle clusters as 100%, and a particle diameter at a point on the cumulative curve where the cumulative volume reaches 90% (cumulative 90% diameter on volume basis).
"melt viscosity of polymer" means a value measured by holding a polymer sample (2g) preheated at a measurement temperature for 5 minutes under a load of 0.7MPa at the measurement temperature using a flow tester and a 2. phi. -8L mold based on ASTM D1238.
"melting point of a polymer" means a temperature corresponding to the maximum of a melting peak measured by Differential Scanning Calorimetry (DSC).
The "viscosity" is a value measured at room temperature (25 ℃) and 30rpm using a B-type viscometer. The measurement was repeated 3 times, and the average of the 3 measurements was taken.
"(meth) acrylate" refers to the generic term acrylate and methacrylate.
"(meth) acrylic acid" refers to the generic name of acrylic acid and methacrylic acid.
The "glass transition temperature (Tg)" of the polymer is a value obtained by differential scanning calorimetry, and in the case where it cannot be measured, a value obtained by the fox equation.
The "weight average molecular weight (Mw)" of the polymer is a value obtained by gel permeation chromatography using polystyrene as a standard sample and tetrahydrofuran as a developing solvent.
The "thermal decomposition start temperature" of the polymer is a temperature at which the mass reduction rate of the polymer (10mg) is 1 mass%/min or more when the polymer is heated at a rate of 10 ℃/min in an atmosphere of a mixed gas (helium gas 90 vol% and oxygen gas 10 vol%) using a thermogravimetric analyzer (TG) and a thermogravimetric differential thermal analyzer (TG-DTA).
The "unit" in the polymer is a general term for an atomic group derived from the monomer 1 molecule and formed by polymerization of the monomer, and an atomic group obtainable by chemical conversion of a part of the atomic group. The unit may be a unit directly formed by a polymerization reaction, or a unit in which a part of the unit is converted into another structure by treating a polymer. Hereinafter, the unit based on the monomer a is also referred to as "monomer a unit". For example, units based on Tetrafluoroethylene (TFE) are also referred to as TFE units.
The dispersion liquid of the present invention comprises a powder of a tetrafluoroethylene polymer (hereinafter also referred to as "TFE polymer"), a (meth) acrylate polymer having a glass transition temperature of 0 to 120 ℃ (hereinafter also referred to as "predetermined polymer"), and a liquid dispersion medium.
In the dispersion liquid, the TFE polymer is dispersed in a liquid dispersion medium, and the dispersion liquid contains 0.1 to 10 parts by mass of a predetermined polymer per 100 parts by mass of the TFE polymer.
When a layer (resin layer) is formed from the dispersion of the present invention, dusting of powder is suppressed, and the formed layer (resin layer) is excellent in electrical characteristics and surface physical properties, and the reason is considered as follows.
It is considered that when a coating layer (a layer formed when the liquid dispersion medium of the dispersion liquid of the present invention is removed) is formed, the rigidity and viscosity of a predetermined polymer are lowered, and the polymer thinly and uniformly penetrates into the gaps between the powder particles. Further, it is considered that the predetermined polymer having a (meth) acryloyloxy group forms a thin and dense matrix in the coating layer by its intermolecular force, so that the dusting of the powder is suppressed.
On the other hand, since a predetermined polymer has lower heat resistance than a TFE-based polymer and is easily lost by thermal decomposition, the physical properties of a layer (resin layer) formed by melting or firing the powder by heating are not easily impaired. Further, since the predetermined polymer is thinly present in the gaps between the powder particles, the physical properties of the layer (resin layer) are not easily impaired by the gas and polymer residue generated by thermal decomposition. As a result, it is considered that a layer (resin layer) having excellent surface properties (heat resistance, chemical resistance, smoothness, gloss, etc.) and electrical characteristics (dielectric constant, electrostatic loss tangent, etc.) is formed from the dispersion of the present invention. The tendency is likely to be remarkable when the thickness of the layer (resin layer) is thin. Therefore, when the dispersion of the present invention is used, a printed circuit board material (e.g., a resin-coated copper foil) having a film-like electrical insulating layer having both surface properties and electrical characteristics can be easily obtained.
The D50 of the powder of the present invention is preferably 0.05 to 6 μm, and particularly preferably 0.1 to 3.0. mu.m. When D50 of the powder is within the above range, not only the powder has excellent flowability and dispersibility, but also the layer or resin layer (hereinafter also referred to as "F layer") formed from the dispersion liquid of the present invention and containing a melt or a fired product of a TFE-based polymer has excellent smoothness. The D90 of the powder is preferably 8.0 μm or less, and particularly preferably 1.5 to 5.0. mu.m. When D90 of the powder is within the above range, the dispersibility of the powder and the homogeneity of the F layer are excellent.
The sparse packing volume density and the dense packing volume density of the powder are preferably 0.08-0.5 g/mL and 0.1-0.8 g/mL in sequence.
The powder in the present invention is a powder containing a TFE-based polymer as a main component. The content of the TFE polymer in the powder is preferably 80% by mass or more, particularly preferably 100% by mass. Examples of other resins that may be contained in the powder include: aromatic polyesters, polyamideimides, thermoplastic polyimides, polyphenylene ethers (plaintext: ポリフェニレンエーテル), polyphenylene ethers (plaintext: ポリフェニレンオキシド), and the like.
The TFE-based polymer in the present invention is a polymer including a Tetrafluoroethylene (TFE) based unit (TFE unit).
The TFE-based polymers are preferably: a homopolymer substantially composed of a TFE unit (hereinafter also referred to as "PTFE"), a copolymer comprising a TFE unit and a perfluoro (alkyl vinyl ether) (PAVE) based unit (PAVE unit), a copolymer comprising a TFE unit and a Hexafluoropropylene (HFP) based unit (HFP unit), or a copolymer comprising a TFE unit and a Fluoroalkylethylene (FAE) based unit (FAE unit).
