JPWO2020137879A1 - Powder dispersion, laminate and printed circuit board - Google Patents
Powder dispersion, laminate and printed circuit board Download PDFInfo
- Publication number
- JPWO2020137879A1 JPWO2020137879A1 JP2020563199A JP2020563199A JPWO2020137879A1 JP WO2020137879 A1 JPWO2020137879 A1 JP WO2020137879A1 JP 2020563199 A JP2020563199 A JP 2020563199A JP 2020563199 A JP2020563199 A JP 2020563199A JP WO2020137879 A1 JPWO2020137879 A1 JP WO2020137879A1
- Authority
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- Japan
- Prior art keywords
- polymer
- powder
- layer
- powder dispersion
- tetrafluoroethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 186
- 239000006185 dispersion Substances 0.000 title claims abstract description 139
- 229920000642 polymer Polymers 0.000 claims abstract description 169
- 229920001721 polyimide Polymers 0.000 claims abstract description 101
- 239000004642 Polyimide Substances 0.000 claims abstract description 95
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 51
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 19
- -1 cyclic ester Chemical class 0.000 claims description 54
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 48
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 35
- 239000011256 inorganic filler Substances 0.000 claims description 28
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 28
- 125000003118 aryl group Chemical group 0.000 claims description 27
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 26
- 125000000524 functional group Chemical group 0.000 claims description 26
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 17
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 17
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 5
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 4
- 150000003950 cyclic amides Chemical class 0.000 claims description 3
- 150000003997 cyclic ketones Chemical class 0.000 claims description 3
- 125000004991 fluoroalkenyl group Chemical group 0.000 claims description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 25
- 239000011248 coating agent Substances 0.000 abstract description 23
- 238000010586 diagram Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 155
- 239000010408 film Substances 0.000 description 48
- 238000000034 method Methods 0.000 description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 32
- 239000011889 copper foil Substances 0.000 description 31
- 239000007789 gas Substances 0.000 description 29
- 239000002245 particle Substances 0.000 description 23
- 239000012298 atmosphere Substances 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 239000011888 foil Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000000945 filler Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 230000001186 cumulative effect Effects 0.000 description 10
- 229910001882 dioxygen Inorganic materials 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 238000010304 firing Methods 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 239000002966 varnish Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000009832 plasma treatment Methods 0.000 description 7
- 229920001187 thermosetting polymer Polymers 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 229920006015 heat resistant resin Polymers 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
- 239000011261 inert gas Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical group 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 150000004984 aromatic diamines Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 238000009423 ventilation Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 3
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004962 Polyamide-imide Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- 229920002312 polyamide-imide Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-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
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-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
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920002614 Polyether block amide Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- AMNPXXIGUOKIPP-UHFFFAOYSA-N [4-(carbamothioylamino)phenyl]thiourea Chemical compound NC(=S)NC1=CC=C(NC(N)=S)C=C1 AMNPXXIGUOKIPP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 238000009835 boiling Methods 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
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- 238000007607 die coating method Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
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- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
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- 239000001307 helium Substances 0.000 description 2
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
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- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
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- 125000006353 oxyethylene group Chemical group 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
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- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
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- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
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- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 description 1
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- OPCJOXGBLDJWRM-UHFFFAOYSA-N 1,2-diamino-2-methylpropane Chemical compound CC(C)(N)CN OPCJOXGBLDJWRM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- XMXCPDQUXVZBGQ-UHFFFAOYSA-N 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound ClC1=C(Cl)C(C(O)=O)=C2C(C(=O)O)=C(Cl)C(Cl)=C(C(O)=O)C2=C1C(O)=O XMXCPDQUXVZBGQ-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- SDWGBHZZXPDKDZ-UHFFFAOYSA-N 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=C(Cl)C(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O SDWGBHZZXPDKDZ-UHFFFAOYSA-N 0.000 description 1
- JZWGLBCZWLGCDT-UHFFFAOYSA-N 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound ClC1=CC(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O JZWGLBCZWLGCDT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NFIHXTUNNGIYRF-UHFFFAOYSA-N 2-decanoyloxypropyl decanoate Chemical compound CCCCCCCCCC(=O)OCC(C)OC(=O)CCCCCCCCC NFIHXTUNNGIYRF-UHFFFAOYSA-N 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
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- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
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- 235000003441 saturated fatty acids Nutrition 0.000 description 1
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- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
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- 238000007764 slot die coating Methods 0.000 description 1
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- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Images
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/096—Nitrogen containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- 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
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- 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
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
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Abstract
【課題】分散性に優れ、層（塗膜）形成時に粉落ちが生じにくく、得られる層（塗膜）の表面の平滑性及びＵＶ加工性を向上し得るパウダー分散液、並びにかかるパウダー分散液を使用して得られる積層体及びプリント基板の提供。【解決手段】本発明のパウダー分散液は、テトラフルオロエチレン系ポリマーのパウダーと、（メタ）アクリレート系ポリマーと、ポリイミド前駆体又はポリイミドと、極性有機溶媒とを含み、前記テトラフルオロエチレン系ポリマーの含有量が１０〜６０質量％であり、前記テトラフルオロエチレン系ポリマーの含有量に対する前記ポリイミド前駆体又はポリイミドの含有量の質量での比が０．３以下である。【選択図】なしPROBLEM TO BE SOLVED: To provide a powder dispersion liquid having excellent dispersibility, less likely to cause powder falling when forming a layer (coating film), and improving the smoothness and UV processability of the surface of the obtained layer (coating film), and such a powder dispersion liquid. Providing laminates and printed circuit boards obtained using. SOLUTION: The powder dispersion liquid of the present invention contains a powder of a tetrafluoroethylene-based polymer, a (meth) acrylate-based polymer, a polyimide precursor or a polyimide, and a polar organic solvent, and is the same as the tetrafluoroethylene-based polymer. The content is 10 to 60% by mass, and the ratio of the content of the polyimide precursor or the polyimide to the content of the tetrafluoroethylene-based polymer by mass is 0.3 or less. [Selection diagram] None
Description
本発明は、テトラフルオロエチレン系ポリマーのパウダーと、ポリイミド前駆体又はポリイミドとを、所定量で含むパウダー分散液、かかる分散液から形成される層を有する積層体及びプリント基板に関する。 The present invention relates to a powder dispersion containing a tetrafluoroethylene polymer powder and a polyimide precursor or a polyimide in a predetermined amount, a laminate having a layer formed from such a dispersion, and a printed circuit board.
ポリテトラフルオロエチレン（ＰＴＦＥ）等のテトラフルオロエチレン系ポリマーは、耐薬品性、撥水撥油性、耐熱性、電気特性等の物性に優れており、パウダー、パウダー分散液、フィルム等の使用形態と、その物性を活用した種々の用途とが知られている。
近年では、電気特性と耐熱性とに優れたプリント基板に加工可能な金属張積層体を作製する際に、テトラフルオロエチレン系ポリマーのパウダーを含むパウダー分散液に、各種材料を更に混合した分散液が検討されている。特許文献１では、かかるパウダーとポリイミド前駆体とを含むパウダー分散液を用いて、金属張積層体を作製している。Tetrafluoroethylene-based polymers such as polytetrafluoroethylene (PTFE) have excellent physical properties such as chemical resistance, water and oil repellency, heat resistance, and electrical properties. , It is known that it has various uses utilizing its physical properties.
In recent years, when producing a metal-clad laminate that can be processed into a printed circuit board with excellent electrical characteristics and heat resistance, a dispersion liquid in which various materials are further mixed with a powder dispersion liquid containing a tetrafluoroethylene polymer powder. Is being considered. In Patent Document 1, a metal-clad laminate is produced by using a powder dispersion liquid containing such a powder and a polyimide precursor.
テトラフルオロエチレン系ポリマーは、ポリイミド前駆体又はポリイミド等の他の各種材料との親和性が総じて低い。このため、上記パウダー分散液は、その状態安定性（分散性、粘度、チキソ性等）が未だ充分とは言えない。より電気特性に優れた層（塗膜）を形成するために、パウダー分散液におけるテトラフルオロエチレン系ポリマーの含有量を高める（相対的にポリイミドの含有量を低める）と、その状態安定性が低下し、層（塗膜）の物性が低下する課題があることを、本発明者らは知見している。 Tetrafluoroethylene-based polymers generally have a low affinity for polyimide precursors or other various materials such as polyimide. Therefore, it cannot be said that the powder dispersion liquid has sufficient state stability (dispersity, viscosity, thixotropic property, etc.). When the content of the tetrafluoroethylene polymer in the powder dispersion is increased (the content of polyimide is relatively decreased) in order to form a layer (coating film) having more excellent electrical characteristics, its state stability is lowered. However, the present inventors have found that there is a problem that the physical properties of the layer (coating film) are deteriorated.
本発明者らは、テトラフルオロエチレン系ポリマーのパウダーとポリイミド前駆体又はポリイミドとを含み、前者の含有量が高いパウダー分散液における、かかる課題を解決すべく鋭意検討を重ねた。その結果、それぞれのポリマーの含有量及び質量比と、（メタ）アクリレート系ポリマーの配合との調整が有効であることを知見した。さらに、この場合のパウダー分散液からは、層（塗膜）形成時に粉落ちが抑制され、表面の平滑性に優れ、吸水率の低い層（塗膜）が形成され、層（塗膜）の接着性及びＵＶ加工性が優れることを知見した。 The present inventors have made extensive studies to solve such a problem in a powder dispersion containing a tetrafluoroethylene polymer powder and a polyimide precursor or a polyimide and having a high content of the former. As a result, it was found that the adjustment between the content and mass ratio of each polymer and the blending of the (meth) acrylate-based polymer is effective. Further, from the powder dispersion liquid in this case, powder falling is suppressed when the layer (coating film) is formed, a layer (coating film) having excellent surface smoothness and low water absorption is formed, and the layer (coating film) is formed. It was found that the adhesiveness and UV processability are excellent.
すなわち、本発明は、かかる知見に基づいてなされた発明であり、その目的は、分散性に優れ、層（塗膜）形成時に粉落ちが生じにくく、得られる層（塗膜）の表面の平滑性及びＵＶ加工性を向上し得るパウダー分散液、並びにかかるパウダー分散液を使用して得られる積層体及びプリント基板の提供にある。 That is, the present invention has been made based on such findings, and the purpose of the present invention is to have excellent dispersibility, to prevent powder falling when forming a layer (coating film), and to smooth the surface of the obtained layer (coating film). It is an object of the present invention to provide a powder dispersion liquid capable of improving properties and UV processability, and a laminate and a printed substrate obtained by using such a powder dispersion liquid.
本発明は、下記の態様を有する。
＜１＞ テトラフルオロエチレン系ポリマーのパウダーと、（メタ）アクリレート系ポリマーと、ポリイミド前駆体又はポリイミドと、極性有機溶媒とを含み、前記テトラフルオロエチレン系ポリマーの含有量が１０〜６０質量％であり、前記テトラフルオロエチレン系ポリマーの含有量に対する前記ポリイミド前駆体又はポリイミドの含有量の質量での比が０．３以下である、パウダー分散液。
＜２＞ 前記比が、０．００５以上０．１以下である、上記＜１＞のパウダー分散液。
＜３＞ 前記ポリイミド前駆体又はポリイミドを、濃度０．５ｇ／ｄＬとなるように、Ｎ−メチル−２−ピロリドンに溶解して溶液を調製したとき、該溶液の３０℃における対数粘度が０．２〜３ｄＬ／ｇである、上記＜１＞又は＜２＞のパウダー分散液。
＜４＞ 前記ポリイミド前駆体又はポリイミドが、芳香族テトラカルボン酸二無水物とジアミンとを反応させてなる、芳香族ポリイミド前駆体又は芳香族ポリイミドである、上記＜１＞〜＜３＞のいずれかのパウダー分散液。
＜５＞ 前記テトラフルオロエチレン系ポリマーの含有量に対する前記（メタ）アクリレート系ポリマーの含有量の質量での比が０．０２〜０．１５である、上記＜１＞〜＜４＞のいずれかのパウダー分散液。
＜６＞ 前記（メタ）アクリレート系ポリマーは、水酸基又はオキシアルキレン基を有する（メタ）アクリレートに基づく単位を含む、上記＜１＞〜＜５＞のいずれかのパウダー分散液。
＜７＞ 前記（メタ）アクリレート系ポリマーは、フルオロアルキル基又はフルオロアルケニル基を有する（メタ）アクリレートに基づく単位を含む、上記＜１＞〜＜６＞のいずれかのパウダー分散液。
＜８＞ 前記極性有機溶媒が、環状エステル、環状ケトン又は環状アミドである、上記＜１＞〜＜７＞のいずれかのパウダー分散液。
＜９＞ さらに、無機フィラーを含む、上記＜１＞〜＜８＞のいずれかのパウダー分散液。
＜１０＞ さらに、無機フィラーを含み、前記テトラフルオロエチレン系ポリマーの含有量に対する前記無機フィラーの含有量の質量での比が０．３以下である、上記＜１＞〜＜９＞のいずれかのパウダー分散液。
＜１１＞ 前記テトラフルオロエチレン系ポリマーが、ペルフルオロ(アルキルビニルエーテル)に基づく単位に基づく単位を含むテトラフルオロエチレン系ポリマー、又は、数平均分子量が２０万以下であるポリテトラフルオロエチレンである、上記＜１＞〜＜１０＞のいずれかのパウダー分散液。
＜１２＞ 前記テトラフルオロエチレン系ポリマーが、ペルフルオロ（アルキルビニルエーテル）に基づく単位を含む極性官能基を有するテトラフルオロエチレン系ポリマー、又は、ペルフルオロ（アルキルビニルエーテル）に基づく単位を全単位に対して２．０〜５．０モル％含む極性官能基を有さないテトラフルオロエチレン系ポリマーである、上記＜１＞〜＜１１＞のいずれかのパウダー分散液。
＜１３＞ 金属基板層と、該金属基板層の表面に設けられ、上記＜１＞〜＜１２＞のいずれかのパウダー分散液から形成されたポリマー層とを有する、積層体。
＜１４＞ 上記＜１３＞の積層体が有する前記金属基板層がパターン回路に加工されてなる、プリント基板。The present invention has the following aspects.
<1> A tetrafluoroethylene polymer powder, a (meth) acrylate polymer, a polyimide precursor or a polyimide, and a polar organic solvent are contained, and the content of the tetrafluoroethylene polymer is 10 to 60% by mass. A powder dispersion in which the ratio of the content of the polyimide precursor or the polyimide to the content of the tetrafluoroethylene-based polymer by mass is 0.3 or less.
<2> The powder dispersion liquid of <1> above, wherein the ratio is 0.005 or more and 0.1 or less.
<3> When a solution was prepared by dissolving the polyimide precursor or polyimide in N-methyl-2-pyrrolidone so as to have a concentration of 0.5 g / dL, the logarithmic viscosity of the solution at 30 ° C. was 0. The powder dispersion of <1> or <2> above, which is 2 to 3 dL / g.
<4> Any of the above <1> to <3>, wherein the polyimide precursor or polyimide is an aromatic polyimide precursor or an aromatic polyimide obtained by reacting an aromatic tetracarboxylic acid dianhydride with a diamine. The powder dispersion.
<5> Any of the above <1> to <4>, wherein the ratio of the content of the (meth) acrylate-based polymer to the content of the tetrafluoroethylene-based polymer by mass is 0.02 to 0.15. Powder dispersion.
<6> The powder dispersion liquid according to any one of <1> to <5> above, wherein the (meth) acrylate-based polymer contains a unit based on (meth) acrylate having a hydroxyl group or an oxyalkylene group.
<7> The powder dispersion according to any one of <1> to <6> above, wherein the (meth) acrylate-based polymer contains a unit based on a (meth) acrylate having a fluoroalkyl group or a fluoroalkenyl group.
<8> The powder dispersion liquid according to any one of <1> to <7> above, wherein the polar organic solvent is a cyclic ester, a cyclic ketone, or a cyclic amide.
<9> The powder dispersion liquid according to any one of <1> to <8> above, further containing an inorganic filler.
<10> Further, any one of the above <1> to <9>, which contains an inorganic filler and the ratio of the content of the inorganic filler to the content of the tetrafluoroethylene polymer by mass is 0.3 or less. Powder dispersion.
<11> The tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer containing a unit based on a unit based on perfluoro (alkyl vinyl ether), or a polytetrafluoroethylene having a number average molecular weight of 200,000 or less. The powder dispersion liquid according to any one of 1> to <10>.
<12> The tetrafluoroethylene polymer has a tetrafluoroethylene polymer having a polar functional group containing a unit based on perfluoro (alkyl vinyl ether), or a unit based on perfluoro (alkyl vinyl ether) for all units. The powder dispersion liquid according to any one of <1> to <11> above, which is a tetrafluoroethylene-based polymer containing 0 to 5.0 mol% and does not have a polar functional group.
<13> A laminate having a metal substrate layer and a polymer layer provided on the surface of the metal substrate layer and formed from the powder dispersion liquid according to any one of <1> to <12>.
<14> A printed circuit board obtained by processing the metal substrate layer of the laminate of <13> into a pattern circuit.
本発明によれば、分散性に優れ、層（塗膜）形成時に粉落ちが生じにくいパウダー分散液、並びに表面の平滑性及びＵＶ加工性に優れる層（塗膜）を有する積層体及びプリント基板が提供される。 According to the present invention, a powder dispersion liquid having excellent dispersibility and less likely to cause powder falling when forming a layer (coating film), and a laminate and a printed circuit board having a layer (coating film) having excellent surface smoothness and UV processability. Is provided.
