WO2022270460A1 - (meth)acrylic resin composition, inorganic fine particle-dispersed slurry composition, and inorganic fine particle-dispersed molded product - Google Patents
(meth)acrylic resin composition, inorganic fine particle-dispersed slurry composition, and inorganic fine particle-dispersed molded product Download PDFInfo
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- WO2022270460A1 WO2022270460A1 PCT/JP2022/024519 JP2022024519W WO2022270460A1 WO 2022270460 A1 WO2022270460 A1 WO 2022270460A1 JP 2022024519 W JP2022024519 W JP 2022024519W WO 2022270460 A1 WO2022270460 A1 WO 2022270460A1
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- meth
- acrylic resin
- inorganic fine
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- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 244
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 244
- 239000000203 mixture Substances 0.000 title claims abstract description 148
- 239000002002 slurry Substances 0.000 title claims abstract description 48
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 93
- 239000010419 fine particle Substances 0.000 claims abstract description 58
- 239000003960 organic solvent Substances 0.000 claims abstract description 58
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 55
- 125000000217 alkyl group Chemical group 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- 239000004014 plasticizer Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 238000000465 moulding Methods 0.000 claims description 12
- 230000002776 aggregation Effects 0.000 abstract description 22
- 238000004220 aggregation Methods 0.000 abstract description 21
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 70
- -1 polyethylene terephthalate Polymers 0.000 description 49
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 48
- 239000000178 monomer Substances 0.000 description 30
- 239000011521 glass Substances 0.000 description 26
- 239000011347 resin Substances 0.000 description 25
- 229920005989 resin Polymers 0.000 description 25
- 239000000843 powder Substances 0.000 description 21
- 239000011572 manganese Substances 0.000 description 18
- 239000012986 chain transfer agent Substances 0.000 description 17
- 239000003505 polymerization initiator Substances 0.000 description 17
- 239000011230 binding agent Substances 0.000 description 16
- 239000000919 ceramic Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 239000003985 ceramic capacitor Substances 0.000 description 8
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- SHLSSLVZXJBVHE-UHFFFAOYSA-N 3-sulfanylpropan-1-ol Chemical compound OCCCS SHLSSLVZXJBVHE-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 235000014692 zinc oxide Nutrition 0.000 description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 3
- MJQWABQELVFQJL-UHFFFAOYSA-N 3-Mercapto-2-butanol Chemical compound CC(O)C(C)S MJQWABQELVFQJL-UHFFFAOYSA-N 0.000 description 3
- XJTWZETUWHTBTG-UHFFFAOYSA-N 8-sulfanyloctan-1-ol Chemical compound OCCCCCCCCS XJTWZETUWHTBTG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229910007472 ZnO—B2O3—SiO2 Inorganic materials 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000011354 acetal resin Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 3
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 2
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 2
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 2
- KIFPIAKBYOIOCS-UHFFFAOYSA-N 2-methyl-2-(trioxidanyl)propane Chemical compound CC(C)(C)OOO KIFPIAKBYOIOCS-UHFFFAOYSA-N 0.000 description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 2
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229910020617 PbO—B2O3—SiO2 Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- IHTSDBYPAZEUOP-UHFFFAOYSA-N bis(2-butoxyethyl) hexanedioate Chemical compound CCCCOCCOC(=O)CCCCC(=O)OCCOCCCC IHTSDBYPAZEUOP-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 125000006226 butoxyethyl group Chemical group 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 2
- WRKRMDNAUJERQT-UHFFFAOYSA-N cumene hydroxyperoxide Chemical compound OOOO.CC(C)C1=CC=CC=C1 WRKRMDNAUJERQT-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 2
- HNBDRPTVWVGKBR-UHFFFAOYSA-N methyl pentanoate Chemical compound CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052844 willemite Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the present invention relates to a (meth)acrylic resin composition, an inorganic fine particle-dispersed slurry composition, and an inorganic fine particle-dispersed molding.
- a composition in which inorganic fine particles such as ceramic powder and glass particles are dispersed in a binder resin is used in the production of laminated electronic components such as laminated ceramic capacitors.
- laminated ceramic capacitors are generally manufactured using the following method. First, after adding additives such as a plasticizer and a dispersant to a solution of a binder resin dissolved in an organic solvent, ceramic raw material powder is added and uniformly mixed using a ball mill or the like to obtain an inorganic fine particle dispersion slurry composition. obtain.
- the resulting inorganic fine particle-dispersed slurry composition is cast on the surface of a support such as a release-treated polyethylene terephthalate film, SUS plate, or the like using a doctor blade, reverse roll coater, or the like, and volatile matter such as an organic solvent is removed. After evaporating, the ceramic green sheet is obtained by peeling off from the support. Next, the resulting ceramic green sheets are coated with a conductive paste that will become internal electrodes by screen printing or the like, and a plurality of these sheets are stacked, heated and pressure-bonded to obtain a laminate.
- the resulting laminate is heated to thermally decompose and remove components such as the binder resin, ie, a so-called degreasing treatment, followed by firing to obtain a fired ceramic body having internal electrodes. Further, external electrodes are applied to the end faces of the fired ceramic body obtained, and fired to complete a laminated ceramic capacitor.
- Patent Literature 1 discloses a method for efficiently dispersing ceramic powder in a configuration using these binders. Specifically, a method is disclosed in which ceramic powder such as calcium titanate is first pulverized in a solvent such as ethanol, and then a resin such as polyvinyl butyral resin or ethyl cellulose resin is added. Further, Patent Document 2 discloses a method using polyvinyl butyral, cellulose-based polymer, acrylic resin, etc. as a binder.
- JP 2011-84433 A Japanese Patent Application Laid-Open No. 2020-109761
- Patent Document 1 has a problem that it has a high decomposition temperature and cannot be applied to applications where low-temperature firing is desirable, such as applications using easily oxidizable metals such as copper or low-melting-point glass.
- Patent Document 2 describes the use of an acrylic resin, but when fine inorganic fine particles having an average particle size of less than 1 ⁇ m are used, there is a problem that the dispersibility deteriorates. Furthermore, the acrylic resin described in Patent Document 2 has a problem that deterioration due to oxidation occurs during degreasing, which requires a high baking temperature.
- An object of the present invention is to provide a (meth)acrylic resin composition that has excellent decomposability at low temperatures and that can improve the dispersibility of inorganic fine particles and the effect of suppressing aggregation.
- Another object of the present invention is to provide an inorganic fine particle-dispersed slurry composition and an inorganic fine particle-dispersed molding using the (meth)acrylic resin composition.