PTFE also includes polymers containing units other than TFE units in very small amounts, and low molecular weight PTFE. The polymer preferably contains more than 99.5 mol% of TFE units, and particularly preferably contains more than 99.9 mol% of TFE units, relative to all units contained in the polymer. The melt viscosity of the polymer at 380 ℃ is preferably 1X 102～1×108Pa · s, particularly preferably 1X 103～1×106Pa·s。
The low-molecular-weight PTFE may be PTFE obtained by irradiating high-molecular-weight PTFE with radiation (polymers described in international publication nos. 2018/026012, 2018/026017, and the like), PTFE obtained by using a chain transfer agent in producing PTFE by polymerizing TFE (polymers described in japanese patent laid-open nos. 2009-1745, 2010/114033, 2015-232082, and the like), or PTFE having a core-shell structure composed of a core portion and a shell portion and having a low molecular weight in only the shell portion (polymers described in japanese patent laid-open nos. 2005-527652, 2016/170918, jp-h 09-087334, and the like).
The standard specific gravity (specific gravity measured based on ASTM D4895-04) of the low molecular weight PTFE is preferably 2.14 to 2.22, more preferably 2.16 to 2.20.
Polymers containing units other than TFE units are also included in the TFE unit-containing polymers. The polymer preferably comprises more than 0.5 mol% of units based on monomers other than TFE units, relative to all units contained in the polymer. The units other than TFE are preferably PAVE units, HFP units, FAE units, or units having a functional group described later.
The TFE unit-containing polymer preferably has at least 1 functional group selected from the group consisting of carbonyl-containing groups, hydroxyl groups, epoxy groups, oxetanyl groups, amino groups, nitro groups, and isocyanate groups. When the TFE-based polymer has the functional group, the interaction between the predetermined polymer and the TFE-based polymer is enhanced, and the dispersion properties (viscosity, color tone, etc.) of the dispersion liquid and the F layer forming properties (adhesiveness, transparency, etc.) are more easily improved. In addition, the carbonyl-containing group comprises an amide group.
The functional group may be contained in a unit constituting the TFE-based polymer, may be contained in a terminal group of the main chain of the polymer, or may be introduced into the TFE-based polymer by plasma treatment or the like. Examples of the TFE-based polymer having the functional group at the end group of the polymer main chain include: TFE polymers having a functional group as an end group derived from a polymerization initiator, a chain transfer agent or the like.
The above functional group is preferably a hydroxyl group or a carbonyl group, more preferably a carbonyl group, particularly preferably a carbonate group, a carboxyl group, a haloformyl group, an alkoxycarbonyl group, an acid anhydride residue or a fatty acid residue, and most preferably a carboxyl group or an acid anhydride residue.
The TFE-based polymer in the present invention preferably contains TFE units; PAVE unit, HFP unit, or FAE unit; a unit having a functional group; the polymer of (1).
The units having a functional group are preferably units based on monomers having a functional group.
As the monomer having a functional group, a monomer having a carbonyl group is preferable, and a cyclic monomer having an acid anhydride residue is particularly preferable.
Examples of the cyclic monomer include: itaconic anhydride, citraconic anhydride, 5-norbornene-2, 3-dicarboxylic anhydride (alias: nadic anhydride; hereinafter also referred to as "NAH") or maleic anhydride, preferably NAH.
As PAVE, CF is mentioned2＝CFOCF3、CF2＝CFOCF2CF3、CF2＝CFOCF2CF2CF3(PPVE)、CF2＝CFOCF2CF2CF2CF3、CF2＝CFO(CF2)8F, preferably PAVE.
As FAEs, there may be mentioned: CH (CH)2＝CH(CF2)2F、CH2＝CH(CF2)3F、CH2＝CH(CF2)4F、CH2＝CF(CF2)3H、CH2＝CF(CF2)4H。
In this case, the TFE unit, PAVE unit, HFP unit, FAE unit, and the unit having a functional group contained in the polymer are preferably 90 to 99 mol%, 0.5 to 9.97 mol%, and 0.01 to 3 mol%, respectively, in this order, based on all the units contained in the polymer. In this case, the TFE polymer preferably has a melting point of 250 to 380 ℃ and particularly preferably 280 to 350 ℃. Specific examples of the TFE polymer include the polymers described in International publication No. 2018/16644.
The polymer specified in the present invention is a (meth) acrylate polymer having a glass transition temperature of 0 to 120 ℃. The (meth) acrylate-based polymer refers to a generic name of a polymer including a (meth) acrylate-based unit.
The predetermined polymer may be dispersed in the dispersion in the form of particles or may be dissolved in the dispersion.
The glass transition temperature of the polymer is preferably 30 to 120 ℃, preferably 40 to 110 ℃, and particularly preferably 60 to 100 ℃. In this case, the fluidity of the predetermined polymer is improved when the coating layer is formed, the dusting of the powder is further suppressed, and the physical properties of the F layer are further easily improved.
The thermal decomposition initiation temperature of the predetermined polymer is preferably 200 ℃ or higher, and particularly preferably 250 to 300 ℃. The thermal decomposition rate of the predetermined polymer at 350 ℃ is preferably 1% by mass/min or more, and particularly preferably 2% by mass/min or more. In this case, in the coating layer formed from the dispersion, a predetermined polymer forms a dense matrix, and the predetermined polymer is easily decomposed when forming the F layer, and the F layer having excellent electrical characteristics is easily formed.
The specified polymer preferably has a hydroxyl group. In this case, not only the interaction between the predetermined polymers is further promoted, but also the interaction between the liquid dispersion medium and the TFE-based polymer is easily promoted. As a result, powder falling is further suppressed, and the physical properties of the F layer are further improved.
The hydroxyl group may be contained in a unit of a predetermined polymer or may be contained at a terminal of a polymer chain (a terminal of a polymer main chain).