以下の用語は、以下の意味を有する。
「パウダーのＤ５０」は、レーザー回折・散乱法によってパウダーの粒度分布を測定し、パウダーを構成する粒子（以下、「パウダー粒子」とも記す。）の集団の全体積を１００％として累積カーブを求め、その累積カーブ上で累積体積が５０％となる点の粒子径（体積基準累積５０％径）である。
「パウダーのＤ９０」は、レーザー回折・散乱法によってパウダーの粒度分布を測定し、パウダー粒子の集団の全体積を１００％として累積カーブを求め、その累積カーブ上で累積体積が９０％となる点の粒子径（体積基準累積９０％径）である。
つまり、パウダーのＤ５０及びＤ９０は、それぞれ、パウダー粒子の体積基準累積５０％径及び体積基準累積９０％径である。
「ポリマーの溶融粘度」は、ＡＳＴＭ Ｄ １２３８に準拠し、フローテスター及び２Φ−８Ｌのダイを用い、予め測定温度にて５分間加熱しておいたポリマーの試料（２ｇ）を０．７ＭＰａの荷重にて測定温度に保持して測定した値である。
「パウダー分散液の粘度」は、Ｂ型粘度計を用いて、室温下（２５℃）で回転数が３０ｒｐｍの条件下でパウダー分散液について測定される値である。測定を３回繰り返し、３回分の測定値の平均値とする。
「パウダー分散液のチキソ比」は、回転数が３０ｒｐｍの条件で測定されるパウダー分散液の粘度η１を、回転数が６０ｒｐｍの条件で測定されるパウダー分散液の粘度η２で除した値（η１／η２）である。
ポリマーにおける「単位」は、重合反応によってモノマーから直接形成された原子団であってもよく、重合反応によって得られたポリマーを所定の方法で処理して、構造の一部が変換された原子団であってもよい。また、モノマーＡに基づく単位をモノマーＡ単位とも記す。The following terms have the following meanings.
For "powder D50", the particle size distribution of the powder is measured by a laser diffraction / scattering method, and the cumulative curve is obtained with the total volume of a group of particles constituting the powder (hereinafter, also referred to as "powder particles") as 100%. , The particle size (volume-based cumulative 50% diameter) at the point where the cumulative volume is 50% on the cumulative curve.
"Powder D90" measures the particle size distribution of powder by laser diffraction / scattering method, obtains a cumulative curve with the total volume of a group of powder particles as 100%, and the cumulative volume is 90% on the cumulative curve. Particle size (volume-based cumulative 90% diameter).
That is, D50 and D90 of the powder are the volume-based cumulative 50% diameter and the volume-based cumulative 90% diameter of the powder particles, respectively.
"Melting viscosity of polymer" is based on ASTM D 1238, and a polymer sample (2 g) preheated at the measurement temperature for 5 minutes using a flow tester and a 2Φ-8L die is loaded with 0.7 MPa. It is a value measured by holding it at the measurement temperature at.
The "viscosity of the powder dispersion" is a value measured for the powder dispersion at room temperature (25 ° C.) and at a rotation speed of 30 rpm using a B-type viscometer. The measurement is repeated 3 times, and the average value of the measured values for 3 times is used.
The "thixotropy of the powder dispersion" is a value obtained by dividing the viscosity η 1 of the powder dispersion measured under the condition of a rotation speed of 30 rpm by the viscosity η 2 of the powder dispersion measured under the condition of a rotation speed of 60 rpm. (Η 1 / η 2 ).
The "unit" in the polymer may be an atomic group formed directly from the monomer by the polymerization reaction, and the polymer obtained by the polymerization reaction is treated by a predetermined method to convert a part of the structure. May be. Further, the unit based on the monomer A is also referred to as a monomer A unit.
本発明のパウダー分散液（本分散液）は、テトラフルオロエチレン系ポリマー（以下、「Ｆポリマー」とも記す。）を含むパウダーと、（メタ）アクリレート系ポリマー（以下、「Ａポリマー」とも記す。）と、ポリイミド前駆体又はポリイミド（以下、まとめて「ＰＩ」とも記す。）と、極性有機溶媒とを含む。上記パウダーは、極性有機溶媒中に分散しているとも言える。
本分散液は、Ｆポリマーの含有量が１０〜６０質量％であり、Ｆポリマーの含有量に対するＰＩの含有量の質量での比が０．３以下である。つまり、本分散液は、Ｆポリマーの含有量が高くＰＩの含有量が低い、Ａポリマーを含む分散液であるとも言える。The powder dispersion liquid (the present dispersion liquid) of the present invention includes a powder containing a tetrafluoroethylene-based polymer (hereinafter, also referred to as “F polymer”) and a (meth) acrylate-based polymer (hereinafter, also referred to as “A polymer”). ), A polyimide precursor or a polyimide (hereinafter, also collectively referred to as “PI”), and a polar organic solvent. It can be said that the powder is dispersed in a polar organic solvent.
This dispersion has an F polymer content of 10 to 60% by mass, and the ratio of the PI content to the F polymer content by mass is 0.3 or less. That is, it can be said that the present dispersion is a dispersion containing the A polymer, which has a high F polymer content and a low PI content.
本分散液が、分散性、粘度、チキソ性等の状態安定性に優れ、層（塗膜）形成時に粉落ちしにくく、表面の平滑性と接着性とＵＶ加工性とに優れ、吸水率の低い層（塗膜）を形成する理由は、必ずしも明確ではないが、以下の様に考えられる。
Ａポリマーが極性有機溶媒に高度に溶解するか分散するため、極性有機溶媒の表面張力は低下する。これにより、本発明における分散媒は、Ｆポリマーと濡れやすい状態になるため、高含有量のＦポリマーのパウダーが高度に分散したと考えられる。また、ＰＩは、少量成分であり、分散媒中で自由度の高い状態にあり、それぞれのポリマーと相互作用しやすいと考えられる。かかる理由により、本分散液は、状態安定性に優れている。This dispersion has excellent state stability such as dispersibility, viscosity, and thixotropy, does not easily remove powder when forming a layer (coating film), has excellent surface smoothness, adhesiveness, and UV processability, and has a water absorption rate. The reason for forming the low layer (coating film) is not always clear, but it is considered as follows.
Since the A polymer is highly soluble or dispersed in the polar organic solvent, the surface tension of the polar organic solvent is reduced. As a result, the dispersion medium in the present invention is in a state of being easily wetted with the F polymer, and it is considered that the powder of the F polymer having a high content is highly dispersed. Further, PI is a small amount component, is in a state of high degree of freedom in the dispersion medium, and is considered to easily interact with each polymer. For this reason, the dispersion is excellent in state stability.
かかるパウダー分散液を、例えば、金属基板の表面に付与及び加熱し、Ｆポリマーを含むポリマー層（以下、「Ｆ層」とも記す。）を金属基板層の表面に形成すると、積層体が得られる。この際、パウダー分散液に均一に存在するＰＩがバインダーとして機能し、Ｆ層の形成に伴うパウダーの脱落（粉落ち）を抑制すると考えられ、結果、表面の平滑性の高いＦ層が形成されたと考えられる。また、ＰＩは、そのままＦ層中に均一に存在するため、接着性とＵＶ加工性とに優れ、吸水率の低いＦ層が形成されたと考えられる。
以上のような効果は、後述する本発明の好ましい態様において、顕著に発現する。When such a powder dispersion liquid is applied to and heated on the surface of a metal substrate, for example, and a polymer layer containing an F polymer (hereinafter, also referred to as “F layer”) is formed on the surface of the metal substrate layer, a laminate is obtained. .. At this time, it is considered that the PI uniformly present in the powder dispersion functions as a binder and suppresses the powder from falling off (powder falling off) accompanying the formation of the F layer, and as a result, the F layer having high surface smoothness is formed. It is thought that it was. Further, since PI is uniformly present in the F layer as it is, it is considered that the F layer having excellent adhesiveness and UV processability and having a low water absorption rate is formed.
The above-mentioned effects are remarkably exhibited in the preferred embodiments of the present invention described later.
本発明におけるパウダーのＤ５０は、０．０５〜６μｍが好ましく、０．０５〜３μｍがより好ましい。この範囲において、パウダーの流動性と分散性とが良好となり、Ｆ層の電気特性（低誘電率等）や耐熱性が最も発現しやすい。パウダーのＤ９０は、８μｍ以下が好ましく、５μｍ以下がさらに好ましい。この範囲において、パウダーの流動性と分散性とが良好となり、Ｆ層の電気特性（低誘電率等）や耐熱性が最も発現しやすい。
パウダーの疎充填嵩密度は、０．０８〜０．５ｇ／ｍＬが好ましい。パウダーの密充填嵩密度は、０．１〜０．８ｇ／ｍＬが好ましい。疎充填嵩密度又は密充填嵩密度が上記範囲にある場合、パウダーのハンドリング性が優れる。The D50 of the powder in the present invention is preferably 0.05 to 6 μm, more preferably 0.05 to 3 μm. In this range, the fluidity and dispersibility of the powder become good, and the electrical characteristics (low dielectric constant, etc.) and heat resistance of the F layer are most likely to be exhibited. The D90 of the powder is preferably 8 μm or less, more preferably 5 μm or less. In this range, the fluidity and dispersibility of the powder become good, and the electrical characteristics (low dielectric constant, etc.) and heat resistance of the F layer are most likely to be exhibited.
The sparse filling bulk density of the powder is preferably 0.08 to 0.5 g / mL. The densely packed bulk density of the powder is preferably 0.1 to 0.8 g / mL. When the sparsely packed bulk density or the densely packed bulk density is within the above range, the handleability of the powder is excellent.
本発明におけるパウダーは、Ｆポリマー以外の樹脂を含んでいてもよく、Ｆポリマーからなるのが好ましい。パウダーにおけるＦポリマーの含有量は、８０質量％以上が好ましく、１００質量％がより好ましい。
上記樹脂としては、芳香族ポリエステル、ポリアミドイミド、熱可塑性ポリイミド、ポリフェニレンエーテル、ポリフェニレンオキシドが挙げられる。The powder in the present invention may contain a resin other than the F polymer, and is preferably made of the F polymer. The content of the F polymer in the powder is preferably 80% by mass or more, more preferably 100% by mass.
Examples of the resin include aromatic polyester, polyamide-imide, thermoplastic polyimide, polyphenylene ether, and polyphenylene oxide.
本発明におけるＦポリマーは、テトラフルオロエチレン（ＴＦＥ）に基づく単位（ＴＦＥ単位）を含むポリマーである。
Ｆポリマーは、ＴＦＥ単位からなるホモポリマー（ＰＴＦＥ）、ＴＦＥ単位とペルフルオロ（アルキルビニルエーテル）（ＰＡＶＥ）に基づく単位（ＰＡＶＥ単位）とを含むコポリマー（ＰＦＡ）、ＴＦＥ単位とヘキサフルオロプロピレン（ＨＦＰ）に基づく単位（ＨＦＰ単位）とを含むコポリマー（ＦＥＰ）又はＴＦＥ単位とフルオロアルキルエチレン（ＦＡＥ）に基づく単位（ＦＡＥ単位）とを含むコポリマーが好ましい。The F polymer in the present invention is a polymer containing a unit (TFE unit) based on tetrafluoroethylene (TFE).
F-polymers are composed of homopolymers consisting of TFE units (PTFE), copolymers (PFA) containing TFE units and units based on perfluoro (alkyl vinyl ether) (PAVE) (PAVE units), TFE units and hexafluoropropylene (HFP). Copolymers containing based units (HFP units) or copolymers containing TFE units and units based on fluoroalkylethylene (FAE) (FAE units) are preferred.
ＰＴＦＥは、ＴＦＥ単位以外の他の単位を極微量含むポリマーも包含される。他の単位を極微量含むポリマーは、このポリマーに含まれる全単位に対して、ＴＦＥ単位を、９９．５モル％以上含むのが好ましく、９９．９モル％以上含むのがより好ましい。
また、かかるポリマーの３８０℃における溶融粘度は、１×１０２〜１×１０８Ｐａ・ｓが好ましく、１×１０３〜１×１０６Ｐａ・ｓがより好ましい。
かかるポリマーとしては、低分子量のＰＴＦＥが挙げられる。PTFE also includes polymers containing trace amounts of units other than TFE units. The polymer containing a very small amount of other units preferably contains 99.5 mol% or more of TFE units, and more preferably 99.9 mol% or more, based on all the units contained in this polymer.
The melt viscosity of the polymer at 380 ° C. is preferably 1 × 10 2 to 1 × 10 8 Pa · s, more preferably 1 × 10 3 to 1 × 10 6 Pa · s.
Examples of such a polymer include low molecular weight PTFE.
低分子量のＰＴＦＥは、高分子量のＰＴＦＥ（溶融粘度が１×１０９〜１×１０１０Ｐａ・ｓ程度）に放射線を照射して得られるＰＴＦＥ（国際公開第２０１８／０２６０１２号、国際公開第２０１８／０２６０１７号等に記載のポリマー）であってもよく、ＴＦＥを重合してＰＴＦＥを製造する際に連鎖移動剤を用いて得られるＰＴＦＥ（特開２００９−１７４５号公報、国際公開第２０１０／１１４０３３号、特開２０１５−２３２０８２号公報等に記載のポリマー）であってもよく、コア部分とシェル部分とからなるコア−シェル構造を有するポリマーであって、シェル部分のみが上記溶融粘度を有するＰＴＦＥ（特表２００５−５２７６５２号公報、国際公開第２０１６／１７０９１８号、特開平０９−０８７３３４号公報等に記載のポリマー）であってもよい。Low-molecular-weight PTFE is obtained by irradiating high-molecular-weight PTFE (melt viscosity is about 1 × 10 9 to 1 × 10 10 Pa · s) with radiation (International Publication No. 2018/026012, International Publication No. 2018). (Polymer described in / 026017 etc.) may be used, and PTFE (Japanese Patent Laid-Open No. 2009-1745, International Publication No. 2010/114033) obtained by using a chain transfer agent when polymerizing TFE to produce PTFE (Japanese Patent Laid-Open No. 2009-1745) may be used. No., Polymer described in Japanese Patent Application Laid-Open No. 2015-232082, etc.), a polymer having a core-shell structure composed of a core portion and a shell portion, and only the shell portion has the above-mentioned melt viscosity. (Polymer described in Japanese Patent Application Laid-Open No. 2005-527652, International Publication No. 2016/170918, Japanese Patent Application Laid-Open No. 09-087334, etc.) may be used.
Ｆポリマーは、ＴＦＥ単位以外の他の単位を含むポリマーも包含される。他の単位を含むポリマーは、このポリマーの全単位に対して、他の単位を０．５モル％超含むのが好ましい。かかる他の単位は、ＰＡＶＥ単位、ＨＦＰ単位、ＦＡＥ単位又は後述する官能基を有する単位が好ましい。
Ｆポリマーは、カルボニル基含有基、ヒドロキシ基、エポキシ基、オキセタニル基、アミノ基、ニトリル基及びイソシアネート基からなる群から選択される少なくとも１種の官能基を有するのが好ましい。Ｆポリマーが上記官能基を有する場合、Ｆ層の接着性がより向上する。なお、カルボニル基含有基には、アミド基が含まれる。The F polymer also includes a polymer containing a unit other than the TFE unit. The polymer containing other units preferably contains more than 0.5 mol% of the other units with respect to all the units of this polymer. Such other units are preferably PAVE units, HFP units, FAE units, or units having a functional group described later.
The F polymer preferably has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an oxetanyl group, an amino group, a nitrile group and an isocyanate group. When the F polymer has the above functional groups, the adhesiveness of the F layer is further improved. The carbonyl group-containing group includes an amide group.
上記官能基は、Ｆポリマーを構成する単位に含まれてもよく、ポリマー主鎖の末端基に含まれてもよく、プラズマ処理等によりＦポリマーに導入してもよい。ポリマー主鎖の末端基に上記官能基が含まれるＦポリマーとしては、重合開始剤、連鎖移動剤等に由来する末端基として官能基を有するＦポリマーが挙げられる。
上記官能基は、ヒドロキシ基又はカルボニル基含有基が好ましく、カルボニル含有基がより好ましく、カーボネート基、カルボキシ基、ハロホルミル基、アルコキシカルボニル基又は酸無水物残基がより好ましく、カルボキシ基又は酸無水物残基がさらに好ましい。
Ｆポリマーは、ＴＦＥ単位と、ＰＡＶＥ単位、ＨＦＰ単位又はＦＡＥ単位と、官能基を有する単位とを含むポリマーが好ましい。The functional group may be contained in a unit constituting the F polymer, may be contained in the terminal group of the polymer main chain, or may be introduced into the F polymer by plasma treatment or the like. Examples of the F polymer containing the functional group in the terminal group of the polymer main chain include an F polymer having a functional group as the terminal group derived from a polymerization initiator, a chain transfer agent and the like.
The functional group is preferably a hydroxy group or a carbonyl group-containing group, more preferably a carbonyl-containing group, more preferably a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group or an acid anhydride residue, and a carboxy group or an acid anhydride. Residues are even more preferred.
The F polymer is preferably a polymer containing a TFE unit, a PAVE unit, an HFP unit or a FAE unit, and a unit having a functional group.
官能基を有する単位は、官能基を有するモノマーに基づく単位が好ましい。
官能基を有するモノマーとしては、ヒドロキシ基又はカルボニル基含有基を有するモノマーが好ましく、酸無水物残基又はカルボキシ基を有するモノマーがより好ましく、酸無水物残基を有する環状モノマーがさらに好ましい。
環状モノマーとしては、無水イタコン酸、無水シトラコン酸、５−ノルボルネン−２，３−ジカルボン酸無水物（別称：無水ハイミック酸；以下、「ＮＡＨ」とも記す。）又は無水マレイン酸が挙げられ、ＮＡＨが好ましい。The unit having a functional group is preferably a unit based on a monomer having a functional group.
As the monomer having a functional group, a monomer having a hydroxy group or a carbonyl group-containing group is preferable, a monomer having an acid anhydride residue or a carboxy group is more preferable, and a cyclic monomer having an acid anhydride residue is further preferable.
Examples of the cyclic monomer include itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride (also known as hymic anhydride; hereinafter also referred to as “NAH”) or maleic anhydride, and NAH. Is preferable.