- the present disclosure (1) is a (meth) acrylic resin and a (meth) acrylic resin composition containing an organic solvent, satisfying any one of the following (1) to (3), the organic solvent A (meth)acrylic resin composition having a weight concentration of OH groups contained therein of 9.0% by weight or more and 28.0% by weight or less.
- the (meth)acrylic resin contains a high molecular weight (meth)acrylic resin (A) having a weight average molecular weight of 120,000 or more and 300,000 or less, and is contained in the high molecular weight (meth)acrylic resin (A).
- the weight concentration of the OH group contained in the polymer is 0.4% by weight or more and 2.0% by weight or less.
- the (meth)acrylic resin contains a high molecular weight (meth)acrylic resin (B) having a weight average molecular weight of more than 300,000 and 500,000 or less, and the high molecular weight (meth)acrylic resin (B) contains The weight concentration of OH groups contained in is 1.3% by weight or more and 3.5% by weight or less.
- the (meth)acrylic resin contains a low-molecular-weight (meth)acrylic resin (C) having a weight-average molecular weight of 5,000 to 100,000, and the low-molecular-weight (meth)acrylic resin (C)
- the weight concentration of OH groups contained therein is 1.3% by weight or more and 3.5% by weight or less, and the weight concentration of S atoms contained in the (meth)acrylic resin is 250 ppm or more and 20000 ppm or less.
- (2) of the present disclosure satisfies (1) and contains a low-molecular-weight (meth)acrylic resin having a weight average molecular weight of 5,000 to 100,000, wherein the low-molecular-weight (meth)acrylic resin contains The weight concentration of the OH group contained is 1.3% by weight or more and 3.5% by weight or less, and the content of the low molecular weight (meth)acrylic resin with respect to 100 parts by weight of the high molecular weight (meth)acrylic resin (A) is 0 (1)
- the (meth)acrylic resin composition of the present disclosure (1) which is 1 part by weight or more and 10 parts by weight or less.
- the present disclosure (3) satisfies (1) or (2), and the solubility of the high-molecular-weight (meth)acrylic resin (A) or (B) in ethanol is 10 parts by weight/100 parts by weight or more of ethanol. It is a (meth)acrylic resin composition of the present disclosure (1).
- the present disclosure (4) satisfies (1) or (2), and the high molecular weight (meth)acrylic resin (A) or (B) is represented by the following formula (a) for all structural units (Meta) of (1) or (3) of the present disclosure containing 79% by weight or more and 96% by weight or less of the structural unit represented by the following formula (b) and 3.1% by weight or more and 17% by weight or less of the structural unit represented by the following formula (b) It is an acrylic resin composition.
- R 1 represents a linear or branched alkyl group having 1 to 8 carbon atoms
- R 2 represents the number of carbon atoms in which at least one hydrogen atom is substituted with an OH group It represents 2 to 4 linear or branched alkyl groups.
- the present disclosure (5) satisfies (1) or (2), and the OH contained in the organic solvent with respect to the weight concentration of OH groups contained in the high molecular weight (meth)acrylic resin (A) or (B)
- the ratio of the weight concentration of groups is 4.5 or more.46.
- the (meth)acrylic resin composition according to (1), (3) or (4) of the present disclosure which is 2 or less.
- the present disclosure (6) satisfies (2), and the (meth)acrylic resin consists only of a high-molecular-weight (meth)acrylic resin (B), and S contained in the (meth)acrylic resin
- the (meth)acrylic resin composition according to (1), (3), (4) or (5) of the present disclosure wherein the weight concentration of atoms is 250 ppm or more and 20000 ppm or less.
- the present disclosure (7) is an inorganic fine particle-dispersed slurry composition containing the (meth)acrylic resin composition according to any one of the present disclosures (1) to (6), inorganic fine particles, and a plasticizer.
- the present disclosure (8) is an inorganic fine particle-dispersed molded product obtained by using the inorganic fine particle-dispersed slurry composition of the present disclosure (7). The present invention will be described in detail below.
- the present inventors have prepared a (meth)acrylic resin having a predetermined weight average molecular weight, OH group weight concentration, and S atom weight concentration, and By using it in combination with an organic solvent, the binder resin exhibits extremely excellent degradability even at low temperatures, and furthermore, the dispersibility of inorganic fine particles and the effect of suppressing aggregation can be improved. Arrived.
- the (meth)acrylic resin composition of the present invention contains a (meth)acrylic resin.
- the (meth)acrylic resin satisfies any one of the following (1) to (3).
- the (meth)acrylic resin contains a high molecular weight (meth)acrylic resin (A) having a weight average molecular weight of 120,000 or more and 300,000 or less, and is contained in the high molecular weight (meth)acrylic resin (A).
- the weight concentration of the OH group contained in the polymer is 0.4% by weight or more and 2.0% by weight or less.
- the (meth)acrylic resin contains a high molecular weight (meth)acrylic resin (B) having a weight average molecular weight of more than 300,000 and 500,000 or less, and the high molecular weight (meth)acrylic resin (B) contains The weight concentration of OH groups contained in is 1.3% by weight or more and 3.5% by weight or less.
- the (meth)acrylic resin contains a low-molecular-weight (meth)acrylic resin (C) having a weight-average molecular weight of 5,000 to 100,000, and is included in the low-molecular-weight (meth)acrylic resin.
- the weight concentration of OH groups contained in the (meth)acrylic resin is 1.3 wt % or more and 3.5 wt % or less, and the weight concentration of S atoms contained in the (meth)acrylic resin is 250 ppm or more and 20000 ppm or less.
- the (meth)acrylic resin contains a high molecular weight (meth)acrylic resin (A).
- the high molecular weight (meth)acrylic resin (A) has a weight average molecular weight of 120,000 or more and 300,000 or less.
- the weight average molecular weight is preferably 150,000 or more, more preferably 180,000 or more, preferably 250,000 or less, and more preferably 220,000 or less. Within the above range, the inorganic fine particle-dispersed slurry composition has a sufficient viscosity, and the printability can be improved.
- the ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the high molecular weight (meth)acrylic resin (A) is preferably 2 or more, and 8 or less. is preferred.
- the component having a low degree of polymerization is appropriately contained, so that the viscosity of the inorganic fine particle-dispersed slurry composition is within a suitable range, and the productivity can be enhanced.
- the sheet strength of the obtained inorganic fine particle-dispersed sheet can be made moderate.
- the surface smoothness of the resulting ceramic green sheet can be sufficiently improved.