The predetermined polymer is preferably a (meth) acrylate-based polymer including a unit based on a (meth) acrylate having a hydroxyl group, or a (meth) acrylate-based polymer having a hydroxyl group at the end of a polymer chain, which is preferably obtained by polymerizing a (meth) acrylate in the presence of a chain transfer agent and an alcohol.
Examples of the (meth) acrylate having a hydroxyl group include: hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monoglycidyl ether or (meth) acrylic esters obtained by addition of glycidol to (meth) acrylic acid.
Examples of the chain transfer agent include: 1-butanethiol, 1-octanethiol, 1-decanethiol, 1-dodecanethiol, 1-hexadecanethiol, cyclohexanethiol, 2-mercaptoethanol, mercaptoacetic acid, methyl mercaptoacetate, 3-mercaptopropionic acid, 2, 4-diphenyl-4-methyl-1-pentene.
Examples of the alcohol include: methanol, ethanol, propanol.
The specified polymer preferably contains a hydrocarbon (meth) acrylate-based unit, and more preferably contains a unit based on at least 1 kind of (meth) acrylate selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth) acrylate. In this case, the glass transition temperature of the predetermined polymer and the thermal decomposition property of the predetermined polymer can be easily adjusted, and the powder falling during the formation of the F layer can be further suppressed, and the physical properties can be further improved. The butyl (meth) acrylate may be any of n-butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl (meth) acrylate.
The weight average molecular weight of the polymer is preferably 10000 to 150000. In this case, not only the fluidity of the predetermined polymer is improved at the time of forming the coating layer, but also the degradability of the predetermined polymer is improved, so that the powder falling of the dispersion of the present invention is further suppressed, and the physical properties of the F layer are further easily improved.
Specific examples of the predetermined polymer include: a polymer comprising the above-mentioned hydroxyl group-containing monomer-based unit and the above-mentioned hydrocarbon (meth) acrylate-based unit and having a weight average molecular weight of 50000 to 150000, and a polymer comprising the above-mentioned hydrocarbon (meth) acrylate-based unit and having a weight average molecular weight of 10000 to 50000. In addition, the latter polymer preferably has a hydroxyl group at the end of the polymer chain.
The former polymer preferably contains 1 to 20 mol% and 80 to 99 mol% of the unit based on the monomer having a hydroxyl group and the above-mentioned unit based on the hydrocarbon (meth) acrylate in this order with respect to all units contained in the polymer.
The polymer is preferably a methacrylate polymer. In addition, the methacrylate-based polymer refers to a generic name of polymers containing a methacrylate-based unit. When the predetermined polymer is a methacrylate polymer, it is considered that intermolecular force based on the steric configuration of the polymer main chain forms a more dense matrix, and hence dusting of the edge portion of the F layer is more easily suppressed.
Specific examples of the methacrylate polymer include: a polymer comprising a unit based on a methacrylate having a hydroxyl group and a unit based on a hydrocarbon methacrylate and having a weight average molecular weight of 50000 to 150000, and a polymer comprising a unit based on a hydrocarbon methacrylate and having a weight average molecular weight of 10000 to 50000.
The former polymer preferably contains 1 to 20 mol% and 80 to 99 mol% of a unit based on a methacrylate having a hydroxyl group and a unit based on a hydrocarbon methacrylate in this order with respect to all units contained in the polymer. The glass transition temperature of the former polymer is preferably 60 to 100 ℃.
The latter polymers preferably have hydroxyl groups at the ends of the polymer chains. In addition, the glass transition temperature of the latter polymer is preferably 0 to 40 ℃.
The hydrocarbon methacrylate is preferably at least 1 methacrylate selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate and benzyl methacrylate, more preferably Methyl Methacrylate (MMA), Ethyl Methacrylate (EMA) or Butyl Methacrylate (BMA). The BMA may be any of n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate.
The methacrylate having a hydroxyl group is preferably hydroxyethyl methacrylate (HEMA), 2-hydroxybutyl methacrylate or 4-hydroxybutyl methacrylate.
The predetermined polymer can be obtained as a commercially available product (e.g., "OLYCOX KC-1700P" manufactured by Kyoeisha chemical Co., Ltd.).
The liquid dispersion medium in the present invention is a compound which is liquid at 25 ℃ and has a function of dispersing the powder of the present invention, and may be an aqueous medium or a nonaqueous medium, and is preferably a nonaqueous medium. The water content of the nonaqueous medium is preferably 20000ppm or less. The lower limit of the water content of the nonaqueous medium is usually 0 ppm.
When the liquid dispersion medium is a nonaqueous medium (particularly an ester or a ketone), the predetermined polymer is more easily dispersed or dissolved in the dispersion liquid, the action (formation of a dense matrix due to the predetermined polymer, etc.) at the time of forming the coating layer is more easily promoted, and the dusting of the powder at the time of forming the thin F layer is particularly easily suppressed.
The compound of the liquid dispersion medium is preferably an organic solvent such as a nitrogen-containing compound, a sulfur-containing compound, an ester, a ketone, a glycol ether, or the like.
The boiling point of the compound of the liquid dispersion medium is preferably 60 to 240 ℃, particularly preferably 80 to 210 ℃.
The boiling point of the compound of the liquid dispersion medium is preferably at least the glass transition temperature of the predetermined polymer. The boiling point of the compounds of the liquid dispersion medium is preferably below the glass transition temperature +150 ℃. In this case, when the coating layer is formed by volatilization of the liquid dispersion medium, the fluidity of the predetermined polymer is improved, the powder falling is further suppressed, and the physical properties of the formed layer (F layer) are further easily improved.