ＰＡＶＥとしては、ＣＦ２＝ＣＦＯＣＦ３、ＣＦ２＝ＣＦＯＣＦ２ＣＦ３、ＣＦ２＝ＣＦＯＣＦ２ＣＦ２ＣＦ３（ＰＰＶＥ）、ＣＦ２＝ＣＦＯＣＦ２ＣＦ２ＣＦ２ＣＦ３、ＣＦ２＝ＣＦＯ（ＣＦ２）８Ｆが挙げられ、ＰＰＶＥが好ましい。
ＦＡＥとしては、ＣＨ２＝ＣＨ（ＣＦ２）２Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）３Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）４Ｆ、ＣＨ２＝ＣＦ（ＣＦ２）３Ｈ、ＣＨ２＝ＣＦ（ＣＦ２）４Ｈが挙げられ、ＣＨ２＝ＣＨ（ＣＦ２）４Ｆ又はＣＨ２＝ＣＨ（ＣＦ２）２Ｆが好ましい。
この場合、Ｆポリマーに含まれる全単位に対して、ＴＦＥ単位は９０〜９９モル％含まれるのが好ましく、ＰＡＶＥ単位、ＨＦＰ単位又はＦＡＥ単位は０．５〜９．９７モル％含まれるのが好ましく、官能基を有する単位は０．０１〜３モル％含まれるのが好ましい。
この場合、Ｆポリマーの溶融温度は、２５０〜３８０℃が好ましく、２８０〜３５０℃がより好ましい。
かかるＦポリマーの具体例としては、国際公開第２０１８／１６６４４号に記載のポリマーが挙げられる。As PAVE, CF 2 = CFOCF 3 , CF 2 = CFOCF 2 CF 3 , CF 2 = CFOCF 2 CF 2 CF 3 (PPVE), CF 2 = CFOCF 2 CF 2 CF 2 CF 3 , CF 2 = CFO (CF 2) ) 8 F is mentioned, and PPVE is preferable.
As FAE, CH 2 = CH (CF 2 ) 2 F, CH 2 = CH (CF 2 ) 3 F, CH 2 = CH (CF 2 ) 4 F, CH 2 = CF (CF 2 ) 3 H, CH 2 = CF (CF 2 ) 4 H is mentioned, and CH 2 = CH (CF 2 ) 4 F or CH 2 = CH (CF 2 ) 2 F is preferable.
In this case, the TFE unit is preferably contained in an amount of 90 to 99 mol%, and the PAVE unit, the HFP unit or the FAE unit is contained in an amount of 0.5 to 9.97 mol% with respect to all the units contained in the F polymer. Preferably, the unit having a functional group is preferably contained in an amount of 0.01 to 3 mol%.
In this case, the melting temperature of the F polymer is preferably 250 to 380 ° C, more preferably 280 to 350 ° C.
Specific examples of such F polymers include the polymers described in WO 2018/16644.
Ｆポリマーの好適な態様としては、ペルフルオロ（アルキルビニルエーテル）に基づく単位を含むテトラフルオロエチレン系ポリマー、又は、数平均分子量が２０万以下であるＰＴＦＥが挙げられる。
なお、上記ＰＴＦＥの数平均分子量は、下式（１）に基づいて算出される値である。
Ｍｎ ＝ ２．１×１０１０×ΔＨｃ−５．１６ ・・・ （１）
式（１）中、Ｍｎは、上記ＰＴＦＥの数平均分子量を、ΔＨｃは、示差走査熱量分析法により測定される前記ＰＴＦＥの結晶化熱量（ｃａｌ／ｇ）を、それぞれ示す。
上記ＰＴＦＥのＭｎは、１０以下が好ましく、５万以下がより好ましい。上記ＰＴＦＥのＭｎは、１万以上が好ましい。Preferable embodiments of the F polymer include a tetrafluoroethylene-based polymer containing a unit based on perfluoro (alkyl vinyl ether), or PTFE having a number average molecular weight of 200,000 or less.
The number average molecular weight of the PTFE is a value calculated based on the following formula (1).
Mn = 2.1 × 10 10 × ΔHc −5.16・ ・ ・ (1)
In the formula (1), Mn indicates the number average molecular weight of the PTFE, and ΔHc indicates the calorie of crystallization (cal / g) of the PTFE measured by the differential scanning calorimetry.
The Mn of the PTFE is preferably 10 or less, more preferably 50,000 or less. The Mn of the above PTFE is preferably 10,000 or more.
Ｆポリマーのより好適な態様としては、ペルフルオロ（アルキルビニルエーテル）に基づく単位を含む官能基を有するテトラフルオロエチレン系ポリマー、又は、ペルフルオロ（アルキルビニルエーテル）に基づく単位を全単位に対して２．０〜５．０モル％含む官能基を有さないテトラフルオロエチレン系ポリマーが挙げられる。
この態様のＦポリマーは、そのパウダーが分散安定性に優れるだけでなく、本分散液から形成されるＦ層において、緻密かつ均一に分布しやすい。さらに、Ｆ層において微小球晶を形成しやすく、他の成分との密着性が高まりやすい。その結果、３成分それぞれの物性を高度に具備したＦ層が、より形成されやすい。As a more preferable embodiment of the F polymer, a tetrafluoroethylene polymer having a functional group containing a unit based on perfluoro (alkyl vinyl ether) or a unit based on perfluoro (alkyl vinyl ether) is 2.0 to 2.0 to all units. Examples thereof include tetrafluoroethylene-based polymers containing 5.0 mol% and having no functional group.
The F polymer of this embodiment not only has excellent dispersion stability of the powder, but also tends to be densely and uniformly distributed in the F layer formed from the present dispersion liquid. Further, microspherulites are likely to be formed in the F layer, and adhesion with other components is likely to be enhanced. As a result, the F layer having the physical characteristics of each of the three components is more likely to be formed.
前者のポリマーは、全単位に対して、ＴＦＥ単位を９０〜９９モル％、ＰＡＶＥ単位を０．５〜９．９７モル％及び官能基を有するモノマーに基づく単位を０．０１〜３モル％、それぞれ含有するのが好ましい。
後者のポリマーにおけるＰＡＶＥ単位の含有量は、全単位に対して、２．１モル％以上が好ましく、２．２モル％以上がより好ましい。
後者のポリマーは、ＴＦＥ単位及びＰＡＶＥ単位のみからなり、全単位に対して、ＴＦＥ単位を９５．０〜９８．０モル％、ＰＡＶＥ単位を２．０〜５．０モル％含有するのが好ましい。The former polymer has 90 to 99 mol% of TFE units, 0.5 to 9.97 mol% of PAVE units, and 0.01 to 3 mol% of units based on a monomer having a functional group, based on all the units. It is preferable to contain each of them.
The content of PAVE units in the latter polymer is preferably 2.1 mol% or more, more preferably 2.2 mol% or more, based on all units.
The latter polymer consists of only TFE units and PAVE units, and preferably contains 95.0 to 98.0 mol% of TFE units and 2.0 to 5.0 mol% of PAVE units with respect to all the units. ..
なお、後者のポリマーが官能基を有さないとは、ポリマー主鎖を構成する炭素原子数の１×１０６個あたりに対して、ポリマーが有する官能基の数が、５００個未満であることを意味する。上記官能基の数は、１００個以下が好ましく、５０個以下がより好ましい。上記官能基の数の下限は、通常、０個である。
後者のポリマーは、ポリマー鎖の末端基として官能基を生じない、重合開始剤や連鎖移動剤等を使用して製造してもよく、官能基を有するＦポリマー（重合開始剤に由来する極性官能基をポリマーの主鎖の末端基に有するＦポリマー等）をフッ素化処理して製造してもよい。フッ素化処理の方法としては、フッ素ガスを使用する方法（特開２０１９−１９４３１４号公報等を参照）が挙げられる。The latter polymer has no functional group means that the number of functional groups of the polymer is less than 500 with respect to 1 × 10 6 carbon atoms constituting the polymer main chain. Means. The number of the functional groups is preferably 100 or less, more preferably 50 or less. The lower limit of the number of functional groups is usually 0.
The latter polymer may be produced by using a polymerization initiator, a chain transfer agent, or the like that does not generate a functional group as a terminal group of the polymer chain, and an F polymer having a functional group (polar functionality derived from the polymerization initiator). An F polymer having a group at the terminal group of the main chain of the polymer) may be fluorinated to produce the polymer. Examples of the fluorination treatment method include a method using fluorine gas (see JP-A-2019-194314, etc.).
本発明における極性有機溶媒は、２５℃で液体の化合物であり、水性溶媒であってもよく、非水性溶媒であってもよい。
極性有機溶媒は、アミド、アルコール、スルホキシド、エステル、ケトン又はグリコールエーテルが好ましく、エステル、ケトン又はアミドがより好ましく、環状エステル、環状ケトン又は環状アミドがさらに好ましい。本発明におけるＡポリマーは、これらの極性有機溶媒との相互作用が高く、よってパウダー分散液の層（塗膜）形成性（チキソ比、接着性、透明性等）が向上しやすい。極性有機溶媒は、１種を単独で使用してもよく、２種以上を併用してもよい。The polar organic solvent in the present invention is a compound that is liquid at 25 ° C., and may be an aqueous solvent or a non-aqueous solvent.
The polar organic solvent is preferably an amide, alcohol, sulfoxide, ester, ketone or glycol ether, more preferably an ester, ketone or amide, and even more preferably a cyclic ester, cyclic ketone or cyclic amide. The A polymer in the present invention has a high interaction with these polar organic solvents, and thus the layer (coating film) formability (thixotropy ratio, adhesiveness, transparency, etc.) of the powder dispersion liquid tends to be improved. One type of polar organic solvent may be used alone, or two or more types may be used in combination.
極性有機溶媒の具体例としては、メタノール、エタノール、イソプロパノール、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、ジメチルスルホキシド、ジエチルエーテル、ジオキサン、乳酸エチル、酢酸エチル、酢酸ブチル、γ−ブチロラクトン、メチルエチルケトン、メチルイソプロピルケトン、シクロペンタノン、シクロヘキサノン、エチレングリコールモノイソプロピルエーテル、セロソルブ（メチルセロソルブ、エチルセロソルブ等）が挙げられる。
極性有機溶媒は、沸点が８０〜２７５℃の化合物がより好ましく、沸点が１２５〜２５０℃の化合物がさらに好ましい。この範囲において、パウダー分散液から極性有機溶媒を加熱留去させた際、極性有機溶媒の揮発とＡポリマーの分解及び流動とが効果的に進行する。
かかる極性有機溶媒は、Ｎ−メチル−２−ピロリドン、γ−ブチロラクトン、シクロヘキサノン又はシクロペンタノンが好ましく、シクロヘキサノン又はＮ−メチル−２−ピロリドンがより好ましい。Specific examples of polar organic solvents include methanol, ethanol, isopropanol, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, diethyl ether, dioxane, ethyl lactate, and ethyl acetate. , Butyl acetate, γ-butyrolactone, methyl ethyl ketone, methyl isopropyl ketone, cyclopentanone, cyclohexanone, ethylene glycol monoisopropyl ether, cellosolve (methyl cellosolve, ethyl cellosolve, etc.).
The polar organic solvent is more preferably a compound having a boiling point of 80 to 275 ° C., and further preferably a compound having a boiling point of 125 to 250 ° C. In this range, when the polar organic solvent is heated and distilled off from the powder dispersion, the volatilization of the polar organic solvent and the decomposition and flow of the A polymer proceed effectively.
The polar organic solvent is preferably N-methyl-2-pyrrolidone, γ-butyrolactone, cyclohexanone or cyclopentanone, and more preferably cyclohexanone or N-methyl-2-pyrrolidone.
本発明におけるＡポリマーは、アクリレート又はメタクリレートの単位を含むポリマーである。なお、Ａポリマーは、Ｆポリマー以外のポリマーである。
Ａポリマーは、水酸基、オキシアルキレン基又は熱分解性基を有する（メタ）アクリレートに基づく単位（以下、「単位Ｈ」とも記す。）を含むのが好ましく、水酸基又はオキシアルキレン基を有する（メタ）アクリレートに基づく単位を含むのがより好ましい。
かかる（メタ）アクリレートとしては、下式（１）〜（３）で表される化合物が挙げられる。
式（１）：ＣＨ２＝ＣＸＨＣ（Ｏ）Ｏ−Ｑ１−Ｒ１
式（２）：ＣＨ２＝ＣＸＨＣ（Ｏ）ＯＣ（−Ｒ２）３
式（３）：ＣＨ２＝ＣＸＨＣ（Ｏ）ＯＣ（−Ｒ３１）（−Ｒ３２）２
式中の記号は、以下の意味を示す。
ＸＨは、水素原子又はメチル基である。
Ｑ１は、ポリオキシアルキレン基であり、ポリオキシエチレン基又はポリオキシプロピレン基が好ましく、ポリオキシエチレン基がより好ましい。
Ｒ１は、水素原子、アルキル基又はアリール基であり、水素原子、メチル基、ノニル基、ラウリル基、ステアリル基、フェニル基、ステアリルフェニル基、ラウリルフェニル基又はノニルフェニル基が好ましく、水素原子又はメチル基がより好ましい。
Ｒ２は、水素原子、アルキル基又はアリール基であり、３個のＲ２の少なくとも１個は、アリール基である。Ｒ２は、炭素数１〜６のアルキル基又はフェニル基が好ましく、メチル基又はフェニル基がより好ましい。
Ｒ３１は、水素原子又はアルコキシ基であり、水素原子又は炭素数１〜３のアルコキシ基が好ましく、水素原子がより好ましい。
２個のＲ３２は、共同してアルキレン基を形成している。The A polymer in the present invention is a polymer containing a unit of acrylate or methacrylate. The A polymer is a polymer other than the F polymer.
The A polymer preferably contains a unit based on a (meth) acrylate having a hydroxyl group, an oxyalkylene group or a thermally decomposable group (hereinafter, also referred to as “unit H”), and has a hydroxyl group or an oxyalkylene group (meth). More preferably, it contains a unit based on acrylate.
Examples of such (meth) acrylate include compounds represented by the following formulas (1) to (3).
Equation (1): CH 2 = CX H C (O) O-Q 1 -R 1
Equation (2): CH 2 = CX H C (O) OC (-R 2) 3
Equation (3): CH 2 = CX H C (O) OC (-R 31) (- R 32) 2
The symbols in the formula have the following meanings.
XH is a hydrogen atom or a methyl group.
Q 1 is a polyoxyalkylene group, preferably a polyoxyethylene group or a polyoxypropylene group, and more preferably a polyoxyethylene group.
R 1 is a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom, a methyl group, a nonyl group, a lauryl group, a stearyl group, a phenyl group, a stearylphenyl group, a laurylphenyl group or a nonylphenyl group, preferably a hydrogen atom or a nonylphenyl group. Methyl groups are more preferred.
R 2 is a hydrogen atom, an alkyl group or an aryl group, at least one of the three R 2 is an aryl group. R 2 is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms, more preferably a methyl group or a phenyl group.
R 31 is a hydrogen atom or an alkoxy group, preferably a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.
The two R 32s jointly form an alkylene group.
かかる（メタ）アクリレートに基づく単位を含むＡポリマーは、パウダー分散液中のＦポリマーのパウダーの分散とＰＩに対する相互作用とを促すだけでなく、パウダー分散液を加熱して層（塗膜）を形成する際には分解しやすいため、パウダー分散液の層（塗膜）形成性を特に向上させやすい。 The A polymer containing such a unit based on (meth) acrylate not only promotes the dispersion of the powder of the F polymer in the powder dispersion and the interaction with PI, but also heats the powder dispersion to form a layer (coating film). Since it is easily decomposed when it is formed, it is particularly easy to improve the layer (coating film) formability of the powder dispersion liquid.
上記化合物の具体例としては、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ−（ＣＨ２ＣＨ２Ｏ）１０−Ｈ、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ−（ＣＨ２ＣＨ２Ｏ）２３−Ｈ、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ−（ＣＨ２ＣＨ２Ｏ）２３−ＣＨ３、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ−（ＣＨ２ＣＨ２Ｏ）６６−ＣＨ３、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ−（ＣＨ２ＣＨ２Ｏ）９０−ＣＨ３、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ−（ＣＨ２ＣＨ２Ｏ）１２０−ＣＨ３、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ−（ＣＨ２ＣＨ２Ｏ）３０−（ＣＨ２）１２Ｈ、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ−（ＣＨ２ＣＨ２Ｏ）６・（ＣＨ２ＣＨ（ＣＨ３）Ｏ）５−Ｐｈ、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）ＯＣＨ２Ｐｈ、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）ＯＣＨ（ＣＨ３）Ｐｈ、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）ＯＣＨ＜Ｎｂ、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ−（ＣＨ２ＣＨ２Ｏ）１０−Ｈ、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ−（ＣＨ２ＣＨ２Ｏ）２３−Ｈ、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ−（ＣＨ２ＣＨ２Ｏ）２３−ＣＨ３、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ−（ＣＨ２ＣＨ２Ｏ）６６−ＣＨ３、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ−（ＣＨ２ＣＨ２Ｏ）９０−ＣＨ３、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ−（ＣＨ２ＣＨ２Ｏ）１２０−ＣＨ３、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ−（ＣＨ２ＣＨ２Ｏ）３０−（ＣＨ２）１２Ｈ、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ−（ＣＨ２ＣＨ２Ｏ）６・（ＣＨ２ＣＨ（ＣＨ３）Ｏ）５−Ｐｈ、ＣＨ２＝ＣＨＣ（Ｏ）ＯＣＨ２Ｐｈ、ＣＨ２＝ＣＨＣ（Ｏ）ＯＣＨ（ＣＨ３）Ｐｈ、ＣＨ２＝ＣＨＣ（Ｏ）ＯＣＨ＜Ｎｂが挙げられる。なお、上記化合物中、Ｐｈはフェニル基を、−ＣＨ＜Ｎｂはイソボルニル基を、示す。Specific examples of the above compounds include CH 2 = C (CH 3 ) C (O) O- (CH 2 CH 2 O) 10- H, CH 2 = C (CH 3 ) C (O) O- (CH 2). CH 2 O) 23- H, CH 2 = C (CH 3 ) C (O) O- (CH 2 CH 2 O) 23- CH 3 , CH 2 = C (CH 3 ) C (O) O- (CH) 2 CH 2 O) 66- CH 3 , CH 2 = C (CH 3 ) C (O) O- (CH 2 CH 2 O) 90- CH 3 , CH 2 = C (CH 3 ) C (O) O- (CH 2 CH 2 O) 120- CH 3 , CH 2 = C (CH 3 ) C (O) O- (CH 2 CH 2 O) 30- (CH 2 ) 12 H, CH 2 = C (CH 3 ) C (O) O- (CH 2 CH 2 O) 6 · (
また、Ａポリマーは、フルオロアルキル基又はフルオロアルケニル基を有する（メタ）アクリレートに基づく単位（以下、「単位Ｆ」とも記す。）を含むのが好ましい。
かかる（メタ）アクリレートとしては、下式Ｆで表される化合物が挙げられる。
式Ｆ：ＣＨ２＝ＣＸＦＣ（Ｏ）Ｏ−ＱＦ−ＲＦ
式中の記号は、以下の意味を示す。
ＸＦは、水素原子、塩素原子又はメチル基である。
ＱＦは、メチレン基、エチレン基、オキシエチレン基又はオキシブチレン基である。ただし、ＲＦが炭素数１〜６のポリフルオロアルキル基又はエーテル性酸素原子を含む炭素数３〜６のポリフルオロアルキル基である場合には、ＱＦはメチレン基又はエチレン基が好ましい。また、ＲＦが炭素数４〜１２のポリフルオロアルケニル基である場合には、ＱＦはオキシエチレン基又はオキシブチレン基が好ましい。
ＲＦは、炭素数１〜６のポリフルオロアルキル基、エーテル性酸素原子を含む炭素数３〜６のポリフルオロアルキル基又は炭素数４〜１２のポリフルオロアルケニル基である。
ＲＦとしては、−（ＣＦ２）４Ｆ、−（ＣＦ２）６Ｆ、−ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ３、−ＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＣＦ３、−ＣＦ（ＣＦ３）Ｃ（＝Ｃ（ＣＦ３）２）（ＣＦ（ＣＦ３）２）又は−Ｃ（ＣＦ３）Ｃ（＝Ｃ（ＣＦ（ＣＦ３）２）２）が好ましく、−（ＣＦ２）４Ｆ、−（ＣＦ２）６Ｆ、−ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ３又は−ＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＣＦ３がより好ましい。中でも、Ｆ層の物性（濡れ性、接着性、平滑性等）が更に優れる観点から、ＲＦは、−（ＣＦ２）４Ｆ又は−（ＣＦ２）６Ｆがさらに好ましく、−（ＣＦ２）６Ｆが特に好ましい。Further, the A polymer preferably contains a unit based on a (meth) acrylate having a fluoroalkyl group or a fluoroalkenyl group (hereinafter, also referred to as “unit F”).