- the above Mw/Mn is more preferably 3 or more, and more preferably 6 or less.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) are average molecular weights in terms of polystyrene, and can be obtained by performing GPC measurement using, for example, a column LF-804 (manufactured by Showa Denko KK) as a column. can.
- the weight concentration of OH groups contained in the high molecular weight (meth)acrylic resin (A) is 0.4% by weight or more and 2.0% by weight or less. By setting the amount within the above range, the binder resin exhibits extremely excellent decomposability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
- the weight concentration of the OH group is preferably 0.5% by weight or more, more preferably 0.6% by weight or more, preferably 1.6% by weight or less, and 1.4% by weight. The following are more preferable.
- the weight concentration of the OH group means the ratio of the weight of the OH group to the total weight of the high-molecular-weight (meth)acrylic resin (A), and can be calculated based on the following formula.
- Weight concentration of OH groups contained in high molecular weight (meth)acrylic resin (A) [weight of OH groups contained in all monomers/(weight of all monomers + weight of polymerization initiator)] x 100
- the (meth)acrylic resin contains a high-molecular-weight (meth)acrylic resin (B).
- the high molecular weight (meth)acrylic resin (A) has a weight average molecular weight of more than 300,000 and 500,000 or less. Within the above range, the dispersibility of the inorganic fine particles can be sufficiently improved when the inorganic fine particle-dispersed slurry composition is prepared. In addition, aggregation of inorganic fine particles can be suppressed.
- the weight average molecular weight is preferably 320,000 or more, more preferably 330,000 or more, preferably 480,000 or less, and more preferably 450,000 or less. Within the above range, the inorganic fine particle-dispersed slurry composition has a sufficient viscosity, and the printability can be improved. Further, the ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the high molecular weight (meth)acrylic resin (B) is preferably 2 or more, and 8 or less. is preferred.
- the component having a low degree of polymerization is appropriately contained, so that the viscosity of the inorganic fine particle-dispersed slurry composition is within a suitable range, and the productivity can be enhanced.
- the sheet strength of the obtained inorganic fine particle-dispersed sheet can be made moderate.
- the surface smoothness of the resulting ceramic green sheet can be sufficiently improved.
- the above Mw/Mn is more preferably 3 or more, and more preferably 6 or less.
- the weight concentration of OH groups contained in the high molecular weight (meth)acrylic resin (B) is 1.3% by weight or more and 3.5% by weight or less.
- the weight concentration of the OH group is preferably 1.5% by weight or more, more preferably 2% by weight or more, preferably 3.3% by weight or less, and 3% by weight or less. is more preferred.
- the weight concentration of the OH group means the ratio of the weight of the OH group to the total weight of the high-molecular-weight (meth)acrylic resin (B), and can be calculated based on the following formula.
- Weight concentration of OH groups contained in high molecular weight (meth)acrylic resin (B) [weight of OH groups contained in all monomers/(weight of all monomers + weight of polymerization initiator)] x 100
- the high molecular weight (meth)acrylic resins (A) and (B) preferably have a structural unit represented by the following formula (a), and preferably have a structural unit represented by the following formula (b). .
- R 1 represents a linear or branched alkyl group having 1 to 8 carbon atoms
- R 2 represents the number of carbon atoms in which at least one hydrogen atom is substituted with an OH group It represents 2 to 4 linear or branched alkyl groups.
- R 1 above is more preferably a linear or branched alkyl group having 1 to 4 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group.
- R 2 is preferably a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one hydrogen atom is substituted with an OH group. -hydroxybutyl group and the like.
- the content of the structural unit represented by the formula (a) in the high-molecular-weight (meth)acrylic resins (A) and (B) is preferably 79% by weight or more and 96% by weight or less. preferable. By setting it as the said range, low-temperature decomposability can fully be improved.
- the content of the structural unit represented by the above formula (a) is more preferably 85% by weight or more, and more preferably 95% by weight or less.
- the content of the structural unit represented by the formula (b) in the high molecular weight (meth)acrylic resins (A) and (B) is preferably 3.1% by weight or more and 17% by weight or less. is preferred. Ethanol is often used as a solvent for binder resins, but acrylic resins generally have lower solubility in ethanol than polyvinyl acetal resins. However, by setting the amount in the above range, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved. Moreover, the solubility in ethanol can be further enhanced.
- the content of the structural unit represented by the above formula (2) is more preferably 4% by weight or more, and more preferably 15% by weight or less.
- the high-molecular-weight (meth)acrylic resins (A) and (B) preferably have segments derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 3 to 4 carbon atoms. By having the above segment, the low-temperature decomposability can be made more excellent.
- Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 3 to 4 carbon atoms include n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-(meth)acrylate. -butyl, isobutyl (meth)acrylate and the like. Among them, isobutyl (meth)acrylate is preferred.
- the content of the segment derived from the (meth)acrylic acid ester having a linear or branched alkyl group having 3 to 4 carbon atoms in the high-molecular-weight (meth)acrylic resins (A) and (B) is 30% by weight. It is preferably 40% by weight or more, more preferably 40% by weight or more, preferably 95% by weight or less, and more preferably 88% by weight or less.
- the high-molecular-weight (meth)acrylic resins (A) and (B) may have segments derived from (meth)acrylic acid esters having alkyl groups of 1 to 2 carbon atoms.
- Examples of the (meth)acrylic acid ester having an alkyl group having 1 to 2 carbon atoms include methyl (meth)acrylate and ethyl (meth)acrylate.
- the content of the segment derived from the (meth)acrylic acid ester having an alkyl group having 1 to 2 carbon atoms in the high-molecular-weight (meth)acrylic resins (A) and (B) is preferably 0% by weight or more. , more preferably 10% by weight or more, preferably 66.8% by weight or less, and more preferably 46% by weight or less.
- the high-molecular-weight (meth)acrylic resins (A) and (B) may have a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 5 to 8 carbon atoms. good.
- Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 5 to 8 carbon atoms include n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, Examples include n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate and 2-ethylhexyl (meth)acrylate.
- (meth)acrylic acid esters having a linear or branched alkyl group having 6 to 8 carbon atoms are preferred, and 2-ethylhexyl (meth)acrylate is more preferred.
- the content of the segment derived from the (meth)acrylic acid ester having a linear or branched alkyl group having 5 to 8 carbon atoms in the high molecular weight (meth)acrylic resins (A) and (B) is 0 weight. % or more, more preferably 9 wt % or more, preferably 25 wt % or less, and more preferably 20 wt % or less.
- the high-molecular-weight (meth)acrylic resins (A) and (B) may have a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 9 or more carbon atoms.
- Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 9 or more carbon atoms include n-nonyl (meth)acrylate, isononyl (meth)acrylate, and n (meth)acrylate.
- the high-molecular-weight (meth)acrylic resins (A) and (B) contain segments derived from (meth)acrylic acid esters having linear or branched alkyl groups in which at least one of the hydrogen atoms is substituted with an OH group. It is preferable to have By having the above segment, the binder resin exhibits extremely excellent degradability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
- the (meth)acrylic acid ester having a linear or branched alkyl group in which at least one of the hydrogen atoms is substituted with an OH group preferably has an OH group weight ratio of 10.5% by weight or more. , more preferably 11.5% by weight or more, and preferably 13.1% by weight or less.
- the high-molecular-weight (meth)acrylic resins (A) and (B) are (meth)acrylic acid having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group. It is preferred to have segments derived from esters.
- Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. is mentioned. Among them, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate are preferred.
- (Meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one hydrogen atom in the high-molecular-weight (meth)acrylic resins (A) and (B) is substituted with an OH group
- the content of the segment derived from is preferably 3.1% by weight or more, more preferably 5.0% by weight or more, preferably 17.0% by weight or less, and 12.2% by weight % or less.
- the high-molecular-weight (meth)acrylic resins (A) and (B) are (meth)acrylic acid esters having a linear or branched alkyl group having 5 or more carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group.
- Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 5 or more carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group include hydroxypentyl (meth)acrylate, (meth) hydroxyhexyl acrylate, hydroxyheptyl (meth)acrylate, hydroxyoctyl (meth)acrylate and the like.
- the high-molecular weight (meth)acrylic resins (A) and (B) include segments derived from the (meth)acrylic acid ester, segments derived from (meth)acrylic acid, and (meth)acrylic acid having a glycidyl group. It may have segments derived from other (meth)acrylic acid esters such as esters.
- the glass transition temperature (Tg) of the high molecular weight (meth)acrylic resins (A) and (B) is preferably 30° C. or higher and 85° C. or lower. By setting the amount within the above range, the amount of the plasticizer to be added can be reduced, and the low-temperature decomposability can be improved.
- the Tg is more preferably 32° C. or higher, still more preferably 42° C. or higher, even more preferably 45° C. or higher, particularly preferably 50° C. or higher, and 80° C. or lower. is more preferable, and 75° C. or less is even more preferable.
- the glass transition temperature (Tg) can be measured using, for example, a differential scanning calorimeter (DSC).
- the above high molecular weight (meth)acrylic resins (A) and (B) preferably have a solubility in ethanol of 10 parts by weight/100 parts by weight or more of ethanol. By setting it as the said range, the dispersibility of an inorganic fine particle and the aggregation inhibitory effect can be improved. In addition, the solubility in organic solvents can be sufficiently increased.
- the solubility in ethanol is more preferably 50 parts by weight or more, and even more preferably 100 parts by weight or more.
- the above-mentioned solubility in ethanol means the amount of resin added required until precipitation occurs when dissolved in 100 parts by weight of ethanol in an environment of 25°C.
- the content of the high molecular weight (meth)acrylic resin (A) in the (meth)acrylic resin composition of the present invention is preferably 5% by weight or more, more preferably 10% by weight or more, and 30% by weight. % or more, preferably 70% by weight or less, and more preferably 60% by weight or less.
- the content of the high molecular weight (meth)acrylic resin (B) in the (meth)acrylic resin composition of the present invention is preferably 5% by weight or more, more preferably 10% by weight or more, and 30% by weight. % or more, preferably 70% by weight or less, and more preferably 60% by weight or less.
- the weight concentration of S atoms contained in the (meth)acrylic resin is preferably 250 ppm or more, and preferably 20000 ppm or less. preferable.
- the binder resin exhibits extremely excellent decomposability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
- the weight concentration of the S atoms is more preferably 400 ppm or more, and more preferably 15000 ppm or less.
- the weight concentration of S atoms means the ratio of the weight of S atoms to the weight of the (meth)acrylic resin, and can be calculated based on the following formula.
- Weight concentration of S atoms contained in (meth)acrylic resin [weight of S atoms contained in chain transfer agent/(weight of all monomers + weight of polymerization initiator + weight of chain transfer agent)] ⁇ 100
- the weight concentration of the S atoms is the weight concentration of the S atoms contained in each (meth)acrylic resin and each (meth)acrylic resin.
- the weight concentration of S atoms can also be determined by ICP-AES (inductively coupled plasma atomic emission spectrometry).
- the method for producing the high molecular weight (meth)acrylic resins (A) and (B) is not particularly limited.
- an organic solvent or the like is added to a raw material monomer mixture containing (meth) acrylic acid ester or the like to prepare a monomer mixture, and a polymerization initiator and a chain transfer agent are added to the obtained monomer mixture, and the above A method of copolymerizing raw material monomers may be mentioned.
- the polymerization method is not particularly limited, and examples thereof include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, and solution polymerization. Among them, solution polymerization is preferred.
- Examples of the polymerization initiator include t-butyl peroxypivalate, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroxyperoxide, t-butyl hydroxyperoxide, cyclohexanone peroxide, disuccinic acid peroxide and the like.
- Examples of the chain transfer agent include 3-mercapto-1,2-propanediol, 3-mercapto-1-propanol, 3-mercapto-2-butanol, 8-mercapto-1-octanol, mercaptosuccinic acid, and mercaptoacetic acid. etc.
- the (meth)acrylic resin contains a low molecular weight (meth)acrylic resin (C).
- the low molecular weight (meth)acrylic resin (C) has a weight average molecular weight of 5,000 or more and 100,000 or less.
- the weight average molecular weight is more preferably 6,000 or more, still more preferably 8,000 or more, more preferably 90,000 or less, and even more preferably 30,000 or less.
- the ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the low molecular weight (meth)acrylic resin (C) is preferably 1.3 or more, and 2 or more. It is more preferable that there is one, and it is preferable that it is 8 or less.
- the content is within the above range, the component having a low degree of polymerization is appropriately contained, so that the viscosity of the inorganic fine particle-dispersed slurry composition is within a suitable range, and the productivity can be enhanced.
- the sheet strength of the obtained inorganic fine particle-dispersed sheet can be made moderate. Furthermore, the surface smoothness of the resulting ceramic green sheet can be sufficiently improved.
- the above Mw/Mn is more preferably 3 or more, and more preferably 6 or less.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) are average molecular weights in terms of polystyrene, and can be obtained by performing GPC measurement using, for example, a column LF-804 (manufactured by Showa Denko KK) as a column. can.