Specific examples of the compound as the liquid dispersion medium include: water, methanol, ethanol, isopropanol, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, diethyl ether, dioxane, ethyl lactate, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isopropyl ketone, γ -butyrolactone, cyclopentanone, cyclohexanone, ethylene glycol monoisopropyl ether, cellosolve (methyl cellosolve, ethyl cellosolve, etc.).
The compound of the liquid dispersion medium is preferably N, N-dimethylacetamide, N-methyl-2-pyrrolidone or γ -butyrolactone.
The dispersion liquid of the present invention may contain a dispersant, an antifoaming agent, an inorganic filler, a dehydrating agent, a plasticizer, a weather resistant agent, an antioxidant, an adhesive, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a colorant, a conductive agent, a mold release agent, a surface treatment agent, a viscosity modifier, a flame retardant.
The dispersion liquid of the present invention preferably contains a dispersant from the viewpoint of improving the dispersibility of the powder of the TFE-based polymer in the dispersion liquid and improving the physical properties of the F layer.
The dispersing agent is a compound having a function of adsorbing chemically and/or physically to the surface of the powder of the TFE-based polymer to stably disperse the powder in the liquid dispersion medium, and is preferably a fluorine-based dispersing agent (fluorine-based surfactant) having a hydrophobic site and a hydrophilic site containing a fluorine atom, and particularly preferably at least 1 kind of compound selected from the group consisting of fluoroalcohols, fluorosilicones, and fluoropolyethers. These compounds are other than the TFE polymer and the predetermined polymer.
Examples of fluoroalcohols include: non-polymeric fluorinated monols, polymeric fluorinated polyols. In addition, a portion of the hydroxyl groups of the polymeric fluoropolyol may be chemically modified .
As the fluorosilicone, there may be mentioned: a polyorganosiloxane in which a part of the side chain contains a C-F bond.
As the fluoropolyether, there may be mentioned: a compound in which a part of hydrogen atoms of a polyoxyalkylene alkyl ether is substituted with a fluorine atom.
The fluorine-based dispersant is preferably a polymeric fluoro polyol, and more preferably a polymer comprising a fluoroalkyl (meth) acrylate or fluoroalkenyl (meth) acrylate and a unit based on an oxyalkylene glycol mono (meth) acrylate.
Specific examples of the former (meth) acrylate include:
CH2＝C(CH3)C(O)OCH2CH2(CF2)6F、CH2＝CHC(O)OCH2CH2(CF2)6F、
CH2＝C(CH3)C(O)OCH2CH2(CF2)4F、CH2＝CClC(O)OCH2CH2(CF2)4F、
CH2＝CHC(O)OCH2CH2CH2CH2OCF(CF3)C(＝C(CF3)2)(CF(CF3)2)、
CH2＝CHC(O)OCH2CH2CH2CH2OC(CF3)C(＝C(CF(CF3)2)2)。
the amount of the former unit is preferably 60 to 90 mol%, particularly preferably 70 to 90 mol%, based on all units contained in the polymer.
Specific examples of the latter (meth) acrylate include:
CH2＝C(CH3)C(O)(OCH2CH2)2OH、CH2＝C(CH3)C(O)(OCH2CH2)9OH、
CH2＝C(CH3)C(O)(OCH2CH2)23OH、CH2＝C(CH3)C(O)(OCH2CH2)66OH、
CH2＝CHC(O)(OCH2CH2)4OH、CH2＝CHC(O)(OCH2CH2)9OH、
CH2＝CHC(O)(OCH2CH2)23OH、CH2＝CHC(O)(OCH2CH2)66OH、
CH2＝C(CH3)C(O)(OCH2CH(CH3))4OH、
CH2＝C(CH3)C(O)(OCH2CH2)4·(OCH2CH(CH3))3OH、
CH2＝C(CH3)C(O)(OCH2CH2)10·(OCH2CH2CH2CH2)5OH。
the amount of the latter unit is preferably 10 to 40 mol%, particularly preferably 10 to 30 mol%, relative to all units contained in the polymer.
The polymer may further comprise other additional units.
The polymer is preferably non-ionic.
The mass average molecular weight of the polymer is preferably 2000 to 80000, and particularly preferably 6000 to 20000.
The polymer may have a hydroxyl group or a carboxyl group at the end of the main chain. In this case, the dispersion liquid of the present invention is easily improved in flatness. The polymer is obtained by adjusting the types of a polymerization initiator and a chain transfer agent used in the production thereof.
The proportion of the powder in the dispersion is preferably 5 to 60% by mass, and particularly preferably 30 to 50% by mass. In this case, the dispersibility of the dispersion and the physical properties of the F layer are easily improved.
The proportion of the liquid dispersion medium in the dispersion liquid is preferably 15 to 65% by mass, and particularly preferably 25 to 50% by mass. In this case, the formation of the coating layer from the dispersion and the physical properties of the F layer are easily improved.
The proportion of the predetermined polymer in the dispersion is preferably 0.05 to 6% by mass, and particularly preferably 0.1 to 5% by mass. In this case, the dispersibility of the dispersion and the physical properties of the F layer are easily improved.
The dispersion liquid of the present invention contains 0.1 to 10 parts by mass of a predetermined polymer per 100 parts by mass of a TFE polymer. The content of the predetermined polymer is preferably 0.5 parts by mass or more, particularly preferably 1 part by mass or more, based on 100 parts by mass of the TFE polymer. The content is preferably 5 parts by mass or less, and particularly preferably less than 5 parts by mass. In this case, dusting of the powder of the coating layer formed from the dispersion of the present invention is further suppressed, and the physical properties of the F layer are more easily improved. Further, a thin film-like electrical insulating layer having surface properties and electrical characteristics can be more easily formed.
When the dispersion liquid of the present invention contains another material, the proportion of the other material in the dispersion liquid is preferably 1 to 50% by mass, and particularly preferably 5 to 30 parts by mass. When the other material contains a dispersant, the proportion of the dispersant in the dispersion is preferably 1 to 10 parts by mass.