Examples of such (meth) acrylate include compounds represented by the following formula F.
Formula F: CH 2 = CX F C (O) O-Q F -R F
The symbols in the formula have the following meanings.
X F is a hydrogen atom, a chlorine atom or a methyl group.
Q F is a methylene group, an ethylene group, an oxyethylene group or an oxybutylene group. However, if R F is a polyfluoroalkyl group having 3 to 6 carbon atoms containing a polyfluoroalkyl group or an etheric oxygen atom 1 to 6 carbon atoms, Q F is a methylene group or an ethylene group is preferred. Further, when R F is a polyfluoroalkenyl group having 4 to 12 carbon atoms, Q F is an oxyethylene group or an oxybutylene group are preferable.
R F is a polyfluoroalkyl group, a polyfluoroalkyl group or polyfluoroalkenyl group having 4 to 12 carbon atoms having 3 to 6 carbon atoms containing an etheric oxygen atom having 1 to 6 carbon atoms.
The R F, - (CF 2) 4 F, - (CF 2) 6 F, -
かかる（メタ）アクリレートに基づく単位を含むＡポリマーは、パウダー分散液中のＦポリマーのパウダーの分散とＰＩに対する相互作用を促すため、特に、パウダー分散液の分散性を向上させやすい。 Since the A polymer containing such a unit based on (meth) acrylate promotes the dispersion of the powder of the F polymer in the powder dispersion and the interaction with PI, it is particularly easy to improve the dispersibility of the powder dispersion.
上記化合物の具体例としては、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＝Ｃ（ＣＨ３）Ｃ（Ｏ）ＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＣＦ（ＣＦ３）Ｃ（＝Ｃ（ＣＦ３）２）（ＣＦ（ＣＦ３）２）、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）ＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＣ（ＣＦ３）Ｃ（＝Ｃ（ＣＦ（ＣＦ３）２）２）が挙げられる。Specific examples of the above compounds include CH 2 = C (CH 3 ) C (O) OCH 2 CH 2 (CF 2 ) 6 F, CH 2 = CHC (O) OCH 2 CH 2 (CF 2 ) 6 F, CH. 2 = C (CH 3 ) C (O) OCH 2 CH 2 (CF 2 ) 4 F, CH 2 = CClC (O) OCH 2 CH 2 (CF 2 ) 4 F, CH 2 = C (CH 3 ) C ( O) OCH 2 CH 2 CH 2 CH 2 OCF (CF 3 ) C (= C (CF 3 ) 2 ) (CF (CF 3 ) 2 ), CH 2 = C (CH 3 ) C (O) OCH 2 CH 2 CH 2 CH 2 OC (CF 3 ) C (= C (CF (CF 3 ) 2 ) 2 ) can be mentioned.
Ａポリマーに含まれる全単位に対する単位Ｈの量は、５〜６０モル％が好ましく、５〜４５モル％がより好ましく、１０〜３０モル％がさらに好ましい。
Ａポリマーに含まれる全単位に対する単位Ｆの量は、４０〜９５モル％が好ましく、５５〜９５モル％がより好ましく、７０〜９０モル％がさらに好ましい。
Ａポリマーに含まれる全単位に対する各単位の量が上記範囲であれば、パウダー分散液の分散性がより向上し、Ｆ層の各種物性がバランスよく発現する。
Ａポリマーは、単位Ｈ及び単位Ｆのみからなっていてもよく、本発明の効果を損なわない範囲において、単位Ｈ及び単位Ｆ以外の追加の単位をさらに含んでいてもよい。The amount of the unit H with respect to all the units contained in the A polymer is preferably 5 to 60 mol%, more preferably 5 to 45 mol%, still more preferably 10 to 30 mol%.
The amount of the unit F with respect to all the units contained in the A polymer is preferably 40 to 95 mol%, more preferably 55 to 95 mol%, still more preferably 70 to 90 mol%.
When the amount of each unit with respect to all the units contained in the A polymer is within the above range, the dispersibility of the powder dispersion is further improved, and various physical properties of the F layer are expressed in a well-balanced manner.
The A polymer may consist of only the unit H and the unit F, and may further contain additional units other than the unit H and the unit F as long as the effects of the present invention are not impaired.
本発明におけるＡポリマーのフッ素含有量は、１０〜６０質量％が好ましく、２０〜５０質量％がより好ましく、２５〜４５質量％がさらに好ましい。フッ素含有量の下限が上記範囲にあれば、パウダー分散液の分散性が優れる。フッ素含有量の上限が上記範囲にあれば、パウダー分散液の各成分に対するＡポリマーの親和性がバランスするため、パウダー分散液の分散性に加えて、その層（塗膜）形成性が向上しやすい。例えば、Ｆ層は、濡れ性が高く、表面の平滑性と接着性とに優れる特徴がある。Ａポリマーのフッ素含有量は、その合成に際するモノマーの種類と、その仕込量から計算できる。 The fluorine content of the A polymer in the present invention is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, and even more preferably 25 to 45% by mass. When the lower limit of the fluorine content is within the above range, the dispersibility of the powder dispersion is excellent. When the upper limit of the fluorine content is within the above range, the affinity of the A polymer for each component of the powder dispersion is balanced, so that the layer (coating film) formability is improved in addition to the dispersibility of the powder dispersion. Cheap. For example, the F layer has high wettability and is characterized by excellent surface smoothness and adhesiveness. The fluorine content of the A polymer can be calculated from the type of monomer used for its synthesis and the amount charged.
本発明におけるＰＩは、ポリイミド前駆体又はポリイミドである。ポリイミド前駆体は、Ｆポリマー（パウダー）の焼成時にイミド化して、ポリイミドとなる化合物である。
ポリイミドとしては、テトラカルボン酸二無水物とジアミンとを反応させてなる芳香族ポリイミドが好ましく、テトラカルボン酸二無水物及びジアミンの少なくとも一方が芳香族環を有する芳香族ポリイミド（半芳香族ポリイミド又は全芳香族ポリイミド）がより好ましく、芳香族テトラカルボン酸二無水物とジアミンとを反応させてなる芳香族ポリイミドがさらに好ましい。
芳香族ポリイミドは、ＵＶレーザーにおいて一般的な波長３５５ｎｍの紫外線に対する吸収性を有するため、得られるＦ層のＵＶ加工性がより向上する。また、Ｆ層を形成する際に、平面性の高い芳香族環同士が積層した状態となりやすいため、Ｆ層の機械的強度や耐熱性も向上する。The PI in the present invention is a polyimide precursor or a polyimide. The polyimide precursor is a compound that is imidized during firing of the F polymer (powder) to become polyimide.
As the polyimide, an aromatic polyimide obtained by reacting a tetracarboxylic acid dianhydride with a diamine is preferable, and an aromatic polyimide (semi-aromatic polyimide or semi-aromatic polyimide) in which at least one of the tetracarboxylic acid dianhydride and the diamine has an aromatic ring. Total aromatic polyimide) is more preferable, and aromatic polyimide obtained by reacting aromatic tetracarboxylic acid dianhydride with diamine is further preferable.
Since the aromatic polyimide has an absorption property for ultraviolet rays having a wavelength of 355 nm, which is common in UV lasers, the UV processability of the obtained F layer is further improved. Further, when the F layer is formed, the aromatic rings having high flatness are likely to be in a laminated state, so that the mechanical strength and heat resistance of the F layer are also improved.
芳香族テトラカルボン酸二無水物としては、ピロメリット酸二無水物、３，３’４，４’−ビフェニルテトラカルボン酸二無水物、２，２’，３，３’−ビフェニルテトラカルボン酸二無水物、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物、３，３’，４，４’−ビフェニルエーテルテトラカルボン酸二無水物、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物、２，２−ビス（３，４−ジカルボキシフェニル）プロパン二無水物、２，２−ビス（２，３−ジカルボキシフェニル）プロパン二無水物、１，１−ビス（２，３−ジカルボキシフェニル）エタン二無水物、１，１−ビス（３，４−ジカルボキシフェニル）エタン二無水物、ビス（２，３−ジカルボキシフェニル）メタン二無水物、ビス（３，４−ジカルボキシフェニル）メタン二無水物、ビス（３，４−ジカルボキシフェニル）スルホン二無水物、３，４，９，１０−ペリレンテトラカルボン酸二無水物、ビス（３，４−ジカルボキシフェニル）エーテル二無水物、ベンゼン−１，２，３，４−テトラカルボン酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、２，３，２’，３’−ベンゾフェノンテトラカルボン酸二無水物、２，３，３’，４’−ベンゾフェノンテトラカルボン酸二無水物、１，２，５，６−ナフタレンテトラカルボン酸二無水物、２，３，６，７−ナフタレンテトラカルボン酸二無水物、１，２，４，５−ナフタレンテトラカルボン酸二無水物、１，４，５，８−ナフタレンテトラカルボン酸二無水物、２，６−ジクロルナフタレン−１，４，５，８−テトラカルボン酸二無水物、２，７−ジクロルナフタレン−１，４，５，８−テトラカルボン酸二無水物、２，３，６，７−テトラクロルナフタレン−１，４，５，８−テトラカルボン酸二無水物、フェナントレン−１，８，９，１０−テトラカルボン酸二無水物、ビス（３，４−ジカルボキシフェニル）ジメチルシラン二無水物、ビス（３，４−ジカルボキシフェニル）メチルフェニルシラン二無水物、ビス（３，４−ジカルボキシフェニル）ジフェニルシラン二無水物、１，４−ビス（３，４−ジカルボキシフェニルジメチルシリル）ベンゼン二無水物、１，３−ビス（３，４−ジカルボキシフェニル）−１，１，３，３−テトラメチルジシクロヘキサン二無水物、ｐ−フェニレンビス（トリメリット酸モノエステル酸無水物）、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン二無水物、２，２−ビス［４−（３，４−ジカルボキシフェノキシ）フェニル］ヘキサフルオロプロパン二無水物、２，２−ビス［４−（３，４−ジカルボキシフェノキシ）フェニル］プロパン二無水物、４，４−ビス（３，４−ジカルボキシフェノキシ）ジフェニルスルフィド二無水物が挙げられる。 Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, 3,3'4,4'-biphenyltetracarboxylic acid dianhydride, and 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride. Anhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'- Diphenylsulfonetetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1 -Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, Bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) 4-Dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic hydride, 3,3', 4,4'-benzophenone tetracarboxylic hydride, 2,3 2', 3'-benzophenone tetracarboxylic acid dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2, 3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,6- Dichlornaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7- Tetrachlornaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, phenanthrene-1,8,9,10-tetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride Thing, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) ) Benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylene bis (trimeritic acid monoesteric acid) Anhydride), 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride) , 2,2-Bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 4,4-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, and the like.
脂肪族テトラカルボン酸二無水物としては、エチレンテトラカルボン酸二無水物、ブタンテトラカルボン酸二無水物、メソ−ブタン−１，２，３，４−テトラカルボン酸二無水物、３，３’，４，４’−ビスシクロヘキサンテトラカルボン酸二無水物、１，２，３，４−シクロブタンテトラカルボン酸二無水物、１，２，３，４−シクロペンタンテトラカルボン酸二無水物、１，２，４，５−シクロヘキサンテトラカルボン酸二無水物、１，２，３，４−テトラメチル−１，２，３，４−シクロブタンテトラカルボン酸二無水物、ビシクロ［２．２．２］オクト−７−エン−２，３，５，６−テトラカルボン酸二無水物、４−（２，５−ジオキソテトラヒドロフラン−３−イル）−１，２，３，４−テトラヒドロナフタレン−１，２−ジカルボン酸無水物、１，１’−ビシクロヘキサン−３，３’，４，４’−テトラカルボン酸二無水物が挙げられる。 Examples of the aliphatic tetracarboxylic dianhydride include ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, mesobutane-1,2,3,4-tetracarboxylic dianhydride, 3,3'. , 4,4'-biscyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1, 2,4,5-Cyclohexanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, bicyclo [2.2.2] octo -7-ene-2,3,5,6-tetracarboxylic dianhydride, 4- (2,5-dioxo tetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2 Examples thereof include -dicarboxylic dianhydride and 1,1'-bicyclohexane-3,3', 4,4'-tetracarboxylic dianhydride.
芳香族ジアミンとしては、ｏ−フェニレンジアミン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、３，３’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル、３，３’−ジアミノジフェニルメタン、３，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルメタン、３，３’−ジアミノジフェニルジフルオロメタン、４，４’−ジアミノジフェニルジフルオロメタン、３，３’−ジアミノジフェニルスルホン、３，４’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルスルホン、３，３’−ジアミノジフェニルスルフィド、３，４’−ジアミノジフェニルスルフィド、４，４’−ジアミノジフェニルスルフィド、３，３’−ジアミノジフェニルケトン、３，４’−ジアミノジフェニルケトン、４，４’−ジアミノジフェニルケトン、２，２−ビス（３−アミノフェニル）プロパン、２，２−（３，４’−ジアミノジフェニル）プロパン、２，２−ビス（４−アミノフェニル）プロパン、２，２−ビス（３−アミノフェニル）ヘキサフルオロプロパン、２，２−（３，４’−ジアミノジフェニル）ヘキサフルオロプロパン、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン、１，３−ビス（３−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン、３，３’−［１，４−フェニレンビス（１−メチルエチリデン）］ビスアニリン、３，４’−［１，４−フェニレンビス（１−メチルエチリデン）］ビスアニリン、４，４’−［１，４−フェニレンビス（１−メチルエチリデン）］ビスアニリン、２，２−ビス［４−（３−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（３−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、ビス［４−（３−アミノフェノキシ）フェニル］スルフィド、ビス［４−（４−アミノフェノキシ）フェニル］スルフィド、ビス［４−（３−アミノフェノキシ）フェニル］スルホン、ビス［４−（４−アミノフェノキシ）フェニル］スルホン、１，３−ビス（４−アミノフェノキシ）プロパン、１，４−ビス（４−アミノフェノキシ）ブタン、１，５−ビス（４−アミノフェノキシ）ヘプタンが挙げられる。 As aromatic diamines, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'- Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3, 4'-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfide, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 3,3′-diaminodiphenyl Ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2- (3,4'-diaminodiphenyl) propane, 2, 2-Bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4) -Aminophenyl) Hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3'-[1,4-phenylenebis (1-methyl) Ethiliden)] bisaniline, 3,4'-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4'-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 2,2 -Bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexa Fluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide , Bis [4- (3-aminophenoxy) phenyl] sulfone, Bis [4- (4-aminophenoxy) phenyl] sulfone, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-) Aminophenoxy) butane, 1,5-bis (4-aminophenoxy) Kishi) Heptane can be mentioned.
脂肪族ジアミンとしては、１，２−エチレンジアミン、１，２−ジアミノプロパン、１，３−ジアミノプロパン、１，４−ジアミノブタン、１，６−ヘキサメチレンジアミン、１，５−ジアミノペンタン、１，１０−ジアミノデカン、１，２−ジアミノ−２−メチルプロパン、２，３−ジアミノ−２，３−ブタンジアミン、２−メチル−１，５−ジアミノペンタン、１，３−ビス（アミノメチル）シクロヘキサン、１，４−ビス（アミノメチル）シクロヘキサン、１，４−ジアミノシクロヘキサン、４，４’−メチレンビス（シクロヘキシルアミン）、４，４’−メチレンビス（２−メチルシクロヘキシルアミン）が挙げられる。 Aliphatic diamines include 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 1,5-diaminopentane, 1, 10-Diaminodecane, 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butanediamine, 2-methyl-1,5-diaminopentane, 1,3-bis (aminomethyl) cyclohexane , 1,4-bis (aminomethyl) cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (2-methylcyclohexylamine).