- the weight concentration of OH groups contained in the low molecular weight (meth)acrylic resin (C) is 1.3% by weight or more and 3.5% by weight or less. By setting the amount within the above range, the binder resin exhibits extremely excellent decomposability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
- the weight concentration of the OH groups is preferably 1.4% by weight or more, preferably 3.3% by weight or less, and more preferably 3.2% by weight or less.
- the weight concentration of OH groups means the ratio of the weight of OH groups to the total weight of the low-molecular-weight (meth)acrylic resin (C), and can be calculated based on the following formula.
- Weight concentration of OH groups contained in the low molecular weight (meth) acrylic resin (C) [(weight of OH groups contained in all monomers + weight of OH groups contained in chain transfer agent) / (weight of all monomers + weight of polymerization initiator + weight of chain transfer agent)] ⁇ 100
- the low-molecular-weight (meth)acrylic resin (C) preferably has a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group with 3 to 4 carbon atoms. By having the above segment, the low-temperature decomposability can be made more excellent.
- the (meth)acrylic acid ester having a linear or branched alkyl group having 3 to 4 carbon atoms include n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-(meth)acrylate. -butyl, isobutyl (meth)acrylate and the like. Among them, isobutyl (meth)acrylate is preferred.
- the content of the segment derived from the (meth)acrylic acid ester having a linear or branched alkyl group having 3 to 4 carbon atoms in the low molecular weight (meth)acrylic resin (C) is 38% by weight or more. , more preferably 50% by weight or more, preferably 80% by weight or less, and more preferably 75% by weight or less.
- the low-molecular-weight (meth)acrylic resin (C) may have a segment derived from a (meth)acrylic acid ester having an alkyl group having 1 to 2 carbon atoms.
- examples of the (meth)acrylic acid ester having an alkyl group having 1 to 2 carbon atoms include methyl (meth)acrylate and ethyl (meth)acrylate.
- the content of the segment derived from the (meth)acrylic acid ester having an alkyl group having 1 to 2 carbon atoms in the low molecular weight (meth)acrylic resin (C) is preferably 0% by weight or more, and 7% by weight. It is more preferably 33% by weight or less, and more preferably 20.5% by weight or less.
- the low-molecular-weight (meth)acrylic resin (C) may have a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group with 5 to 8 carbon atoms.
- Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 5 to 8 carbon atoms include n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, Examples include n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate and 2-ethylhexyl (meth)acrylate.
- (meth)acrylic acid esters having a linear or branched alkyl group having 6 to 8 carbon atoms are preferred, and 2-ethylhexyl (meth)acrylate is more preferred.
- the content of the segment derived from the (meth)acrylic acid ester having a linear or branched alkyl group having 5 to 8 carbon atoms in the low molecular weight (meth)acrylic resin (C) is 0% by weight or more. It is preferably 10% by weight or more, more preferably 40% by weight or less, and more preferably 30% by weight or less.
- the low-molecular-weight (meth)acrylic resin (C) may have a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group with 9 or more carbon atoms.
- Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 9 or more carbon atoms include n-nonyl (meth)acrylate, isononyl (meth)acrylate, and n (meth)acrylate.
- the low-molecular-weight (meth)acrylic resin (C) preferably has a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group in which at least one of the hydrogen atoms is substituted with an OH group.
- the binder resin exhibits extremely excellent degradability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
- the (meth)acrylic acid ester having a linear or branched alkyl group in which at least one of the hydrogen atoms is substituted with an OH group preferably has an OH group weight ratio of 10.5% by weight or more. , more preferably 11.5% by weight or more, and preferably 13.1% by weight or less.
- the low-molecular-weight (meth)acrylic resin (C) is derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group. It is preferred to have segments.
- Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. is mentioned. Among them, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate are preferred.
- a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one of the hydrogen atoms in the low molecular weight (meth)acrylic resin (C) is substituted with an OH group is preferably 7% by weight or more, more preferably 10% by weight or more, preferably 20% by weight or less, and more preferably 16% by weight or less.
- the low-molecular-weight (meth)acrylic resin (C) is a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 5 or more carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group. It is preferred to have Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 5 or more carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group include hydroxypentyl (meth)acrylate, (meth) hydroxyhexyl acrylate, hydroxyheptyl (meth)acrylate, hydroxyoctyl (meth)acrylate and the like.
- the low-molecular-weight (meth)acrylic resin (C) includes segments derived from the (meth)acrylic acid ester, segments derived from (meth)acrylic acid, glycidyl group-containing (meth)acrylic acid esters, and the like. may have a segment derived from the (meth)acrylic acid ester of.
- the weight concentration of S atoms contained in the (meth)acrylic resin is 250 ppm or more and 20000 ppm or less.
- the binder resin exhibits extremely excellent decomposability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
- the weight concentration of the S atoms is preferably 1500 ppm or more, more preferably 3000 ppm or more, preferably 18000 ppm or less, and more preferably 10000 ppm or less.
- the weight concentration of S atoms means the ratio of the weight of S atoms to the weight of the (meth)acrylic resin, and can be calculated based on the following formula.
- Weight concentration of S atoms contained in (meth)acrylic resin [weight of S atoms contained in chain transfer agent/(weight of all monomers + weight of polymerization initiator + weight of chain transfer agent)] ⁇ 100
- the weight concentration of the S atoms is the weight concentration of the S atoms contained in each (meth)acrylic resin and each (meth)acrylic resin.
- the weight concentration of S atoms can also be determined by ICP-AES (inductively coupled plasma atomic emission spectrometry).
- the glass transition temperature (Tg) of the low molecular weight (meth)acrylic resin (C) is 30°C or higher and 60°C or lower. By setting the amount within the above range, the amount of the plasticizer to be added can be reduced, and the low-temperature decomposability can be improved.
- the Tg is preferably 32° C. or higher, more preferably 42° C. or higher, even more preferably 45° C. or higher, preferably 58° C. or lower, and more preferably 50° C. or lower. preferable.
- the glass transition temperature (Tg) can be measured using, for example, a differential scanning calorimeter (DSC).
- the content of the low molecular weight (meth)acrylic resin (C) in the (meth)acrylic resin composition of the present invention is preferably 0.006% by weight or more, more preferably 0.01% by weight or more. It is preferably 10% by weight or less, more preferably 8% by weight or less.
- the (meth)acrylic resin is, in addition to the high molecular weight (meth)acrylic resin (A), further the low molecular weight (meth) ) It is preferable to contain an acrylic resin (B). Further, by containing the low-molecular-weight (meth)acrylic resin (C), the dispersibility of the inorganic fine particles can be further improved.