The dispersion liquid of the present invention can be produced by mixing a liquid dispersion medium, a powder of a TFE-based polymer, and a predetermined polymer, and is preferably produced by mixing a liquid dispersion medium, a predetermined polymer, and a powder of a TFE-based polymer.
In the mixing, it is preferable to perform a dispersion treatment using a homomixer or homogenizer to improve the dispersion state. When the dispersion of the present invention stored at 0 to 40 ℃ is used, it is preferable to perform the dispersion treatment and then use it.
In the present invention, the dispersion liquid of the present invention is applied to the surface of a metal foil to form a coating layer, and the TFE polymer is further melted or fired by heating to form a TFE polymer-containing resin layer (F layer). Thus, a metal foil with resin having a metal foil and a resin layer containing a TFE polymer provided in contact with the surface of the metal foil can be provided.
In the production method of the present invention, the ranges of the TFE-based polymer, its powder, the predetermined polymer, and the liquid dispersion medium, including preferred embodiments, are the same as those in the polymer dispersion liquid of the present invention. In the production method of the present invention, the resin layer may be formed on at least one surface of the metal foil, may be formed only on one surface of the metal foil, or may be formed on both surfaces of the metal foil.
Examples of the material of the metal foil include copper, copper alloy, stainless steel, nickel alloy (including 42 alloy), aluminum alloy, titanium, and titanium alloy.
The metal foil is preferably a copper foil such as a rolled copper foil or an electrolytic copper foil.
The surface of the metal foil may be provided with a rust-proofing treatment layer and a heat-resistant layer. Further, the surface of the metal foil may be surface-treated with a silane coupling agent.
The thickness of the metal foil may be any thickness that can sufficiently function in the application of the laminate. The thickness of the metal foil is preferably 2 to 40 μm, which is equal to or more than ten-point average roughness of the surface. As the metal foil, a carrier-attached metal foil composed of a carrier copper foil (thickness of 10 to 35 μm) and an extra thin copper foil (thickness of 2 to 5 μm) laminated on the carrier copper foil with a release layer interposed therebetween can be used. Further, the thickness of the metal foil is preferably larger than that of the F resin layer.
Examples of the method for applying the dispersion include: spray coating, roll coating, spin coating, gravure coating, microgravure coating, gravure offset coating, knife coating, kiss roll coating (japanese: キスコート method), bar coating, die coating, jet meyer bar coating (japanese: ファウンテンメイヤーバー method), slit die coating.
The coating layer is preferably formed by heating the metal foil at a temperature equal to or higher than the glass transition temperature of the predetermined polymer to remove the liquid dispersion medium. In this case, it is not necessary to completely volatilize the liquid dispersion medium, and the liquid dispersion medium may be volatilized to such an extent that a stable self-supporting film can be formed from the coating layer formed by coating the dispersion liquid. Specifically, it is preferable to volatilize 50 mass% or more of the liquid dispersion medium contained in the dispersion liquid. In addition, the non-volatile liquid dispersion medium can be completely removed in the subsequent melting or firing stage.
The temperature in this case is preferably 50 to 150 ℃, more preferably 80 to 120 ℃.
The time in this case is preferably 0.1 to 30 minutes, more preferably 0.5 to 20 minutes.
The temperature at which the coating layer is heated to melt or fire the TFE polymer to form the TFE polymer-containing resin layer is preferably 250 to 400 ℃, particularly preferably 300 to 400 ℃.
Examples of the heating method include a method using an oven, a method using a forced air drying oven, and a method of irradiating heat rays such as infrared rays. In order to improve the surface smoothness of the F layer, the pressing may be performed by a hot plate, a hot roller, or the like. The temperature during heating generally represents the temperature of the atmosphere. The effective wavelength band of infrared rays is particularly preferably 3 to 7 μm from the viewpoint of homogeneously melting or firing a TFE polymer.
The oxygen concentration in the atmosphere during heating is preferably 100 to 500ppm in order to suppress oxidation of the metal foil and the F layer. The atmosphere is preferably an inert gas atmosphere (nitrogen or the like) or a reducing gas atmosphere (hydrogen or the like).
The thickness of the formed resin layer is preferably less than 20 μm, more preferably less than 10 μm. The thickness of the resin layer is preferably 1 μm or more. In the dispersion liquid of the present invention, the content of the predetermined polymer is within a predetermined range with respect to the content of the TFE-based polymer, and when the thin resin layer is formed, not only a dense layer of the TFE-based polymer can be formed by the action of the predetermined polymer, but also the predetermined polymer is less likely to remain in the resin layer. As a result, a film-like resin layer having excellent surface properties and electrical characteristics can be easily formed, and a resin-coated copper foil which is less likely to warp can be easily obtained.
In the metal foil with resin of the present invention, the surface of the resin layer may be subjected to a surface treatment in order to control the linear expansion coefficient of the resin layer and further improve the adhesion of the resin layer.
As the surface treatment, there may be mentioned: annealing treatment, corona discharge treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, UV ozone treatment, excimer treatment, chemical etching, silane coupling treatment, surface micro-roughening treatment, and the like.
The temperature of the annealing treatment is preferably 80-190 ℃. The pressure of the annealing treatment is preferably 0.001 to 0.030 MPa. The time of the annealing treatment is preferably 10 to 300 minutes.
Examples of the plasma irradiation device in the plasma processing include a high-frequency induction system, a capacitive coupling electrode system, a corona discharge electrode-plasma spray system, a parallel plate system, a remote plasma system, an atmospheric pressure plasma system, and an ICP high-density plasma system.
Examples of the gas used for the plasma treatment include oxygen, nitrogen, a rare gas (such as argon), hydrogen, and ammonia, and a rare gas or nitrogen is preferable. Specific examples of the gas used for the plasma treatment include argon gas, a mixed gas of hydrogen gas and nitrogen gas, and a mixed gas of hydrogen gas, nitrogen gas, and argon gas.