芳香族ポリイミドとしては、芳香族テトラカルボン酸二無水物と芳香族ジアミン及び／又は脂肪族ジアミンとを反応させてなる半芳香族又は全芳香族ポリイミドが好ましく、芳香族テトラカルボン酸二無水物と芳香族ジアミンとを反応させてなる全芳香族ポリイミドがより好ましい。
芳香族テトラカルボン酸二無水物としては、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’−ビフェニルエーテルテトラカルボン酸二無水物、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物、ピロメリット酸二無水物からなる群から選ばれる少なくとも１種が好ましい。一方、芳香族ジアミンとして、ｏ−フェニレンジアミン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、３，３’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルエーテル、及び３，４’−ジアミノジフェニルエーテルからなる群から選ばれる少なくとも１種が好ましい。
これらのモノマーを少なくとも含むＰＩであれば、Ｆ層のＵＶ加工性をより向上できるとともに、Ｆ層に対して、プリント基板として使用する際に要求される優れた耐熱性及び低吸水性を付与できる。As the aromatic polyimide, a semi-aromatic or total aromatic polyimide obtained by reacting an aromatic tetracarboxylic acid dianhydride with an aromatic diamine and / or an aliphatic diamine is preferable, and the aromatic tetracarboxylic acid dianhydride is used. A total aromatic polyimide obtained by reacting with an aromatic diamine is more preferable.
Examples of the aromatic tetracarboxylic acid dianhydride include 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3. At least one selected from the group consisting of', 4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, and pyromellitic acid dianhydride. Is preferable. On the other hand, the aromatic diamine consists of a group consisting of o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl ether. At least one selected is preferred.
A PI containing at least these monomers can further improve the UV processability of the F layer and can impart the excellent heat resistance and low water absorption required for use as a printed circuit board to the F layer. ..
また、本発明におけるＰＩの対数粘度（ηｉｈｎ）は、０．２〜３ｄＬ／ｇが好ましく、０．５〜２ｄＬ／ｇがより好ましい。なお、対数粘度は、下式で表される値である。
式：ηｉｈｎ＝［ｌｎ（η／η０）］／Ｃ
式中、ηは、ＰＩを濃度０．５ｇ／ｄＬとなるように、Ｎ−メチル−２−ピロリドン（ＮＭＰ）に溶解して溶液を調製し、この溶液の約３０℃（３０±０．０１℃）における粘度をウベローデ粘度計で測定した値であり、η０は、同溶媒の同温度における粘度を同粘度計で測定した値であり、Ｃは、濃度０．５ｇ／ｄＬである。
ここで、ＰＩの対数粘度（固有粘度）は、ＰＩの分子量と相関している。
ＰＩの対数粘度が上記範囲であれば、ＰＩの分子量及び粘度が適度になるため、ＰＩのパウダーの沈降抑制効果が好適に発揮され、パウダーのパウダー分散液中での分散性が良好になるとともに、ＰＩがバインダーとして好適に機能し、Ｆ層形成時における粉落ち防止効果がより向上する。The logarithmic viscosity (ηihn) of PI in the present invention is preferably 0.2 to 3 dL / g, more preferably 0.5 to 2 dL / g. The logarithmic viscosity is a value represented by the following formula.
Formula: ηihn = [ln (η / η0)] / C
In the formula, η prepared a solution by dissolving PI in N-methyl-2-pyrrolidone (NMP) so as to have a concentration of 0.5 g / dL, and prepared a solution of this solution at about 30 ° C. (30 ± 0.01). ℃) is the value measured by the Ubbelohde viscous meter, η0 is the value measured by the same viscosity meter at the same temperature of the same solvent, and C is the concentration 0.5 g / dL.
Here, the logarithmic viscosity (intrinsic viscosity) of PI correlates with the molecular weight of PI.
When the logarithmic viscosity of PI is within the above range, the molecular weight and viscosity of PI become appropriate, so that the effect of suppressing the sedimentation of the powder of PI is suitably exhibited, and the dispersibility of the powder in the powder dispersion is improved. , PI functions suitably as a binder, and the effect of preventing powder falling during the formation of the F layer is further improved.
本分散液中のパウダー（Ｆポリマー）の割合（含有量）は、１０質量％以上であり、２５質量％以上がより好ましく、３０質量％以上がさらに好ましい。上記割合は、６０質量％以下であり、５０質量％以下がより好ましい。この範囲において、表面の平滑性と電気特性と耐熱性とに優れたＦ層を形成しやすい。
本分散液中の極性有機溶媒の割合（含有量）は、３０〜７０質量％が好ましく、４０〜６０質量％がより好ましい。この範囲において、パウダー分散液の塗布性が優れ、かつ層形成性が向上しやすい。
本分散液中において、パウダー（Ｆポリマー）の含有量に対するＡポリマーの含有量の質量での比は、０．０２〜０．１５が好ましく、０．０５〜０．１２がより好ましい。この範囲において、パウダー分散液の分散性がより向上し、さらにＦ層の物性（電気特性、接着性、表面の平滑性等）がより向上しやすい。The proportion (content) of the powder (F polymer) in the dispersion is 10% by mass or more, more preferably 25% by mass or more, still more preferably 30% by mass or more. The above ratio is 60% by mass or less, more preferably 50% by mass or less. In this range, it is easy to form an F layer having excellent surface smoothness, electrical characteristics, and heat resistance.
The proportion (content) of the polar organic solvent in the dispersion is preferably 30 to 70% by mass, more preferably 40 to 60% by mass. In this range, the coating property of the powder dispersion liquid is excellent, and the layer forming property is likely to be improved.
In this dispersion, the ratio of the content of the A polymer to the content of the powder (F polymer) by mass is preferably 0.02 to 0.15, more preferably 0.05 to 0.12. In this range, the dispersibility of the powder dispersion is further improved, and the physical properties of the F layer (electrical characteristics, adhesiveness, surface smoothness, etc.) are more likely to be improved.
本分散液中において、パウダー（Ｆポリマー）の含有量に対するＰＩの含有量の質量での比は、０．３以下であり、０．１以下が好ましく、０．１未満がより好ましく、０．０９以下がさらに好ましく、０．０５以下が特に好ましい。
上記質量の比は、０．００５以上が好ましく、０．０１以上がより好ましい。
上記質量の比の範囲は、０．００５以上０．１未満が好ましく、０．０１〜０．０９がより好ましく、０．０１〜０．０５がさらに好ましい。この範囲において、パウダーの沈降が抑制されるのでパウダー分散液の分散性がより向上し、さらにＦ層におけるパウダーの粉落ち防止効果及びＦ層のＵＶ加工性付与効果もより向上しやすい。
特に、本発明では、パウダー（Ｆポリマー）、Ａポリマー及びＰＩの含有量や質量比を上記範囲に設定するので、Ｆ層形成時における粉落ちの発生が効果的に抑制されるとともに、Ｆ層において各種物性（平滑性、電気特性、耐熱性、低吸水性）が良好なバランスで発揮される。In this dispersion, the ratio of the content of PI to the content of powder (F polymer) by mass is 0.3 or less, preferably 0.1 or less, more preferably less than 0.1, and 0. 09 or less is more preferable, and 0.05 or less is particularly preferable.
The mass ratio is preferably 0.005 or more, more preferably 0.01 or more.
The range of the mass ratio is preferably 0.005 or more and less than 0.1, more preferably 0.01 to 0.09, and even more preferably 0.01 to 0.05. In this range, the sedimentation of the powder is suppressed, so that the dispersibility of the powder dispersion is further improved, and further, the effect of preventing the powder from falling off in the F layer and the effect of imparting UV processability of the F layer are likely to be further improved.
In particular, in the present invention, since the contents and mass ratios of the powder (F polymer), A polymer and PI are set in the above range, the occurrence of powder falling during the formation of the F layer is effectively suppressed and the F layer is formed. Various physical properties (smoothness, electrical characteristics, heat resistance, low water absorption) are exhibited in a good balance.
本分散液は、本発明の効果を損なわない範囲で、他の材料を含んでいてもよい。他の材料は、パウダー分散液に溶解してもよく、溶解しなくてもよい。
かかる他の材料は、非硬化性樹脂、無機フィラーが挙げられる。
非硬化性樹脂としては、硬化性樹脂の硬化物等の非溶融性樹脂、熱可塑性樹脂、硬化性樹脂の熱溶融性の硬化物等の熱溶融性樹脂が挙げられる。
熱可塑性樹脂としては、ポリエステル樹脂、ポリオレフィン樹脂、スチレン樹脂、ポリカーボネート、ポリアリレート、ポリスルホン、ポリアリルスルホン、芳香族ポリアミド、芳香族ポリエーテルアミド、ポリフェニレンスルファイド、ポリアリルエーテルケトン、ポリアミドイミド、液晶性ポリエステル、ポリフェニレンエーテルが挙げられ、熱可塑性ポリイミド、液晶性ポリエステル、液晶性ポリエステルアミド又はポリフェニレンエーテルが好ましい。The dispersion may contain other materials as long as the effects of the present invention are not impaired. Other materials may or may not be dissolved in the powder dispersion.
Examples of such other materials include non-curable resins and inorganic fillers.
Examples of the non-curable resin include non-meltable resins such as cured products of curable resins, thermoplastic resins, and thermosetting resins such as thermosetting cured products of curable resins.
Examples of the thermoplastic resin include polyester resin, polyolefin resin, styrene resin, polycarbonate, polyarylate, polysulfone, polyallylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylensulfide, polyallyl etherketone, polyamideimide, and liquid crystal. Examples thereof include polyester and polyphenylene ether, and thermoplastic polyimide, liquid crystal polyester, liquid crystal polyester amide or polyphenylene ether is preferable.
無機フィラーとしては、窒化物フィラー、無機酸化物フィラーが挙げられ、窒化ホウ素フィラー、べリリア（ベリリウムの酸化物）、シリカフィラー又は金属酸化物（酸化セリウム、アルミナ、ソーダアルミナ、酸化マグネシウム、酸化亜鉛、酸化チタン等）フィラーが好ましい。
本分散液は、極性ポリマーとも言える、（メタ）アクリレート系ポリマーとポリイミド前駆体又はポリイミドとを含み、その液物性（粘度、チキソ比等）に優れ、無機フィラーを含んでいても分散性に優れる。また、それからＦ層を形成する際、無機フィラーが粉落ちしにくいだけでなく、それが均一に分布したＦ層が形成されやすい。Examples of the inorganic filler include a nitride filler and an inorganic oxide filler, such as boron nitride filler, verilia (oxide of berylium), silica filler or metal oxide (cerium oxide, alumina, soda alumina, magnesium oxide, zinc oxide). , Titanium oxide, etc.) Filler is preferable.
This dispersion contains a (meth) acrylate-based polymer, which can be said to be a polar polymer, and a polyimide precursor or polyimide, and has excellent liquid physical characteristics (viscosity, thixotropy, etc.) and excellent dispersibility even if it contains an inorganic filler. .. Further, when the F layer is formed from it, not only the inorganic filler is less likely to fall off, but also the F layer in which the inorganic filler is uniformly distributed is likely to be formed.
無機フィラーの形状は、粒状であってもよく、非粒状（鱗片状、層状）であってもよく、繊維状であってもよく、微細構造を有する無機フィラーを使用するのが好ましい。
かかる微細構造を有する無機フィラーの具体例としては、球状の無機フィラー、繊維状の無機フィラーが挙げられる。
前者の無機フィラーの平均粒子径は、０．００１〜３μｍが好ましく、０．０１〜１μｍがより好ましい。この場合、無機フィラーは、パウダー分散液中の分散性により優れ、Ｆ層中においてより均一に分布しやすい。
後者の無機フィラーにおいて、長さは繊維長であり、径は繊維径である。繊維長は、１〜１０μｍが好ましい。繊維径は、０．０１〜１μｍが好ましい。
本分散液が無機フィラーを含む場合、その含有量は、Ｆポリマーの含有量に対して質量での比において０．１以下が好ましい。The shape of the inorganic filler may be granular, non-granular (scaly, layered), fibrous, and it is preferable to use an inorganic filler having a fine structure.
Specific examples of the inorganic filler having such a fine structure include a spherical inorganic filler and a fibrous inorganic filler.
The average particle size of the former inorganic filler is preferably 0.001 to 3 μm, more preferably 0.01 to 1 μm. In this case, the inorganic filler is more excellent in dispersibility in the powder dispersion and is more likely to be distributed more uniformly in the F layer.
In the latter inorganic filler, the length is the fiber length and the diameter is the fiber diameter. The fiber length is preferably 1 to 10 μm. The fiber diameter is preferably 0.01 to 1 μm.
When the dispersion contains an inorganic filler, the content thereof is preferably 0.1 or less in terms of the ratio by mass to the content of the F polymer.
無機フィラーは、その表面の少なくとも一部が、有機物、無機物（ただし、無機フィラーを形成する無機物とは異なる無機物である。）、又は、その両方によって、被覆処理（表面処理）されていてもよい。
かかる被覆処理に用いられる有機物としては、多価アルコール（トリメチロールエタン、ペンタエリストール、プロピレングリコール等）、飽和脂肪酸（ステアリン酸、ラウリン酸等）、そのエステル、アルカン―ルアミン、アミン（トリメチルアミン、トリエチルアミン等）、パラフィンワックス、シランカップリング剤、シリコーン、ポリシロキサンが挙げられる。
かかる被覆処理に用いられる無機物としては、アルミニウム、ケイ素、ジルコニウム、スズ、チタニウム、アンチモン等の、酸化物、水酸化物、水和酸化物又はリン酸塩が挙げられる。At least a part of the surface of the inorganic filler may be coated (surface-treated) with an organic substance, an inorganic substance (however, an inorganic substance different from the inorganic substance forming the inorganic filler), or both. ..
Organic substances used in such coating treatment include polyhydric alcohols (trimethylolethane, pentaeristol, propylene glycol, etc.), saturated fatty acids (stearic acid, lauric acid, etc.), esters thereof, alkane-luamines, amines (trimethylamine, triethylamine, etc.). Etc.), paraffin wax, silane coupling agent, silicone, polysiloxane, etc.
Examples of the inorganic substance used in such coating treatment include oxides, hydroxides, hydrated oxides and phosphates such as aluminum, silicon, zirconium, tin, titanium and antimony.
本分散液に含有させる無機フィラーは、形成されるＦ層に付与する物性に応じて決定すればよい。
例えば、ＵＶ加工性を一層向上させつつ、その反りを高度に抑制したＦ層を形成する場合には、本分散液は、無機フィラーとして、球状のシリカフィラーを含むのが好ましい。
この場合、球状のシリカフィラーの平均粒子径は、Ｆポリマーのパウダーの平均粒子径（Ｄ５０）より小さいのが好ましい。具体的には、Ｆポリマーのパウダーの平均粒子径が０．２〜３μｍであり、球状のシリカフィラーの平均粒子径が０．０１〜０．１μｍであるのが好ましい。また、この場合の球状のシリカフィラーの含有量は、Ｆポリマーの含有質量に対して質量での比において０．０１〜０．１が好ましい。かかる構成により、Ｆ層の表面におけるシリカフィラーの露出を抑制しつつ、シリカフィラーがＦ層中に均一分散したＦ層を容易に形成できる。The inorganic filler to be contained in the dispersion liquid may be determined according to the physical properties imparted to the F layer to be formed.
For example, when forming an F layer in which the warpage is highly suppressed while further improving the UV processability, the dispersion liquid preferably contains a spherical silica filler as an inorganic filler.
In this case, the average particle size of the spherical silica filler is preferably smaller than the average particle size (D50) of the F polymer powder. Specifically, it is preferable that the average particle size of the F polymer powder is 0.2 to 3 μm, and the average particle size of the spherical silica filler is 0.01 to 0.1 μm. Further, the content of the spherical silica filler in this case is preferably 0.01 to 0.1 in terms of the ratio by mass to the content mass of the F polymer. With such a configuration, it is possible to easily form the F layer in which the silica filler is uniformly dispersed in the F layer while suppressing the exposure of the silica filler on the surface of the F layer.
かかる無機フィラーの好適な具体例としては、アミノシランカップリング剤で表面処理された平均粒子径１μｍ以下のシリカフィラー（アドマテックス社製、「アドマファイン」シリーズ等）、ジカプリン酸プロピレングリコール等のエステルで表面処理された平均粒子径０．１μｍ以下の酸化亜鉛（堺化学工業株式会社製、「ＦＩＮＥＸ」シリーズ等）、平均粒子径０．５μｍ以下かつ最大粒子径１μｍ未満の球状溶融シリカ（デンカ社製、「ＳＦＰグレード」等）、多価アルコール及び無機物で被覆処理された平均粒子径０．５μｍ以下のルチル型酸化チタン（石原産業社製、「タイペーク」シリーズ等）、アルキルシランで表面処理された平均粒子径０．１μｍ以下のルチル型酸化チタン（テイカ社製、「ＪＭＴ」シリーズ等）が挙げられる。 Preferable specific examples of such an inorganic filler include a silica filler having an average particle diameter of 1 μm or less (manufactured by Admatex, “Admafine” series, etc.) surface-treated with an aminosilane coupling agent, an ester such as propylene glycol dicaprate. Surface-treated zinc oxide with an average particle diameter of 0.1 μm or less (manufactured by Sakai Chemical Industry Co., Ltd., “FINEX” series, etc.), spherical molten silica with an average particle diameter of 0.5 μm or less and a maximum particle diameter of less than 1 μm (manufactured by Denka Co., Ltd.) , "SFP grade", etc.), rutile-type titanium oxide with an average particle size of 0.5 μm or less (manufactured by Ishihara Sangyo Co., Ltd., "Typake" series, etc.) coated with polyhydric alcohol and inorganic substances, and surface-treated with alkylsilane. Examples thereof include rutile-type titanium oxide having an average particle size of 0.1 μm or less (manufactured by Teika, “JMT” series, etc.).
本分散液が無機フィラーを含む場合、本分散液中において、パウダー（Ｆポリマー）の含有量に対する無機フィラーの含有量の質量での比は、０．３以下が好ましく、０．１以下がより好ましい。
上記比は、０．０１以上が好ましい。
上記比の範囲は、０．０１〜０．３が好ましく、０．０１〜０．１がより好ましい。この範囲において、個々の無機フィラーが有する物性が、Ｆ層において高度に発現しやすい。When the present dispersion contains an inorganic filler, the ratio of the content of the inorganic filler to the content of the powder (F polymer) in the present dispersion is preferably 0.3 or less, more preferably 0.1 or less. preferable.