- the content of the low molecular weight (meth)acrylic resin (C) is based on 100 parts by weight of the high molecular weight (meth)acrylic resin (A). Therefore, it is preferably 0.1 parts by weight or more, and preferably 10 parts by weight or less. By setting it as the said range, the dispersibility of an inorganic fine particle can be improved more.
- the content of the low-molecular-weight (meth)acrylic resin (C) with respect to 100 parts by weight of the high-molecular-weight (meth)acrylic resin is more preferably 0.3 parts by weight or more, and is preferably 7.5 parts by weight or less. more preferred.
- the method for producing the low molecular weight (meth)acrylic resin (C) is not particularly limited.
- an organic solvent or the like is added to a raw material monomer mixture containing (meth) acrylic acid ester or the like to prepare a monomer mixture, and a polymerization initiator and a chain transfer agent are added to the obtained monomer mixture, and the above A method of copolymerizing raw material monomers may be mentioned.
- the polymerization method is not particularly limited, and examples thereof include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, and solution polymerization. Among them, solution polymerization is preferred.
- polymerization initiator examples include t-butyl peroxypivalate, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroxyperoxide, t-butyl hydroxyperoxide, cyclohexanone peroxide, disuccinic acid peroxide and the like.
- chain transfer agent examples include 3-mercapto-1,2-propanediol, 3-mercapto-1-propanol, 3-mercapto-2-butanol, 8-mercapto-1-octanol, mercaptosuccinic acid, and mercaptoacetic acid. etc.
- the (meth)acrylic resin composition of the present invention contains an organic solvent.
- the weight concentration of OH groups contained in the organic solvent is 9.0% by weight or more and 28.0% by weight or less. By containing the above organic solvent, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
- the weight concentration of the OH group is preferably 11.0% by weight or more, more preferably 13.0% by weight or more, preferably 26.0% by weight or less, and 24% by weight or less. more preferably 22.5% by weight or less.
- the weight concentration of the OH group means the ratio of the weight of the OH group to the weight of the entire organic solvent, and can be calculated based on the following formula.
- Weight concentration of OH groups contained in organic solvent (weight of OH groups contained in all organic solvents/weight of all organic solvents) x 100
- Ratio of weight concentration of OH groups contained in the organic solvent to weight concentration of OH groups contained in the high molecular weight (meth)acrylic resins (A) and (B) (weight of OH groups contained in the organic solvent
- the concentration/weight concentration of OH groups contained in the high molecular weight (meth)acrylic resin) is preferably 4.5 or more and preferably 46.2 or less.
- the above ratio is more preferably 8.1 or more, more preferably 10 or more, more preferably 40 or less, still more preferably 30 or less, and even more preferably 25 or less. It is preferably 20 or less, and particularly preferably 20 or less.
- the organic solvent contains an organic solvent having an OH group.
- organic solvents having an OH group include aliphatic alcohols, cyclic alcohols, and alicyclic alcohols.
- the aliphatic alcohol include ethanol, propanol, isopropanol, heptanol, octanol, decanol, tridecanol, lauryl alcohol, tetradecyl alcohol, cetyl alcohol, 2-ethyl-1-hexanol, octadecyl alcohol, hexadecenol, oleyl alcohol, texanol.
- the cyclic alcohol include cresol and eugenol.
- the alicyclic alcohols include cycloalkanols such as cyclohexanol, terpene alcohols such as terpineol and dihydroterpineol, and the like. Among them, aliphatic alcohols are preferred, and ethanol, isopropanol, 2-butyl-2-ethyl-1,3-propanediol, neopentyl glycol and texanol are preferred.
- the organic solvent having an OH group preferably has a molecular weight of 46 or more, more preferably 60 or more, preferably 220 or less, and more preferably 160 or less.
- the organic solvent having an OH group preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms, preferably 12 or less carbon atoms, and more preferably 10 or less carbon atoms.
- the weight ratio of OH groups contained in the organic solvent having OH groups is preferably 7.5% by weight or more, more preferably 15% by weight or more, and is preferably 21% by weight or more. More preferably, it is 37% by weight or less.
- the content of the organic solvent having an OH group with respect to the entire organic solvent is preferably 29% by weight or more, more preferably 43% by weight or more, preferably 79% by weight or less, and 61% by weight. The following are more preferable.
- the organic solvent may contain an organic solvent other than the organic solvent having an OH group.
- organic solvents include ketones such as acetone, methyl ethyl ketone, dipropyl ketone and diisobutyl ketone, aromatic hydrocarbons such as toluene and xylene, methyl propionate, ethyl propionate, butyl propionate, and butanoic acid.
- toluene, butyl acetate and methyl ethyl ketone are preferred.
- the content of the other organic solvent relative to the total organic solvent is preferably 21% by weight or more, more preferably 39% by weight or more, preferably 71% by weight or less, and 57% by weight or less. is more preferable.
- the content of the organic solvent in the (meth)acrylic resin composition of the present invention is preferably 20% by weight or more, more preferably 30% by weight or more, and preferably 95% by weight or less, It is more preferably 70% by weight or less, and even more preferably 60% by weight or less.
- the content of the organic solvent in the (meth)acrylic resin composition of the present invention is preferably 25 parts by weight or more, more preferably 100 parts by weight or more, relative to 100 parts by weight of the (meth)acrylic resin. More preferably, it is 2000 parts by weight or less, and more preferably 1500 parts by weight or less.
- the content of the organic solvent in the (meth)acrylic resin composition of the present invention is preferably 25 parts by weight or more with respect to 100 parts by weight of the high molecular weight (meth)acrylic resin (A), and is 42.9 parts by weight. It is more preferably 1900 parts by weight or less, more preferably 233.3 parts by weight or less, and more preferably 150 parts by weight or less.
- the content of the organic solvent in the (meth)acrylic resin composition of the present invention is preferably 25 parts by weight or more and 100 parts by weight with respect to 100 parts by weight of the high molecular weight (meth)acrylic resin (B). It is more preferably 2000 parts by weight or less, and more preferably 1500 parts by weight or less.
- the content of the organic solvent in the (meth)acrylic resin composition of the present invention is preferably 25 parts by weight or more and 1000 parts by weight with respect to 100 parts by weight of the low molecular weight (meth)acrylic resin (C). It is more preferably 1,500,000 parts by weight or less, and more preferably 1,000,000 parts by weight or less.
- the boiling point of the organic solvent is preferably 90 to 160°C.
- the evaporation does not become too fast and the handleability is excellent.