The atmosphere in the plasma treatment is preferably an atmosphere in which the volume fraction of a rare gas or nitrogen gas is 70 vol% or more, and particularly preferably an atmosphere of 100 vol%. In this range, the Ra of the surface of the F resin layer is adjusted to 2.5 μm or less, and fine irregularities are likely to be formed on the surface of the F layer with the resin-coated metal foil.
The Ra of the surface of the F layer in the resin-attached metal foil is preferably 2nm to 2.5. mu.m, and particularly preferably 5nm to 1 μm. The surface Rz of the F layer is preferably 15nm to 2.5. mu.m, particularly preferably 50nm to 2 μm. In this range, the adhesiveness between the resin-coated metal foil and the prepreg and the surface processability of the F layer are easily balanced.
As a method of laminating a prepreg on the surface of the F layer with a resin-containing metal foil, a method of hot-pressing a resin-containing metal foil and a prepreg can be cited.
The pressing temperature is preferably not higher than the melting point of the TFE polymer, and particularly preferably 160 to 220 ℃. Within this range, thermal degradation of the prepreg can be suppressed, and the F layer and the prepreg can be firmly bonded.
The hot pressing is particularly preferably performed under a vacuum of 20kPa or less. In this range, the deterioration due to the incorporation and oxidation of bubbles at the interface of each of the metal foil, the F layer, and the cured layer in the laminate can be suppressed. In the hot pressing, it is preferable to raise the temperature after the degree of vacuum is reached.
The pressure in the hot pressing is preferably 0.2-10 MPa. Within this range, breakage of the prepreg can be suppressed, and the F layer and the prepreg can be firmly bonded.
Since the resin-coated metal foil of the present invention uses a TFE-based polymer having excellent physical properties such as electrical characteristics and chemical resistance (etching resistance) as a resin layer, the resin-coated metal foil of the present invention can be used for the production of a printed circuit board as a flexible metal-clad laminate or a rigid metal-clad laminate.
For example, a printed circuit board can be manufactured from the metal foil with resin of the present invention by a method of processing the metal foil with resin of the present invention into a conductor circuit (transmission circuit) of a predetermined pattern by etching, or a method of processing the metal foil with resin of the present invention into a transmission circuit by an electroplating method (a semi-additive method (SAP method), a modified semi-additive method (MSAP method), or the like).
The printed substrate produced from the resin-coated metal foil of the present invention preferably has a transmission circuit, an F layer, and a cured product layer in this order. Examples of the layer structure of the printed circuit board of the present invention include: transmission circuit/F layer/cured layer, transmission circuit/F layer/cured layer/F layer/transmission circuit.
In the production of the printed board, after the transfer circuit is formed, an interlayer insulating film may be formed on the transfer circuit, and the transfer circuit may be further formed on the interlayer insulating film. For example, an interlayer insulating film may be formed by the dispersion of the present invention.
In the production of the printed circuit board, a solder resist may be laminated on the transmission circuit. A solder resist can be formed by the dispersion of the present invention.
In the production of the printed circuit board, a cover film may be laminated on the transmission circuit. The coating film can also be formed from the dispersion of the present invention.
Examples
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
Various evaluations were performed by the following methods.
< dusting of coating layer (one) >)
The metal foil in a state where the dispersion was applied and dried to form a coating layer was wound into a roll and stored for 10 days. Then, the metal foil 10m long was discharged from the roll, and the amount of the powder (detached powder) adhering to the back surface (surface on which the coating layer was not formed) side of the metal foil was visually confirmed and evaluated by the following criteria.
O: the number of detached powder is less than 5.
X: the number of detached powder was 5 or more.
< dusting of coating layer (two thereof) >)
The edge portion of the metal foil in a state where the dispersion liquid was applied and dried to form a coating layer was visually confirmed and evaluated by the following criteria.
O: no defects were found.
Δ: defects are found at a portion of the locations.
X: the defect also extends to the peripheral portion.
Smoothness of resin-coated copper foil
The surface of the F layer of the resin-coated copper foil was irradiated with light, visually observed from obliquely above, and evaluated by the following criteria.
O: no grapefruit peel pattern was found.
X: a shaddock peel pattern was found.
The detailed description and abbreviations for the materials used are as follows.
< TFE polymers >
Polymer F1: a copolymer comprising, in this order, 97.9 mol%, 0.1 mol% and 2.0 mol% of TFE units, NAH units and PPVE units is a polymer having a melting point of 300 ℃.
(meth) acrylate polymer
Polymer a 1: a polymer comprising, in order, 60 mol%, 20 mol%, and 10 mol% EMA units, MMA units, and HEMA units, having a Tg of 75 ℃ and a Mw of 120000.
Polymer a 2: a polymer comprising BMA units and having a Tg of 25 ℃ and an Mw of 25000.
Polymer a 3: a polymer comprising, in order, 60 mol%, 20 mol%, and 10 mol% EMA units, MMA units, and HEMA units, having a Tg of 65 ℃ and an Mw of 100000.
< liquid dispersion Medium >
NMP: n-methylpyrrolidone (boiling point: 202 ℃ C.)
Example 1 preparation of Dispersion
Example 1-1 preparation of Dispersion 1
Powder F1 (D50: 2.6 μm, D90: 7.1 μm) of polymer F1 was obtained by the method described in paragraph [0123] of International publication No. 2016/017801.
3209g of powder F1, 320.9g of a fluorine-based dispersant (Ftergent 710FL available from Bell chemical Co., Ltd.), 2888g of NMP and 97.7g of polymer A1 were charged in a pot of a horizontal ball mill, and dispersed with zirconium beads having a diameter of 15mm to obtain a dispersion 1 of a powder in which polymer A1 was dispersed. The viscosity of the dispersion 1 was 180 mPas at 60 rpm.