The above ratio is preferably 0.01 or more.
The range of the above ratio is preferably 0.01 to 0.3, more preferably 0.01 to 0.1. In this range, the physical characteristics of the individual inorganic fillers are highly likely to be expressed in the F layer.
本発明における、かかる他の材料としては、チキソ性付与剤、消泡剤、反応性アルコキシシラン、脱水剤、可塑剤、耐候剤、酸化防止剤、熱安定剤、滑剤、帯電防止剤、増白剤、着色剤、導電剤、離型剤、表面処理剤、粘度調節剤、難燃剤も挙げられる。 Other such materials in the present invention include thixo-imparting agents, defoaming agents, reactive alkoxysilanes, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, and whitening agents. Examples include agents, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, and flame retardants.
本分散液の粘度は、５０〜１０００ｍＰａ・ｓが好ましく、７５〜５００ｍＰａ・ｓがより好ましい。この場合、パウダー分散液の分散性に優れるだけでなく、その塗工性や異種のポリマーのワニスとの混合性にも優れている。
本分散液のチキソ比は、１．０〜２．２が好ましく、１．４〜２．０がより好ましい。この場合、パウダー分散液の分散性に優れるだけでなく、パウダー分散液の塗工性も良好であり、Ｆ層の均質性が向上しやすい。また、かかるパウダー分散液は、異種のポリマーのワニスとの混合性がより高まる。The viscosity of this dispersion is preferably 50 to 1000 mPa · s, more preferably 75 to 500 mPa · s. In this case, not only is the powder dispersion excellent in dispersibility, but it is also excellent in its coatability and mixability with varnishes of different polymers.
The thixotropy of the dispersion is preferably 1.0 to 2.2, more preferably 1.4 to 2.0. In this case, not only the dispersibility of the powder dispersion is excellent, but also the coatability of the powder dispersion is good, and the homogeneity of the F layer is likely to be improved. In addition, the powder dispersion is more compatible with varnishes of different polymers.
本分散液は、各種基板の表面に付与すれば、層（塗膜）形成時に粉落ちが生じるのを抑制しつつ、その表面の平滑性及びＵＶ加工性に優れるＦ層を形成できる。
本発明の積層体は、金属基板層と、この金属基板層の表面に設けられ、上記パウダー分散液から形成された層（Ｆ層）とを有する。
金属基板層の材質としては、銅、銅合金、ステンレス鋼、ニッケル、ニッケル合金（４２合金も含む。）、アルミニウム、アルミニウム合金、チタン、チタン合金が挙げられる。
金属基板層は、圧延銅箔、電解銅箔等の金属箔で構成するのが好ましい。かかる金属箔の表面は、防錆処理（クロメート等の酸化物皮膜等）されていてもよく、粗化処理されていてもよい。
金属箔の厚さは、積層体の用途において充分な機能が発揮できる厚さであればよい。金属箔の厚さは、その表面の十点平均粗さ以上の厚さであり、２〜４０μｍが好ましい。金属箔として、キャリア銅箔（厚さ：１０〜３５μｍ）と、剥離層を介してキャリア銅箔上に積層された極薄銅箔（厚さ：２〜５μｍ）とからなるキャリア付金属箔を使用してもよい。また、金属箔の厚さは、Ｆ樹脂層の厚さより大きいのが好ましい。When this dispersion is applied to the surface of various substrates, it is possible to form an F layer having excellent surface smoothness and UV processability while suppressing powder falling during layer (coating film) formation.
The laminate of the present invention has a metal substrate layer and a layer (F layer) provided on the surface of the metal substrate layer and formed from the powder dispersion liquid.
Examples of the material of the metal substrate layer include copper, copper alloy, stainless steel, nickel, nickel alloy (including 42 alloy), aluminum, aluminum alloy, titanium, and titanium alloy.
The metal substrate layer is preferably composed of a metal foil such as a rolled copper foil or an electrolytic copper foil. The surface of the metal foil may be rust-proofed (an oxide film such as chromate) or roughened.
The thickness of the metal foil may be a thickness that can exhibit sufficient functions in the application of the laminated body. The thickness of the metal foil is at least the ten-point average roughness of the surface thereof, and is preferably 2 to 40 μm. As the metal foil, a metal foil with a carrier composed of a carrier copper foil (thickness: 10 to 35 μm) and an ultrathin copper foil (thickness: 2 to 5 μm) laminated on the carrier copper foil via a release layer. You may use it. Further, the thickness of the metal foil is preferably larger than the thickness of the F resin layer.
金属箔の表面の十点平均粗さは、０．２〜１．５μｍが好ましい。この場合、Ｆ層との接着性が良好となりやすい。
金属箔の厚さは、積層体の用途において機能が発揮できる厚さであればよい。
金属箔の表面は、シランカップリング剤により処理されていてもよい。この場合、金属箔の表面の全体がシランカップリング剤により処理されていてもよく、金属箔の表面の一部がシランカップリング剤により処理されていてもよい。The ten-point average roughness of the surface of the metal foil is preferably 0.2 to 1.5 μm. In this case, the adhesiveness with the F layer tends to be good.
The thickness of the metal foil may be any thickness as long as it can exert its function in the application of the laminated body.
The surface of the metal foil may be treated with a silane coupling agent. In this case, the entire surface of the metal foil may be treated with a silane coupling agent, or a part of the surface of the metal foil may be treated with a silane coupling agent.
本発明の積層体は、金属基板層の少なくとも一方の表面にＦ層を有する。つまり、積層体は、金属基板層の片面のみにＦ層を有していてもよく、金属基板層の両面にＦ層を有していてもよい。
積層体の反り率は、２５％以下が好ましく、７％以下がより好ましい。この場合、積層体をプリント基板に加工する際のハンドリング性と、得られるプリント基板の伝送特性とが優れる。
積層体の寸法変化率は、±１％以下が好ましく、±０．２％以下がより好ましい。この場合、積層体をプリント基板に加工し、さらにそれを多層化しやすい。The laminate of the present invention has an F layer on at least one surface of the metal substrate layer. That is, the laminate may have the F layer on only one side of the metal substrate layer, or may have the F layer on both sides of the metal substrate layer.
The warpage rate of the laminated body is preferably 25% or less, more preferably 7% or less. In this case, the handleability when processing the laminated body into a printed circuit board and the transmission characteristics of the obtained printed circuit board are excellent.
The dimensional change rate of the laminate is preferably ± 1% or less, more preferably ± 0.2% or less. In this case, it is easy to process the laminated body into a printed circuit board and further multi-layer it.
Ｆ層の表面の水接触角は、７０〜１００°が好ましく、７０〜９０°がより好ましい。この場合、Ｆ層と他の基板との接着性がより優れる。上記範囲が下限値以上であれば、積層体をプリント基板に加工した際の電気特性がより優れる。
Ｆ層の厚さは、１〜５０μｍが好ましく、５〜１５μｍがより好ましい。この範囲において、積層体をプリント基板に加工した際の電気特性と積層体の反り抑制とをバランスさせやすい。積層体が金属基板の両面にＦ層を有する場合、２つのＦ層の組成及び厚さは、積層体の反りを抑制する点から同じであるのが好ましい。
Ｆ層の厚さの好適な態様としては、２５μｍ以下が好ましく、２０μｍ以下がより好ましい。また、Ｆ層の厚さは、１μｍ以上が好ましい。本分散液は、Ｆポリマー及びＰＩのそれぞれの含有量が所定の範囲にあり、任意の厚さのＦ層の形成においても、ＰＩが均一に分散したＴＦＥ系ポリマーの緻密な層が形成できる。その結果、耐熱性と耐薬品性と電気特性とを具備した任意の厚さのＦ層を形成できる。
Ｆ層の比誘電率は、２．０〜３．５が好ましく、２．０〜３．０がより好ましい。この場合、低誘電率が求められるプリント基板等に積層体を好適に使用できる。
Ｆ層の誘電正接は、０．００３以下が好ましい。The water contact angle on the surface of the F layer is preferably 70 to 100 °, more preferably 70 to 90 °. In this case, the adhesiveness between the F layer and another substrate is more excellent. When the above range is at least the lower limit value, the electrical characteristics when the laminated body is processed into a printed circuit board are more excellent.
The thickness of the F layer is preferably 1 to 50 μm, more preferably 5 to 15 μm. In this range, it is easy to balance the electrical characteristics when the laminated body is processed into a printed circuit board and the suppression of warpage of the laminated body. When the laminate has F layers on both sides of the metal substrate, the composition and thickness of the two F layers are preferably the same from the viewpoint of suppressing warpage of the laminate.
As a preferred embodiment of the thickness of the F layer, 25 μm or less is preferable, and 20 μm or less is more preferable. The thickness of the F layer is preferably 1 μm or more. In this dispersion, the contents of the F polymer and the PI are in a predetermined range, and even when the F layer having an arbitrary thickness is formed, a dense layer of the TFE polymer in which the PI is uniformly dispersed can be formed. As a result, an F layer having an arbitrary thickness having heat resistance, chemical resistance, and electrical characteristics can be formed.
The relative permittivity of the F layer is preferably 2.0 to 3.5, more preferably 2.0 to 3.0. In this case, the laminate can be suitably used for a printed circuit board or the like that requires a low dielectric constant.
The dielectric loss tangent of the F layer is preferably 0.003 or less.
パウダー分散液の金属基板への付与は、塗布による行うのが好ましい。
塗布方法は、塗布後の金属基板の表面にパウダー分散液からなる安定したウェット膜（液状被膜）が形成される方法であればよく、スプレー法、ロールコート法、スピンコート法、グラビアコート法、マイクログラビアコート法、グラビアオフセット法、ナイフコート法、キスコート法、バーコート法、ダイコート法、ファウンテンメイヤーバー法、スロットダイコート法が挙げられる。
パウダー分散液の塗布後、金属基板を加熱するに際しては、低温領域の温度に保持して、溶媒を留去（すなわち乾燥）するのが好ましい。低温領域（以下、「乾燥領域」とも記す。）の温度としては、８０℃以上１８０℃未満が好ましく、１２０〜１７０℃がより好ましい。乾燥領域の温度は、乾燥における雰囲気の温度を意味する。
低温領域の温度での保持は、１段階で実施してもよく、異なる温度にて２段階以上で実施してもよい。
低温領域の温度に保持する方法としては、オーブンを用いる方法、通風乾燥炉を用いる方法、赤外線等の熱線を照射する方法等が挙げられる。The powder dispersion liquid is preferably applied to the metal substrate by coating.
The coating method may be any method as long as a stable wet film (liquid film) composed of a powder dispersion is formed on the surface of the metal substrate after coating, and the spray method, roll coating method, spin coating method, gravure coating method, etc. Examples include the micro gravure coating method, the gravure offset method, the knife coating method, the kiss coating method, the bar coating method, the die coating method, the fountain Mayer bar method, and the slot die coating method.
When heating the metal substrate after applying the powder dispersion liquid, it is preferable to keep the temperature in a low temperature region and distill off (that is, dry) the solvent. The temperature in the low temperature region (hereinafter, also referred to as “dry region”) is preferably 80 ° C. or higher and lower than 180 ° C., more preferably 120 to 170 ° C. The temperature of the dry region means the temperature of the atmosphere in drying.
Holding at a temperature in the low temperature region may be carried out in one step, or may be carried out in two or more steps at different temperatures.
Examples of the method of maintaining the temperature in the low temperature region include a method using an oven, a method using a ventilation drying furnace, a method of irradiating heat rays such as infrared rays, and the like.
低温領域の温度に保持する際の雰囲気は、常圧下、減圧下のいずれの状態であってよい。また、上記雰囲気は、酸化性ガス雰囲気、還元性ガス雰囲気、不活性ガス雰囲気のいずれであってもよい。
不活性ガスとしては、ヘリウムガス、ネオンガス、アルゴンガス、窒素ガスが挙げられ、窒素ガスが好ましい。
還元性ガスとしては、水素ガスが挙げられる。
酸化性ガスとしては、酸素ガスが挙げられる。The atmosphere when maintaining the temperature in the low temperature region may be either under normal pressure or under reduced pressure. Further, the atmosphere may be any of an oxidizing gas atmosphere, a reducing gas atmosphere, and an inert gas atmosphere.
Examples of the inert gas include helium gas, neon gas, argon gas and nitrogen gas, and nitrogen gas is preferable.
Examples of the reducing gas include hydrogen gas.
Examples of the oxidizing gas include oxygen gas.
低温領域の温度に保持する際の雰囲気は、Ａポリマーの酸化分解を促し、よりＦ層の接着性を向上させる観点から、酸素ガスを含む雰囲気が好ましい。
酸素ガスを含む雰囲気における酸素ガス濃度（体積基準）は、１×１０２〜３×１０５ｐｐｍが好ましく、０．５×１０３〜１×１０４ｐｐｍがより好ましい。この範囲において、Ａポリマーの酸化分解と、金属基板の酸化抑制とをバランスさせやすい。
低温領域の温度に保持する時間は、０．１〜１０分間が好ましく、０．５〜５分間がより好ましい。The atmosphere when the temperature is maintained in the low temperature region is preferably an atmosphere containing oxygen gas from the viewpoint of promoting oxidative decomposition of the A polymer and further improving the adhesiveness of the F layer.
The oxygen gas concentration (volume basis) in an atmosphere containing
The time for maintaining the temperature in the low temperature region is preferably 0.1 to 10 minutes, more preferably 0.5 to 5 minutes.
本発明の積層体の製造方法においては、さらに、低温領域での保持温度を超える温度領域（以下、「焼成領域」とも記す。）にて、Ｆポリマーを焼成させて金属基板の表面にＦ層を形成するのが好ましい。焼成領域の温度は、焼成における雰囲気の温度を意味する。
本発明におけるＦ層の形成は、パウダー粒子が密にパッキングし、Ｆポリマーが融着して進行すると考えられる。なお、パウダー分散液が熱溶融性樹脂を含めば、Ｆポリマーと溶解性樹脂との混合物からなるＦ層が形成され、パウダー分散液が熱硬化性樹脂を含めば、Ｆポリマーと熱硬化性樹脂の硬化物とからなるＦ層が形成される。In the method for producing a laminate of the present invention, an F polymer is further fired in a temperature region exceeding the holding temperature in a low temperature region (hereinafter, also referred to as a “firing region”) to form an F layer on the surface of a metal substrate. It is preferable to form. The temperature of the firing region means the temperature of the atmosphere in firing.
It is considered that the formation of the F layer in the present invention proceeds by tightly packing the powder particles and fusing the F polymer. If the powder dispersion contains a thermosetting resin, an F layer composed of a mixture of the F polymer and the soluble resin is formed, and if the powder dispersion contains the thermosetting resin, the F polymer and the thermosetting resin are formed. An F layer composed of the cured product of is formed.
焼成の方法としては、オーブンを用いる方法、通風乾燥炉を用いる方法、赤外線等の熱線を照射する方法等が挙げられる。Ｆ層の表面の平滑性を高めるために、加熱板、加熱ロール等で加圧してもよい。加熱の方法としては、短時間で焼成でき、遠赤外線炉が比較的コンパクトである点から、遠赤外線を照射する方法が好ましい。加熱の方法は、赤外線加熱と熱風加熱とを組み合わせてもよい。
遠赤外線の有効波長帯は、Ｆポリマーの均質な融着を促す点から、２〜２０μｍが好ましく、３〜７μｍがより好ましい。Examples of the firing method include a method using an oven, a method using a ventilation drying furnace, a method of irradiating heat rays such as infrared rays, and the like. In order to improve the smoothness of the surface of the F layer, pressure may be applied with a heating plate, a heating roll, or the like. As a heating method, a method of irradiating far infrared rays is preferable because it can be fired in a short time and the far infrared furnace is relatively compact. The heating method may be a combination of infrared heating and hot air heating.
The effective wavelength band of far infrared rays is preferably 2 to 20 μm, more preferably 3 to 7 μm, from the viewpoint of promoting homogeneous fusion of the F polymer.
焼成における雰囲気は、常圧下、減圧下のいずれの状態であってよい。また、焼成における雰囲気は、酸化性ガス雰囲気、還元性ガス雰囲気、不活性ガス雰囲気のいずれであってもよく、金属基板及び形成されるＦ層のそれぞれの酸化劣化を抑制する観点から、還元性ガス雰囲気又は不活性ガス雰囲気が好ましい。
不活性ガスとしては、ヘリウムガス、ネオンガス、アルゴンガス、窒素ガスが挙げられ、窒素ガスが好ましい。
還元性ガスとしては、水素ガスが挙げられる。
酸化性ガスとしては、酸素ガスが挙げられる。The atmosphere in firing may be either under normal pressure or under reduced pressure. Further, the atmosphere in firing may be any of an oxidizing gas atmosphere, a reducing gas atmosphere, and an inert gas atmosphere, and is reducible from the viewpoint of suppressing oxidative deterioration of each of the metal substrate and the F layer to be formed. A gas atmosphere or an inert gas atmosphere is preferred.
Examples of the inert gas include helium gas, neon gas, argon gas and nitrogen gas, and nitrogen gas is preferable.
Examples of the reducing gas include hydrogen gas.
Examples of the oxidizing gas include oxygen gas.
焼成における雰囲気は、不活性ガスから構成され酸素ガス濃度が低いガス雰囲気が好ましく、窒素ガスから構成され酸素ガス濃度（体積基準）が５００ｐｐｍ未満のガス雰囲気がより好ましい。酸素ガス濃度（体積基準）は、３００ｐｐｍ以下が特に好ましい。また、酸素ガス濃度（体積基準）は、通常、１ｐｐｍ以上である。この範囲において、Ａポリマーのさらなる酸化分解が抑制され、Ｆ層の親水性を向上させやすい。
焼成領域の温度は、２５０〜４００℃が好ましく、３００〜３８０℃がより好ましい。
焼成領域の温度に保持する時間は、３０秒〜５分間が好ましく、１〜２分間がより好ましい。The atmosphere in firing is preferably a gas atmosphere composed of an inert gas and having a low oxygen gas concentration, and more preferably a gas atmosphere composed of nitrogen gas and having an oxygen gas concentration (volume basis) of less than 500 ppm. The oxygen gas concentration (volume basis) is particularly preferably 300 ppm or less. The oxygen gas concentration (volume basis) is usually 1 ppm or more. In this range, further oxidative decomposition of the A polymer is suppressed, and the hydrophilicity of the F layer is likely to be improved.