- the boiling point By setting the boiling point to 160° C. or lower, it is possible to improve the strength of the inorganic fine particle dispersed sheet.
- the method for producing the (meth)acrylic resin composition of the present invention is not particularly limited. A method of mixing a (meth)acrylic resin containing at least one of the meth)acrylic resins (C), the above organic solvent, and other additives added as necessary.
- the (meth)acrylic resin composition of the present invention has excellent low-temperature decomposability, excellent dispersibility of inorganic fine particles, and excellent aggregation-inhibiting effect. can be used for
- An inorganic fine particle-dispersed slurry composition containing the (meth)acrylic resin composition of the present invention, inorganic fine particles and a plasticizer is also one aspect of the present invention.
- the inorganic fine particle-dispersed slurry composition of the present invention contains inorganic fine particles.
- the inorganic fine particles are not particularly limited, and examples thereof include glass powder, ceramic powder, phosphor fine particles, silicon oxide, and metal fine particles.
- the glass powder is not particularly limited. Examples include glass powders of various silicon oxides such as 3 -SiO 2 system and LiO 2 -Al 2 O 3 -SiO 2 system. Further, as the glass powder, SnO--B 2 O 3 --P 2 O 5 --Al 2 O 3 mixture, PbO--B 2 O 3 --SiO 2 mixture, BaO--ZnO--B 2 O 3 ---SiO 2 mixture, ZnO -Bi 2 O 3 -B 2 O 3 -SiO 2 mixture, Bi 2 O 3 -B 2 O 3 -BaO-CuO mixture, Bi 2 O 3 -ZnO-B 2 O 3 -Al 2 O 3 -SrO mixture, ZnO - Bi2O3 - B2O3 mixture, Bi2O3 - SiO2 mixture , P2O5 - Na2O - CaO - BaO - Al2O3 - B2O3 mixture , P2O5 -Sn
- R is an element selected from the group consisting of Zn, Ba, Ca, Mg, Sr, Sn, Ni, Fe and Mn.
- glass powders of PbO-B 2 O 3 -SiO 2 mixtures, lead-free BaO-ZnO-B 2 O 3 -SiO 2 mixtures or ZnO-Bi 2 O 3 -B 2 O 3 -SiO 2 mixtures, etc. of lead-free glass powder is preferred.
- the ceramic powder is not particularly limited, and examples thereof include alumina, ferrite, zirconia, zircon, barium zirconate, calcium zirconate, titanium oxide, barium titanate, strontium titanate, calcium titanate, magnesium titanate, zinc titanate, Lanthanum titanate, neodymium titanate, lead zirconium titanate, alumina nitride, silicon nitride, boron nitride, boron carbide, barium stannate, calcium stannate, magnesium silicate, mullite, steatite, cordierite, forsterite, etc. be done.
- ITO, FTO, niobium oxide, vanadium oxide, tungsten oxide, lanthanum strontium manganite, lanthanum strontium cobalt ferrite, yttrium-stabilized zirconia, gadolinium-doped ceria, nickel oxide, lanthanum chromite, and the like can also be used.
- the phosphor fine particles are not particularly limited, and for example, blue phosphor substances, red phosphor substances, green phosphor substances, etc., which are conventionally known as phosphor substances for displays, are used.
- Blue phosphor materials include, for example, MgAl 10 O 17 :Eu, Y 2 SiO 5 :Ce system, CaWO 4 :Pb system, BaMgAl 14 O 23 :Eu system, BaMgAl 16 O 27 :Eu system, BaMg 2 Al 14 O 23 : Eu system, BaMg 2 Al 14 O 27 : Eu system, ZnS: (Ag, Cd) system is used.
- red phosphor materials include Y2O3 :Eu system, Y2SiO5 :Eu system, Y3Al5O12 :Eu system, Zn3 ( PO4 ) 2 : Mn system , YBO3 :Eu.
- Green phosphor materials include, for example, Zn2SiO4 :Mn-based, BaAl12O19 :Mn-based, SrAl13O19 : Mn -based, CaAl12O19 : Mn -based, YBO3 : Tb - based, and BaMgAl14O . 23 :Mn system, LuBO3 :Tb system, GdBO3 :Tb system , ScBO3 : Tb system, and Sr6Si3O3Cl4 :Eu system.
- ZnO Zn system
- ZnS (Cu, Al) system
- ZnS Ag system
- Y 2 O 2 S Eu system
- ZnS Zn system
- (Y, Cd) BO 3 Eu system
- BaMgAl 12 O 23 Eu-based ones
- the fine metal particles are not particularly limited, and examples thereof include powders of iron, copper, nickel, palladium, platinum, gold, silver, aluminum, tungsten, and alloys thereof.
- metals such as copper and iron, which have good adsorption properties with carboxyl groups, amino groups, amide groups, etc. and are easily oxidized, can also be suitably used. These metal powders may be used alone or in combination of two or more.
- various carbon blacks, carbon nanotubes, and the like may be used as the metal fine particles.
- the inorganic fine particles preferably contain lithium or titanium.
- low-melting-point glass such as LiO 2 ⁇ Al 2 O 3 ⁇ SiO 2 -based inorganic glass
- Lithium cobalt composite oxides such as LiCeO2
- Lithium manganese composite oxides such as LiMnO4
- lithium titanium phosphate LiTi2 ( PO4) 3 )
- lithium titanate Li4Ti5O12
- Li4 / 3Ti5 / 3O 4 LiCoO 2
- lithium germanium phosphate LiGe 2 (PO 4 ) 3
- the content of the inorganic fine particles in the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited, but the preferred lower limit is 10% by weight and the preferred upper limit is 90% by weight. When the amount is 10% by weight or more, sufficient viscosity and excellent coatability can be obtained.
- the inorganic fine particle-dispersed slurry composition of the present invention further contains a plasticizer.
- the plasticizer include di(butoxyethyl) adipate, dibutoxyethoxyethyl adipate, triethylene glycol dibutyl, triethylene glycol bis(2-ethylhexanoate), triethylene glycol dihexanoate, acetyl triethyl citrate, acetyl tributyl citrate, acetyl diethyl citrate, acetyl citrate dibutyl, dibutyl sebacate, triacetin, diethyl acetyloxymalonate, diethyl ethoxymalonate and the like.
- plasticizers it is possible to reduce the amount of plasticizer added compared to the case of using a normal plasticizer (when about 30% by weight is added to the binder, 25% by weight hereinafter, it can be further reduced to 20% by weight or less).