Examples 1 and 2 production of Dispersion 2
In addition to being a fluorine-based dispersant, a dispersant containing 81 mol% and 19 mol% in this order based on CH was used2＝C(CH3)C(O)OCH2CH2(CF2)6Units of F and
CH2＝C(CH3)C(O)(OCH2CH2)23dispersion 2 was obtained in the same manner as in example 1-1, except that a polymer A2 was used in place of polymer A1. The viscosity of the dispersion 2 was 160 mPas at 60 rpm.
Examples 1 to 3 production of Dispersion 3
Dispersion 3 was obtained in the same manner as in example 1-1, except that polymer A3 was used in place of polymer A1. The viscosity of the dispersion 3 was 150 mPas at 60 rpm.
Examples 1 to 4 production of Dispersion 4
Dispersion 4 was obtained in the same manner as in example 1-1, except that polymer a2 was used in place of polymer a1, and 15 parts by mass of polymer a2 was used with respect to 100 parts by mass of polymer F1.
Further, when the dispersions 1 to 3 were applied to the surface of a copper foil immediately after preparation and heated, a resin-coated copper foil having an F layer (thickness of 5 μm) containing the polymer F1 could be produced. The resin-coated copper foil having the F layer with a thickness of 7 μm and a thickness of 10 μm was also produced without any problem.
Example 2 production of Metal foil with resin
[ example 2-1]
The dispersion 1 was stirred with a paint stirrer for 1 hour, stirred with a homomixer at 3000rpm for 30 minutes, filtered through a screen (pore size 100 μm), and introduced into a pot connected to a gravure coater through a liquid feed line. A stirring device with a stirring blade is installed in the tank and operated, and a filter is installed in the liquid feeding line.
The dispersion 1 was applied to a roughened surface of a long copper foil (manufactured by Futian Metal foil powder industries, CF-T4X-SV, 640mm in width, 18 μm in thickness) moving at a carrying speed of 10 m/min by using a gravure coater so as to have a thickness of 5 μm, thereby forming a wet film on the roughened surface. Next, the long copper foil with the wet film was passed through a through-air drying oven to volatilize the liquid dispersion medium to form a coating layer. The conditions in the air drying furnace were set to 100 ℃ for 1.5 minutes.
Further, the copper foil was passed through a far infrared furnace (RtoR NORITAKE, Wu K.K.) while moving at a conveying speed of 5 m/min2Atmospheric furnace, length 4.7m), and polymer F1 were melt-fired to obtain a long resin-coated copper foil having an F layer containing polymer F1. The heating condition in the far infrared furnace was set to 370 ℃ for 1 minute in a nitrogen atmosphere having an oxygen concentration of 200 ppm.
The surface of the F layer with the resin copper foil obtained was subjected to plasma treatment. As the plasma treatment apparatus, a roll-to-roll type vacuum plasma apparatus of NVC-R series/RollVIA system manufactured by Nichikon corporation was used. The plasma processing conditions were: the output power is 4.5kW, the introduced gas is argon, and the introduced gas flow rate is 50cm3Per minute, pressure 50mTorr (6.7Pa), treatment time 2 minutes.
On the surface of the F layer with a resin copper foil within 72 hours after the plasma treatment, FR-4 (GEA-67N 0.2t (HAN) manufactured by Hitachi chemical Co., Ltd., reinforcing fiber, glass fiber, matrix resin, epoxy resin, and a thickness of 0.2mm) was laminated as a prepreg, and vacuum hot pressing was performed under conditions of a pressing temperature of 185 ℃, a pressing pressure of 3.0MPa, and a pressing time of 60 minutes to obtain a laminate. The evaluation results of the smoothness of the coating layer (first), the coating layer (second), and the resin-coated copper foil were "o".
[ examples 2-2] to 2-4]
A resin-coated copper foil was produced in the same manner as in example 2-1, except that the dispersions 2 and 3 or the dispersion 1 (dispersion C) to which a (meth) acrylate polymer was not blended were used instead of the dispersion 1. The evaluation results of the coating layers of the copper foils with resin are shown in Table 1.
[ Table 1]
| Example 2-1 | Examples 2 to 2 | Examples 2 to 3 | Examples 2 to 4 | |
| Kind of dispersion | 1 | 2 | 3 | C |
| (meth) acrylic acid vinyl polymer | A1 | A2 | A3 | Is not blended with |
| Dusting of coating layer | ○ | ○ | ○ | × |
| Dusting of coating layer (the second) | ○ | ○ | △ | × |
| Smoothness of copper foil with resin | ○ | ○ | ○ | ○ |
Example 3 production of Metal foil with resin (second example)
[ example 3-1]
On the same copper foil as in example 2, the dispersion 2 was roll-to-roll applied by the gravure reverse method to form a wet film. Subsequently, the coating layer was formed by passing through a drying oven at 120 ℃ for 5 minutes, heating and drying. Then, the dried film was heated at 380 ℃ for 3 minutes in a nitrogen furnace. Thus, a resin-coated copper foil having an F layer (thickness of 4 μm) formed by melt-firing polymer F1 on the surface of the copper foil was obtained.
The resin-coated copper foil was subjected to plasma treatment in the same manner as in example 2, and a prepreg was stacked in the same manner as in example 2 to obtain a laminate having a copper foil, an F layer, and a cured product layer of the prepreg in this order. In the solder heat resistance test in which the laminate was suspended in a solder bath, even if the laminate was suspended 5 times in a solder bath at 288 ℃ for 5 seconds, the phenomenon of swelling (swelling phenomenon) at the interface between the F layer and the cured layer and the phenomenon of lifting of the copper foil from the F layer (lifting phenomenon) did not occur.
[ examples 3-2]
A laminate having a copper foil, an F layer, and a cured product layer of a prepreg in this order was obtained in the same manner as in example 3-1, except that the dispersion liquid 4 was used instead of the dispersion liquid 2.