The temperature of the firing region is preferably 250 to 400 ° C, more preferably 300 to 380 ° C.
The time for keeping the temperature of the firing region is preferably 30 seconds to 5 minutes, more preferably 1 to 2 minutes.
本発明における積層体には、Ｆ層の線膨張を制御したり、Ｆ層の接着性をさらに改善したりするために、Ｆ層の表面に表面処理をしてもよい。
Ｆ層の表面にする表面処理方法としては、アニール処理、コロナ放電処理、大気圧プラズマ処理、真空プラズマ処理、ＵＶオゾン処理、エキシマ処理、ケミカルエッチング、シランカップリング処理、微粗面化処理等が挙げられる。
アニール処理における温度は、１２０〜１８０℃が好ましい。
アニール処理における圧力は、０．００５〜０．０１５ＭＰａが好ましい。
アニール処理の時間は、３０〜１２０分間が好ましい。In the laminated body in the present invention, the surface of the F layer may be surface-treated in order to control the linear expansion of the F layer and further improve the adhesiveness of the F layer.
Surface treatment methods for the surface of the F layer include annealing treatment, corona discharge treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, UV ozone treatment, excimer treatment, chemical etching, silane coupling treatment, and fine roughening treatment. Can be mentioned.
The temperature in the annealing treatment is preferably 120 to 180 ° C.
The pressure in the annealing treatment is preferably 0.005 to 0.015 MPa.
The annealing treatment time is preferably 30 to 120 minutes.
プラズマ処理におけるプラズマ照射装置としては、高周波誘導方式、容量結合型電極方式、コロナ放電電極−プラズマジェット方式、平行平板型、リモートプラズマ型、大気圧プラズマ型、ＩＣＰ型高密度プラズマ型等が挙げられる。
プラズマ処理に用いるガスとしては、酸素ガス、窒素ガス、希ガス（アルゴン等）、水素ガス、アンモニアガス等が挙げられ、希ガス、水素ガス又は窒素ガスが好ましい。プラズマ処理に用いるガスの具体例としては、アルゴンガス、水素ガスと窒素ガスとの混合ガス、水素ガスと窒素ガスとアルゴンガスとの混合ガスが挙げられる。Examples of the plasma irradiation device in plasma processing include a high frequency induction method, a capacitance coupling type electrode method, a corona discharge electrode-plasma jet method, a parallel plate type, a remote plasma type, an atmospheric pressure plasma type, and an ICP type high density plasma type. ..
Examples of the gas used for the plasma treatment include oxygen gas, nitrogen gas, rare gas (argon and the like), hydrogen gas, ammonia gas and the like, and rare gas, hydrogen gas or nitrogen gas 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.
本発明の積層体において、Ｆ層の表面は、接着性に優れるため、他の基板と容易かつ強固に接合できる。
他の基板としては、耐熱性樹脂フィルム、繊維強化樹脂板の前駆体であるプリプレグ、耐熱性樹脂フィルム層を有する積層体、プリプレグ層を有する積層体が挙げられる。
プリプレグは、強化繊維（ガラス繊維、炭素繊維等）の基材（トウ、織布等）に熱硬化性樹脂又は熱可塑性樹脂を含浸させたシート状の基板である。
耐熱性樹脂フィルムは、耐熱性樹脂の１種以上を含むフィルムであり、単層フィルムであっても多層フィルムであってもよい。
耐熱性樹脂としては、ポリイミド、ポリアリレート、ポリスルホン、ポリアリルスルホン、芳香族ポリアミド、芳香族ポリエーテルアミド、ポリフェニレンスルフィド、ポリアリルエーテルケトン、ポリアミドイミド、液晶性ポリエステル、液晶性ポリエステルアミド等が挙げられる。In the laminate of the present invention, the surface of the F layer has excellent adhesiveness, so that it can be easily and firmly bonded to another substrate.
Examples of other substrates include a heat-resistant resin film, a prepreg which is a precursor of a fiber-reinforced resin plate, a laminate having a heat-resistant resin film layer, and a laminate having a prepreg layer.
The prepreg is a sheet-like substrate in which a base material (toe, woven fabric, etc.) of reinforcing fibers (glass fibers, carbon fibers, etc.) is impregnated with a thermosetting resin or a thermoplastic resin.
The heat-resistant resin film is a film containing one or more of heat-resistant resins, and may be a single-layer film or a multilayer film.
Examples of the heat-resistant resin include polyimide, polyallylate, polysulfone, polyallylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyallyl ether ketone, polyamideimide, liquid crystal polyester, and liquid crystal polyester amide. ..
本発明の積層体において、Ｆ層の表面に他の基板を積層する方法としては、積層体と他の基板とを熱プレスする方法が挙げられる。
他の基板がプリプレグである場合のプレス温度は、Ｆポリマーの溶融温度以下が好ましく、１２０〜３００℃がより好ましい。他の基板が耐熱性樹脂フィルムである場合のプレス温度は、３１０〜４００℃が好ましい。
熱プレスは、気泡混入を抑制し、酸化による劣化を抑制する観点から、２０ｋＰａ以下の真空度で行うのが特に好ましい。
また、熱プレス時には上記真空度に到達した後に昇温することが好ましい。上記真空度に到達する前に昇温すると、Ｆ層が軟化した状態、すなわち一定程度の流動性、密着性がある状態にて圧着されてしまい、気泡の原因となる場合がある。
熱プレスにおける圧力は、基板の破損を抑制しつつ、Ｆ層と基板とを強固に密着させる観点から、０．２〜１０ＭＰａが好ましい。In the laminated body of the present invention, as a method of laminating another substrate on the surface of the F layer, a method of heat-pressing the laminated body and the other substrate can be mentioned.
When the other substrate is a prepreg, the press temperature is preferably equal to or lower than the melting temperature of the F polymer, more preferably 120 to 300 ° C. When the other substrate is a heat-resistant resin film, the press temperature is preferably 310 to 400 ° C.
The hot press is particularly preferably performed at a vacuum degree of 20 kPa or less from the viewpoint of suppressing air bubble mixing and suppressing deterioration due to oxidation.
Further, at the time of hot pressing, it is preferable to raise the temperature after reaching the above vacuum degree. If the temperature is raised before reaching the degree of vacuum, the F layer may be crimped in a softened state, that is, in a state of having a certain degree of fluidity and adhesion, which may cause air bubbles.
The pressure in the hot press is preferably 0.2 to 10 MPa from the viewpoint of firmly adhering the F layer and the substrate while suppressing damage to the substrate.
本発明の積層体やその多層積層体は、フレキシブル銅張積層板やリジッド銅張積層板として、プリント基板の製造に使用できる。
本発明のプリント基板は、例えば、本発明の積層体における金属基板をエッチング等によって所定のパターンの導体回路（パターン回路）に加工する方法や、本発明の積層体を電解めっき法（セミアディティブ法（ＳＡＰ法）、モディファイドセミアディティブ法（ＭＳＡＰ法）等）によってパターン回路に加工する方法を使用すれば、本発明の積層体からプリント基板を製造できる。
プリント基板の製造においては、パターン回路を形成した後に、パターン回路上に層間絶縁膜を形成し、層間絶縁膜上にさらに導体回路を形成してもよい。層間絶縁膜は、本分散液によって形成してもよい。
プリント基板の製造においては、パターン回路上にソルダーレジストを積層してもよい。ソルダーレジストは、本分散液によって形成してもよい。
プリント基板の製造においては、パターン回路上にカバーレイフィルムを積層してもよい。The laminate of the present invention and the multilayer laminate thereof can be used for manufacturing a printed circuit board as a flexible copper-clad laminate or a rigid copper-clad laminate.
The printed circuit board of the present invention is, for example, a method of processing a metal substrate in the laminate of the present invention into a conductor circuit (pattern circuit) having a predetermined pattern by etching or the like, or an electrolytic plating method (semi-additive method) of the laminate of the present invention. (SAP method), modified semi-additive method (MSAP method), etc.) can be used to process a printed circuit board from the laminate of the present invention.
In the manufacture of the printed circuit board, after forming the pattern circuit, an interlayer insulating film may be formed on the pattern circuit, and a conductor circuit may be further formed on the interlayer insulating film. The interlayer insulating film may be formed by the present dispersion liquid.
In the production of the printed circuit board, a solder resist may be laminated on the pattern circuit. The solder resist may be formed by the present dispersion.
In the production of the printed circuit board, the coverlay film may be laminated on the pattern circuit.
以上、本発明のパウダー分散液、積層体及びプリント基板について説明したが、本発明は、上述した実施形態の構成に限定されない。
例えば、本発明のパウダー分散液、積層体及びプリント基板は、それぞれ上前述した実施形態に構成において、他の任意の構成を追加してもよいし、同様の機能を発揮する任意の構成と置換されていてよい。Although the powder dispersion liquid, the laminate, and the printed circuit board of the present invention have been described above, the present invention is not limited to the configuration of the above-described embodiment.
For example, the powder dispersion liquid, the laminate, and the printed circuit board of the present invention may be added with any other configuration in the configuration described above, respectively, or may be replaced with an arbitrary configuration exhibiting the same function. May be done.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されない。
１．各成分の準備
［Ｆポリマー］
・Ｆポリマー１：ＴＦＥに基づく単位、ＮＡＨに基づく単位及びＰＰＶＥに基づく単位を、この順に９８．０モル％、０．１モル％、１．９モル％含むコポリマー（溶融温度：３００℃、３８０℃の溶融粘度：３×１０５Ｐａ・ｓ）
・Ｆポリマー２：ＴＦＥに基づく単位及びＰＰＶＥに基づく単位を、この順に９８．０モル％及び２．０モル％含むポリマー（溶融温度：３０５℃、３８０℃の溶融粘度：３×１０５Ｐａ・ｓ）
［パウダー］
・パウダー１：Ｄ５０が２．６μｍ、Ｄ９０が７．１μｍである、Ｆポリマー１からなるパウダー１
・パウダー２：Ｄ５０が３．５μｍ、Ｄ９０が９．２μｍである、Ｆポリマー２からなるパウダー２
なお、Ｄ５０及びＤ９０は、レーザー回折・散乱式粒度分布測定装置（堀場製作所社製、「ＬＡ−９２０測定器」）を用い、パウダーを水中に分散させて測定した。Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
1. 1. Preparation of each component [F polymer]
F Polymer 1: Copolymer containing 98.0 mol%, 0.1 mol%, and 1.9 mol% of units based on TFE, NAH, and PPVE in this order (melting temperature: 300 ° C., 380). Melt viscosity at ° C: 3 × 10 5 Pa · s)
· F Polymer 2: the units based on units and PPVE based on TFE, 98.0 mol% in this order, and 2.0 mole% containing polymer (melt temperature: 305 ° C., a melt viscosity of 380 ℃: 3 × 10 5 Pa · s)
[powder]
-Powder 1: Powder 1 made of F polymer 1 having D50 of 2.6 μm and D90 of 7.1 μm.
-Powder 2:
D50 and D90 were measured by dispersing the powder in water using a laser diffraction / scattering type particle size distribution measuring device (“LA-920 measuring device” manufactured by HORIBA, Ltd.).
［ＰＩのワニス］
・ポリイミド前駆体のワニス：３，３’４，４’−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）とｐ−フェニレンジアミン（ＰＰＤ）との共重合体（モル比＝１：１）を、濃度０．５ｇ／ｄＬとなるように、Ｎ−メチル−２−ピロリドン（ＮＭＰ）に溶解した溶液
このワニスを、ポリイミドの濃度が０．５ｇ／ｄＬとなるように、ＮＭＰで濃度調整した溶液の３０℃における対数粘度は、２．０ｄＬ／ｇであった。
・ポリイミドのワニス：３，３’４，４’−ベンゾフェノンテトラカルボン酸二無水物と、２、４−ジアミノトルエンと、３，３’４，４’−ビフェニルテトラカルボン酸二無水物と、２、２−ビス｛４−（４−アミノフェノキシ）フェニル｝プロパンとのブロック共重合体（モル比＝１：１：１：１）を、ＮＭＰに溶解した溶液
このワニスを、ポリイミドの濃度が０．５ｇ／ｄＬとなるように、ＮＭＰで濃度調整した溶液の３０℃における対数粘度は、１．２ｄＬ／ｇであった。
［Ａポリマー］
ＣＨ２＝ＣＨＣＯＯ（ＣＨ２）４ＯＣＦ（ＣＦ３）（Ｃ（ＣＦ（ＣＦ３）２）（＝Ｃ（ＣＦ３）２）とＣＨ２＝ＣＨＣＯＯ（ＣＨ２ＣＨ２Ｏ）８ＯＨとの共重合体（モル比＝１：１）
なお、かかる共重合体は、ノニオン性のフルオロポリオール（重量平均分子量：約１００００）である。[PI varnish]
Polyimide precursor varnish: Concentration of a copolymer (molar ratio = 1: 1) of 3,3'4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and p-phenylenediamine (PPD). A solution dissolved in N-methyl-2-pyrrolidone (NMP) so as to have a concentration of 0.5 g / dL 30 of a solution prepared by adjusting the concentration of this varnish with NMP so as to have a polyimide concentration of 0.5 g / dL. The logarithmic viscosity at ° C. was 2.0 dL / g.
Polyimide varnish: 3,3'4,4'-benzophenone tetracarboxylic acid dianhydride, 2,4-diaminotoluene, 3,3'4,4'-biphenyltetracarboxylic acid dianhydride, 2 , 2-Bis {4- (4-aminophenoxy) phenyl} Propane block copolymer (molar ratio = 1: 1: 1: 1) dissolved in NMP This varnish has a polyimide concentration of 0. The logarithmic viscosity of the solution whose concentration was adjusted by NMP so as to be .5 g / dL at 30 ° C. was 1.2 dL / g.
[A polymer]
CH 2 = CHCOO (CH 2 ) 4 OCF (CF 3 ) (C (CF (CF 3 ) 2 ) (= C (CF 3 ) 2 ) and CH 2 = CHCOO (CH 2 CH 2 O) 8 OH Polymer (molar ratio = 1: 1)
The copolymer is a nonionic fluoropolyol (weight average molecular weight: about 10,000).
２．パウダー分散液の調製
（例１）
まず、４７質量部のＮＭＰと、２．５質量部のＡポリマーと、５０質量部のパウダー１とをポットに投入した後、ポット内にジルコニアボールを投入した。その後、１５０ｒｐｍ×１時間の条件でポットをころがし、パウダー１を分散して、混合液を得た。
次に、この混合液に、ポリイミドのワニスを、攪拌機を５００ｒｐｍの回転数で撹拌しつつ、パウダー分散液中のポリイミド（固形分）の量が０．５質量％となるように添加して、パウダー分散液Ａを調製した。
なお、パウダー１（Ｆポリマー１）の含有量に対するポリイミド（ＰＩ）の含有量の質量での比は、０．０１である。2. Preparation of powder dispersion (Example 1)
First, 47 parts by mass of NMP, 2.5 parts by mass of A polymer, and 50 parts by mass of powder 1 were put into a pot, and then zirconia balls were put into the pot. Then, the pot was rolled under the condition of 150 rpm × 1 hour to disperse the powder 1 to obtain a mixed solution.
Next, a polyimide varnish was added to this mixture while stirring the stirrer at a rotation speed of 500 rpm so that the amount of polyimide (solid content) in the powder dispersion was 0.5% by mass. A powder dispersion A was prepared.
The ratio of the content of polyimide (PI) to the content of powder 1 (F polymer 1) by mass is 0.01.
（例２〜７）
各成分の種類及び量（配合比率）を変更した以外は、例１と同様にして、パウダー分散液Ｂ（例２）、パウダー分散液Ｃ（例３）、パウダー分散液Ｄ（例４）、パウダー分散液Ｅ（例５）、パウダー分散液Ｆ（例６）及びパウダー分散液Ｇ（例７）を得た。それぞれのパウダー分散液の成分を、下表１にまとめて示す。(Examples 2 to 7)
Powder dispersion B (Example 2), powder dispersion C (Example 3), powder dispersion D (Example 4), in the same manner as in Example 1 except that the type and amount (blending ratio) of each component were changed. Powder dispersion E (Example 5), powder dispersion F (Example 6) and powder dispersion G (Example 7) were obtained. The components of each powder dispersion are shown in Table 1 below.
３．測定及び評価（その１）
３−１．調製時凝集性の評価
各パウダー分散液を調製した直後に、パウダー分散液の分散性を目視で確認し、以下の基準に従って評価した。
○（良） ：凝集が見られない。
△（可） ：ポット底部に沈殿は見られないが、側壁に細かな凝集物が付着している。
×（不可）：ポット底部に凝集したパウダーが沈殿している。3. 3. Measurement and evaluation (1)
3-1. Evaluation of cohesiveness at the time of preparation Immediately after each powder dispersion was prepared, the dispersibility of the powder dispersion was visually confirmed and evaluated according to the following criteria.
○ (Good): No agglutination is seen.
Δ (Yes): No precipitation was observed at the bottom of the pot, but fine agglomerates were attached to the side walls.
× (impossible): Aggregated powder is settled on the bottom of the pot.
３−２．保管後沈降性の評価
各パウダー分散液を常温で１か月静置し、１か月後にポットの撹拌を行い、再分散の程度を目視で確認し、以下の基準に従って評価した。
○（良） ：ポットの撹拌のみで、均一な分散となった。
△（可） ：均一な分散だが、凝集体が一部みられる。
×（不可）：沈降した凝集体が固形物となり、分散しない。3-2. Evaluation of sedimentation after storage Each powder dispersion was allowed to stand at room temperature for 1 month, and after 1 month, the pot was stirred to visually confirm the degree of redispersion and evaluated according to the following criteria.
◯ (Good): Uniform dispersion was achieved only by stirring the pot.
Δ (Yes): Uniform dispersion, but some aggregates are seen.
× (impossible): The settled aggregate becomes a solid substance and does not disperse.
３−３．粉落ちの評価
各パウダー分散液を、電解銅箔（福田金属箔粉工業社製、「ＣＦ−Ｔ４９Ａ−ＤＳ−ＨＤ２」、厚み：１２μｍ、Ｒｚｊｉｓ：１．２μｍ）に、ダイコートによりロールツーロールで塗工して、液状被膜を形成した。この液状被膜を乾燥炉に、１２０℃×３０分間で通過させて加熱により乾燥して、乾燥被膜を得た。得られた乾燥被膜の粉落ちについて、以下の基準に従って評価した。
〇（良） ：乾燥被膜の全面に粉落ちが見られない。
△（可） ：乾燥被膜の縁部に粉落ちが見られる。
×（不可）：乾燥被膜の全面に粉落ちが見られる。3-3. Evaluation of powder removal Each powder dispersion is applied to electrolytic copper foil (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., "CF-T49A-DS-HD2", thickness: 12 μm, Rzjis: 1.2 μm) by roll-to-roll by die coating. It was coated to form a liquid film. This liquid film was passed through a drying oven at 120 ° C. for 30 minutes and dried by heating to obtain a dry film. The powder removal of the obtained dry film was evaluated according to the following criteria.
〇 (Good): No powder falling off on the entire surface of the dry film.
Δ (Yes): Powder falling off is seen at the edge of the dry film.
× (impossible): Powder falling is seen on the entire surface of the dry film.
３−４．吸水率の評価
まず、上記で得られた乾燥被膜を、窒素オーブン下で３８０℃×１５分間で加熱した。これにより、銅箔の表面にＦ層が形成されたＦ層付銅箔を得た。なお、Ｆ層の厚さは１２μｍであった。次に、Ｆ層付銅箔を、塩化第二鉄水溶液でエッチングし、銅箔を除去して、Ｆ層単体を得た。
このＦ層を、ＡＳＴＭ Ｄ５７０に準拠して、５０℃×４８時間で予備乾燥した後、２３℃の純水に２４時間浸漬した。純水に浸漬する前後のＦ層の質量を測定し、以下の式に基づき、吸水率を求めた。
吸水率（％）＝（水浸漬後質量−予備乾燥後質量）／予備乾燥後質量×１００3-4. Evaluation of Water Absorption First, the dry film obtained above was heated in a nitrogen oven at 380 ° C. for 15 minutes. As a result, a copper foil with an F layer having an F layer formed on the surface of the copper foil was obtained. The thickness of the F layer was 12 μm. Next, the copper foil with the F layer was etched with an aqueous ferric chloride solution to remove the copper foil to obtain a simple substance of the F layer.
This F layer was pre-dried at 50 ° C. for 48 hours according to ASTM D570, and then immersed in pure water at 23 ° C. for 24 hours. The mass of the F layer before and after immersion in pure water was measured, and the water absorption rate was determined based on the following formula.
Water absorption rate (%) = (mass after immersion in water-mass after pre-drying) / mass after pre-drying x 100
３−５．波長３５５ｎｍの紫外線の透過率の測定
Ｆ層について、波長３５５ｎｍの紫外線の透過率を、分光光度計（株式会社島津製作所製、「ＵＶ−３６００」）を使用して測定した。
３−６．接着力の測定
Ｆ層付銅箔を１ｃｍ幅に切り出し、引張試験機により銅箔をＦ層から、９０°の角度で５０ｍｍ／ｍｉｎの速度で剥離し、その際の接着力（ｋＮ／ｍ）を測定した。3-5. Measurement of the transmittance of ultraviolet rays having a wavelength of 355 nm For the F layer, the transmittance of ultraviolet rays having a wavelength of 355 nm was measured using a spectrophotometer (“UV-3600” manufactured by Shimadzu Corporation).
3-6. Measurement of adhesive strength A copper foil with an F layer is cut out to a width of 1 cm, and the copper foil is peeled off from the F layer at a speed of 50 mm / min at a 90 ° angle using a tensile tester, and the adhesive strength (kN / m) at that time. Was measured.
３−７．ＵＶ加工性の評価
レーザー加工機（ｅｓｉ５３３０）を使用して、Ｆ層付銅箔に対して、直径１００μｍの円周上を周回するように、波長３５５ｎｍのＵＶ−ＹＡＧレーザーを照射した。これにより、Ｆ層付銅箔に円形の貫通孔を形成した。なお、レーザー出力は１．５Ｗ、レーザー焦点径を２５μｍ、円周上の周回回数は１６回、発振周波数は４０ｋＨｚとした。
その後、貫通孔を含むＦ層付銅箔の断片を切り出し、熱硬化性エポキシ樹脂で固めた。次いで、貫通孔の断面が露出するまで研磨し、貫通孔が形成された部分の断面を顕微鏡で観察した。
そして、貫通孔が形成された部分の断面において、銅箔とＦ層との間における剥離の有無を確認し、以下の基準に従って評価した。
○：剥離は全く見られない。
△：５μｍ未満の長さの剥離が見られる。
×：５μｍ以上の長さの剥離が見られる。3-7. Evaluation of UV Workability Using a laser processing machine (esi5330), a copper foil with an F layer was irradiated with a UV-YAG laser having a wavelength of 355 nm so as to orbit around a circumference of 100 μm in diameter. As a result, a circular through hole was formed in the copper foil with the F layer. The laser output was 1.5 W, the laser focal diameter was 25 μm, the number of orbits on the circumference was 16, and the oscillation frequency was 40 kHz.
Then, a fragment of the copper foil with an F layer including the through hole was cut out and hardened with a thermosetting epoxy resin. Then, the polishing was performed until the cross section of the through hole was exposed, and the cross section of the portion where the through hole was formed was observed with a microscope.
Then, in the cross section of the portion where the through hole was formed, the presence or absence of peeling between the copper foil and the F layer was confirmed, and the evaluation was made according to the following criteria.
◯: No peeling is observed.
Δ: Peeling with a length of less than 5 μm is observed.
X: Peeling with a length of 5 μm or more is observed.
３−８．誘電正接の測定
ファブリペロー共振器及びベクトルネットワークアナライザ（キーコム社製）を使用して、Ｆ層付銅箔のＦ層について１０ＧＨｚの誘電正接を測定した。
以上の結果を、以下の表１に示す。3-8. Measurement of Dissipation Factor Using a Fabry-Perot resonator and a vector network analyzer (manufactured by Keycom), the dielectric loss tangent of 10 GHz was measured for the F layer of the copper foil with the F layer.
The above results are shown in Table 1 below.
（例８）
同じ銅箔の粗化表面にメイヤーバーを用いてパウダー分散液Ａを塗布して、粗化表面にウェット膜を形成し、通風乾燥炉（炉温：１００℃）に１．５分間、通過させて溶媒を揮発させて塗工層を形成させた。さらに、遠赤外線炉（炉温度３７０℃）に１分間で通過させ、パウダー１（Ｆポリマー１）を溶融焼成して、表面にＦポリマー１を含むＦ層（厚さ：４μｍ）が形成されたＦ層付銅箔を得た。このＦ層付銅箔のＦ層の表面をプラズマ処理（出力：４．５ｋＷ、導入ガス：アルゴンガス、導入ガス流量：５０ｃｍ３／分間、圧力：５０ｍＴｏｒｒ、処理時間：２分間）した。(Example 8)
Powder dispersion A is applied to the roughened surface of the same copper foil using a Mayer bar to form a wet film on the roughened surface, and the mixture is passed through a ventilation drying furnace (furnace temperature: 100 ° C.) for 1.5 minutes. The solvent was volatilized to form a coating layer. Further, the powder 1 (F polymer 1) was melt-fired by passing it through a far-infrared furnace (furnace temperature 370 ° C.) for 1 minute to form an F layer (thickness: 4 μm) containing the F polymer 1 on the surface. A copper foil with an F layer was obtained. The surface of the F layer of the copper foil with the F layer was subjected to plasma treatment (output: 4.5 kW, introduction gas: argon gas, introduction gas flow rate: 50 cm 3 / min, pressure: 50 mTorr, treatment time: 2 minutes).
プラズマ処理後のＦ層付銅箔のＦ層の表面に、プリプレグとしてＦＲ−４（日立化成社製、「ＧＥＡ−６７Ｎ ０．２ｔ（ＨＡＮ）」；強化繊維：ガラス繊維、マトリックス樹脂：エポキシ樹脂、厚さ：０．２ｍｍ）を積層し、真空熱プレス（プレス温度：１８５℃、プレス圧力：３．０ＭＰａ、プレス時間：６０分間）して、プリプレグの硬化物層を有する積層体を得た。
この積層体は、はんだ浴に浮かべるはんだ耐熱性試験において、２８８℃のはんだ浴に５秒間、５回浮かべても、Ｆ層と硬化物層の界面に膨れる現象（膨れ現象）と、Ｆ層から銅箔が浮く現象（浮き現象）とが発生しなかった。FR-4 (manufactured by Hitachi Kasei Co., Ltd., "GEA-67N 0.2t (HAN)"; Reinforcing fiber: Glass fiber, Matrix resin: Epoxy resin on the surface of the F layer of the copper foil with F layer after plasma treatment. , Thickness: 0.2 mm) and vacuum hot press (press temperature: 185 ° C., press pressure: 3.0 MPa, press time: 60 minutes) to obtain a laminate having a cured product layer of prepreg. ..
In the solder heat resistance test of floating in a solder bath, this laminate has a phenomenon of swelling at the interface between the F layer and the cured product layer (swelling phenomenon) even if it is floated in a solder bath at 288 ° C. for 5
パウダー分散液Ａ〜Ｄ及びこれらを使用して得られたＦ層付銅箔は、各種特性に優れていた。また、分散剤Ａと分散剤Ｄとを比較すると、いずれも再分散が可能であったが、パウダー分散液Ａの方がより優れていた。これは、パウダー分散液Ａに含まれるパウダー１が官能基を有していることで、ポリイミドとの相互作用が高まり、より分散性が向上したためであると考えられる。 The powder dispersions A to D and the copper foil with an F layer obtained by using them were excellent in various properties. Further, when the dispersant A and the dispersant D were compared, both were able to be redispersed, but the powder dispersion liquid A was more superior. It is considered that this is because the powder 1 contained in the powder dispersion liquid A has a functional group, so that the interaction with the polyimide is enhanced and the dispersibility is further improved.
Ｆ層付銅箔を比較すると、パウダー分散液Ｅを使用したＦ層付銅箔では、Ｆ層形成時にパウダーが容易に脱落（粉落ち）し、ロールに付着していた。一方で、ポリイミドを添加したパウダー分散液Ａを使用したＦ層付銅箔では、ポリイミドがパウダー粒子のつなぎとなり、パウダーの脱落が抑制されたと考えられる。
また、パウダー分散液Ｅを使用したＦ層付銅箔は、ＵＶ波長域の光を吸収し得るポリイミドを含有しないため、３５５ｎｍの透過率は９０％となった。このため、ＵＶレーザーの大半が透過するため、ＵＶ加工性が低下したと考えらえる。Comparing the copper foils with the F layer, in the copper foils with the F layer using the powder dispersion liquid E, the powder easily fell off (powder fell off) when the F layer was formed and adhered to the roll. On the other hand, in the copper foil with an F layer using the powder dispersion A to which polyimide was added, it is considered that the polyimide served as a binder for the powder particles and the powder was suppressed from falling off.
Further, since the copper foil with an F layer using the powder dispersion E does not contain polyimide capable of absorbing light in the UV wavelength range, the transmittance at 355 nm was 90%. Therefore, it is considered that the UV processability is deteriorated because most of the UV laser is transmitted.
また、プリント基板材料の一態様である積層体（Ｆ層付銅箔とプリプレグの硬化物との積層体）において、パウダー分散液Ａから製造した積層体は、はんだ耐熱性試験で良好な結果を示し、耐熱性と耐薬品性を具備していた。 Further, in the laminate (a laminate of a copper foil with an F layer and a cured product of a prepreg), which is one aspect of a printed circuit board material, the laminate produced from the powder dispersion A gives good results in a solder heat resistance test. It showed heat resistance and chemical resistance.
さらに、パウダー分散液Ａの１００質量部に対して、アルミナとポリオールで被覆処理された酸化チタン（粒径：０．２５μｍ；石原産業社製、「タイペーク ＣＲ−５０−２」）の１質量部を、さらに配合してパウダー分散液Ａ’を調製した。パウダー分散液Ａ’の取扱性（上記「３−１．」〜「３−３．」の評価結果）は、パウダー分散液Ａと同等であった。このパウダー分散液Ａ’を使用して得られるＦ層付銅箔のＦ層の３５５ｎｍ透過率は５％未満であり、そのＵＶ吸収性がさらに向上していることを確認した。 Further, 1 part by mass of titanium oxide (particle size: 0.25 μm; manufactured by Ishihara Sangyo Co., Ltd., “Typake CR-50-2”) coated with alumina and polyol with respect to 100 parts by mass of the powder dispersion liquid A. Was further blended to prepare a powder dispersion A'. The handleability of the powder dispersion liquid A'(evaluation results of the above-mentioned "3-1." To "3-3.") Was equivalent to that of the powder dispersion liquid A. It was confirmed that the 355 nm transmittance of the F layer of the copper foil with the F layer obtained by using this powder dispersion liquid A'was less than 5%, and the UV absorption thereof was further improved.
４．フィルムの作製
（例９）
厚さ５０μｍのポリイミドフィルム（ＳＫＣ Ｋｏｌｏｎ ＰＩ社製、「ＦＳ−２００」）２の一方の面に、パウダー分散液Ａをダイコートで塗布し、通風乾燥炉（炉温：１４０℃）に３分間で通過させ、溶媒を揮発させて塗工層を形成した。さらに、ポリイミドフィルム２の他方の面にもパウダー分散液Ａを、同様に塗工し、溶媒を揮発させて塗工層を形成した。さらに、この両面に塗工層が形成されたポリイミドフィルム２を遠赤外線炉（炉温度：３７０℃）に２０分間で通過させ、パウダー１を溶融焼成して、ポリマー１を含むＦ層３をポリイミドフィルム（ＰＩ層）２の両面に有するフィルムＡを得た。Ｆ層の厚さは、それぞれ２５μｍであった。
（例１０）
パウダー分散液Ａに代えて、パウダー分散液Ｅを使用した以外は、例９と同様にして、フィルムＥを得た。4. Fabrication of film (Example 9)
Powder dispersion A is applied with a die coat to one surface of a polyimide film (SKC Kolon PI, "FS-200") 2 having a thickness of 50 μm, and placed in a ventilation drying oven (furnace temperature: 140 ° C.) in 3 minutes. It was allowed to pass and the solvent was volatilized to form a coating layer. Further, the powder dispersion liquid A was similarly applied to the other surface of the
(Example 10)
A film E was obtained in the same manner as in Example 9 except that the powder dispersion liquid E was used instead of the powder dispersion liquid A.
５．測定及び評価（その２）
各フィルムＡ、Ｅの両面に電解銅箔（福田金属箔粉工業株式会社製、「ＣＦ−Ｔ４９Ａ−ＤＳ−ＨＤ２−１２」）４を配し、３４０℃にて２０分間、真空下でプレスして両面銅張積層体１を得た。
レーザー出力を１．５Ｗ、レーザー焦点径を２５μｍ、円周上の周回回数を１６回、発振周波数を４０ｋＨｚとした以外は、上記「３−７．ＵＶ加工性の評価」と同様にして、各両面銅張積層体１に対してＵＶ−ＹＡＧレーザーを照射して、円形の貫通孔５を形成した。5. Measurement and evaluation (2)
Electrolytic copper foil (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., "CF-T49A-DS-HD2-12") 4 is placed on both sides of each film A and E, and pressed at 340 ° C. for 20 minutes under vacuum. A double-sided copper-clad laminate 1 was obtained.
Each is the same as the above "3-7. Evaluation of UV workability" except that the laser output is 1.5 W, the laser focal diameter is 25 μm, the number of orbits on the circumference is 16 times, and the oscillation frequency is 40 kHz. The double-sided copper-clad laminate 1 was irradiated with a UV-YAG laser to form a circular through
各両面銅張積層体１における貫通孔５の周辺の断面を撮影した顕微鏡写真を、それぞれ図１、図２に示す。
フィルムＡから得られた両面銅張積層体１では、Ｆ層３がポリイミドを含むので、ＵＶ加工性が良好である。このため、図１の顕微鏡写真に示す通り、貫通孔５の周囲においてＵＶによるＦ層３及びポリイミドフィルム（ＰＩ層）２の劣化の程度が抑制された。
一方、フィルムＥから得られた両面銅張積層体１では、Ｆ層３がポリイミドを含まないため、貫通孔５を形成するのにＵＶの照射時間を長くせざるを得なかった。このため、図２の顕微鏡写真に示す通り、貫通孔５の周囲においてＵＶによるＦ層３及びポリイミドフィルム（ＰＩ層）２の劣化の程度が激しかった。Micrographs of the periphery of the through
In the double-sided copper-clad laminate 1 obtained from the film A, the
On the other hand, in the double-sided copper-clad laminate 1 obtained from the film E, since the
本発明の分散剤を使用して得られる層は、電気特性及びＵＶ加工性に優れるため、かかる層を有する積層体は、アンテナ部品、プリント基板、航空機用部品、自動車用部品等に加工して使用できる。 Since the layer obtained by using the dispersant of the present invention is excellent in electrical characteristics and UV processability, the laminate having such a layer is processed into antenna parts, printed circuit boards, aircraft parts, automobile parts, and the like. Can be used.
１…両面銅張積層体、２…ポリイミドフィルム（ＰＩ層）、３…Ｆ層、４…電解銅箔、５…貫通孔、Ａ，Ｅ…フィルム 1 ... Double-sided copper-clad laminate, 2 ... Polyimide film (PI layer), 3 ... F layer, 4 ... Electrolytic copper foil, 5 ... Through holes, A, E ... Film
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| JP2012082329A (en) * | 2010-10-13 | 2012-04-26 | Sony Chemical & Information Device Corp | Polyamic acid varnish, polyimide varnish, method for producing these, and connection structure |
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