The results of the solder heat resistance test of each laminate are summarized in table 2. The value of "polymer a 2/polymer F1" in the table is the content (parts by mass) of polymer a2 per 100 parts by mass of polymer F1 in the dispersion used.
[ Table 2]
Possibility of industrial utilization
The dispersion liquid of the present invention can form an article having a layer (F layer) of a TFE-based polymer excellent in electrical characteristics and surface properties while suppressing dusting at the time of forming the layer (F layer), and the article can be used for a film, a fiber-reinforced film, a prepreg, a resin-coated metal foil, a metal-clad laminate, a printed board, and the like. The dispersion of the present invention is useful as a material for antenna parts, printed wiring boards, aircraft parts, automobile parts, sports equipment, food industry products, saws, sliding bearings, and the like.
In addition, the entire contents of the specification, claims and abstract of japanese patent application No. 2018-.
Claims (15)
1. A dispersion liquid which comprises a powder of a tetrafluoroethylene polymer, a (meth) acrylate polymer having a glass transition temperature of 0 to 120 ℃, and a liquid dispersion medium in which the tetrafluoroethylene polymer is dispersed, wherein the (meth) acrylate polymer is contained in an amount of 0.1 to 10 parts by mass per 100 parts by mass of the tetrafluoroethylene polymer.
2. The dispersion liquid according to claim 1, wherein the (meth) acrylate polymer is contained in an amount of 0.1 part by mass or more and less than 5 parts by mass based on 100 parts by mass of the tetrafluoroethylene polymer.
3. The dispersion liquid according to claim 1 or 2, wherein the liquid dispersion medium is a nonaqueous medium.
4. A dispersion as claimed in any one of claims 1 to 3 wherein the liquid dispersing medium is an ester or amide.
5. The dispersion liquid according to any one of claims 1 to 4, wherein the tetrafluoroethylene-based polymer has at least 1 kind of functional group selected from a carbonyl group-containing group, a hydroxyl group, an epoxy group, an oxetanyl group, an amino group, a nitro group and an isocyanate group.
6. The dispersion liquid according to any one of claims 1 to 5, wherein the (meth) acrylate polymer has a hydroxyl group.
7. The dispersion liquid according to any one of claims 1 to 6, wherein the (meth) acrylate-based polymer comprises units based on at least 1 kind of (meth) acrylate selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobornyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth) acrylate.
8. The dispersion as claimed in any one of claims 1 to 7, wherein the (meth) acrylate polymer is a methacrylate polymer.
9. The dispersion liquid according to any one of claims 1 to 8, wherein the (meth) acrylate polymer has a weight average molecular weight of 10000 to 150000.
10. The dispersion liquid according to any one of claims 1 to 9, further comprising a fluorine-based dispersant.
11. The dispersion liquid according to any one of claims 1 to 10, further comprising at least 1 fluorine-based dispersant selected from the group consisting of fluoroalcohols, fluorosilicones and fluoropolyethers.
12. A method for producing a resin-equipped metal foil having a metal foil and a resin layer containing a tetrafluoroethylene polymer and provided in contact with the surface of the metal foil,
applying the dispersion liquid according to any one of claims 1 to 11 to the surface, forming a coating layer from the dispersion liquid, and further heating to remove the liquid dispersion medium, thereby melting or firing the tetrafluoroethylene polymer to form the resin layer.
13. The production method according to claim 12, wherein the formation of the coating layer is performed at a temperature equal to or higher than a glass transition temperature of the (meth) acrylate polymer.
14. The production method according to claim 12 or 13, wherein the formation of the resin layer is performed at 250 to 400 ℃.
15. The production method according to any one of claims 12 to 14, wherein the thickness of the resin layer is less than 20 μm.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-188254 | 2018-10-03 | ||
| JP2018188254 | 2018-10-03 | ||
| JP2018-218320 | 2018-11-21 | ||
| JP2018218320 | 2018-11-21 | ||
| JP2019071907 | 2019-04-04 | ||
| JP2019-071907 | 2019-04-04 | ||
| PCT/JP2019/038793 WO2020071382A1 (en) | 2018-10-03 | 2019-10-01 | Dispersion and method for manufacturing resin-coated metal foil |
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| CN112789320A true CN112789320A (en) | 2021-05-11 |
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| CN201980065447.8A Pending CN112789320A (en) | 2018-10-03 | 2019-10-01 | Dispersion liquid and method for producing metal foil with resin |
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| JP (1) | JP7363797B2 (en) |
| CN (1) | CN112789320A (en) |
| TW (1) | TWI813783B (en) |
| WO (1) | WO2020071382A1 (en) |
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| JP2021004322A (en) * | 2019-06-27 | 2021-01-14 | 三菱鉛筆株式会社 | Non-aqueous dispersion of polytetrafluoroethylene |
| JP7089210B2 (en) | 2020-11-06 | 2022-06-22 | ダイキン工業株式会社 | Water-based paint composition and painted articles |
| CN116390993A (en) | 2020-11-06 | 2023-07-04 | 大金工业株式会社 | Aqueous coating composition and coated article |
| EP4349596A1 (en) | 2021-05-25 | 2024-04-10 | Daikin Industries, Ltd. | Coating material composition and layered body |
| WO2022270460A1 (en) * | 2021-06-21 | 2022-12-29 | 積水化学工業株式会社 | (meth)acrylic resin composition, inorganic fine particle-dispersed slurry composition, and inorganic fine particle-dispersed molded product |
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| JPWO2020071382A1 (en) | 2021-09-16 |
| JP7363797B2 (en) | 2023-10-18 |
| TW202033652A (en) | 2020-09-16 |
| WO2020071382A1 (en) | 2020-04-09 |
| TWI813783B (en) | 2023-09-01 |
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