- a non-aromatic plasticizer that does not contain an aromatic ring such as a benzene ring in its structure, and it is more preferable to use a component derived from adipic acid, triethylene glycol, citric acid or succinic acid.
- a plasticizer having an aromatic ring is not preferable because it is likely to burn and become soot.
- the plasticizer preferably has an alkyl group with 2 or more carbon atoms such as ethyl or butyl, and more preferably has an alkyl group with 4 or more carbon atoms.
- the plasticizer suppresses the absorption of water into the plasticizer and prevents defects such as voids and swelling in the obtained inorganic fine particle dispersion sheet. can do.
- the alkyl group of the plasticizer is preferably located at the molecular terminal.
- the plasticizer preferably has a functional group having 2 carbon atoms such as an ethyl group, a functional group having 4 carbon atoms such as a butyl group, and a functional group such as a butoxyethyl group.
- the functional group is present at the terminal molecular chain.
- a plasticizer with a functional group with 2 carbon atoms such as an ethyl group in the terminal molecular chain has good compatibility with a segment derived from ethyl methacrylate, and a plasticizer with a functional group with 4 carbon atoms such as a butyl group in the terminal molecule.
- the agent is compatible with segments derived from butyl methacrylate.
- a plasticizer having a functional group with 2 or 4 carbon atoms has good compatibility with the high-molecular-weight (meth)acrylic resin according to the present invention, and can preferably improve the brittleness of the resin. Furthermore, a butoxyethyl group is compatible with the composition of both the segment derived from ethyl methacrylate and the segment derived from butyl methacrylate, and can be preferably used.
- the plasticizer preferably has a carbon:oxygen ratio of 5:1 to 3:1.
- the carbon:oxygen ratio By setting the carbon:oxygen ratio within the above range, it is possible to improve the combustibility of the plasticizer and prevent the generation of residual carbon. Moreover, compatibility with (meth)acrylic resin can be improved, and a plasticizing effect can be exhibited even with a small amount of plasticizer.
- high-boiling organic solvents having a propylene glycol skeleton or a trimethylene glycol skeleton can be preferably used as long as they contain an alkyl group having 4 or more carbon atoms and have a carbon:oxygen ratio of 5:1 to 3:1.
- the boiling point of the plasticizer is preferably 240°C or higher and lower than 390°C.
- the boiling point is 240° C. or higher, it becomes easy to evaporate in the drying step, and can be prevented from remaining in the molded article.
- the temperature is less than 390°C, residual carbon can be prevented from being generated.
- the said boiling point means the boiling point in a normal pressure.
- the content of the plasticizer in the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited, but the preferred lower limit is 0.1% by weight and the preferred upper limit is 3.0% by weight. By setting it within the above range, it is possible to reduce the baking residue of the plasticizer.
- the content of the (meth)acrylic resin composition in the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited, but the preferred lower limit is 0.5% by weight and the preferred upper limit is 10% by weight.
- the inorganic fine particle-dispersed slurry composition can be degreased even when fired at a low temperature, and has excellent dispersibility of the inorganic fine particles and an effect of suppressing aggregation of the inorganic fine particles.
- a more preferable lower limit to the content of the (meth)acrylic resin composition is 1% by weight, and a more preferable upper limit is 7% by weight.
- the inorganic fine particle-dispersed slurry composition of the present invention may further contain additives such as surfactants.
- the surfactant is not particularly limited, and examples thereof include cationic surfactants, anionic surfactants, and nonionic surfactants.
- the nonionic surfactant is not particularly limited, it is preferably a nonionic surfactant having an HLB value of 10 or more and 20 or less.
- the HLB value is used as an index representing the hydrophilicity and lipophilicity of a surfactant, and several calculation methods have been proposed. is defined as S, the acid value of the fatty acid constituting the surfactant as A, and the HLB value as 20 (1-S/A).
- nonionic surfactants having polyethylene oxide in which an alkylene ether is added to the fatty chain are suitable, and specifically, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, etc. are preferably used. be done.
- the above nonionic surfactant has good thermal decomposability, but if added in a large amount, the thermal decomposability of the inorganic fine particle-dispersed slurry composition may decrease, so the preferred upper limit of the content is 5% by weight. .
- the viscosity of the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited.
- a preferable upper limit is 100 Pa ⁇ s.
- the obtained inorganic fine particle-dispersed sheet can maintain a predetermined shape after being coated by a die coat printing method or the like. Further, by setting the viscosity to 100 Pa ⁇ s or less, it is possible to prevent problems such as not erasing the coating marks of the die, and to achieve excellent printability.
- the method for producing the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited, and conventionally known stirring methods can be mentioned. Examples thereof include a method of stirring other components such as a solvent and optionally added plasticizer with a three-roll roller or the like. The addition order of the components of the inorganic fine particle-dispersed slurry composition can be appropriately set.
- the inorganic fine particle dispersion slurry composition of the present invention is applied onto a support film that has been subjected to mold release treatment on one side, the organic solvent is dried, and an inorganic fine particle dispersion molding can be produced by molding.
- an inorganic fine particle dispersion molding is also one aspect of the present invention.
- the shape of the inorganic fine particle-dispersed molding of the present invention is not particularly limited, but may be, for example, a sheet shape.
- the inorganic fine particle dispersion slurry composition of the present invention is uniformly coated on a support film by a coating method such as a roll coater, a die coater, a squeeze coater, a curtain coater, or the like. A method of forming a film and the like can be mentioned.
- a coating method such as a roll coater, a die coater, a squeeze coater, a curtain coater, or the like.
- a method of forming a film and the like can be mentioned.
- the polymerization liquid it is preferable to use the polymerization liquid as it is as an inorganic fine particle dispersed slurry composition and process it into an inorganic fine particle dispersed molded product without drying the high molecular weight (meth)acrylic resin.
- the support film used in producing the inorganic fine particle-dispersed molded article of the present invention is a flexible resin having heat resistance and solvent resistance.
- a film is preferred. Since the support film has flexibility, the inorganic fine particle-dispersed slurry composition can be applied to the surface of the support film by a roll coater, a blade coater, or the like, and the resulting inorganic fine particle-dispersed sheet-forming film is wound into a roll. It can be stored and supplied as is.
- the resin forming the support film examples include fluorine-containing resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose.
- the thickness of the support film is preferably 20 to 100 ⁇ m, for example.
- it is preferable that the surface of the support film is subjected to a release treatment, so that the support film can be easily peeled off in the transfer step.
- An inorganic fine particle-dispersed molding can be produced by coating and drying the inorganic fine particle-dispersed slurry composition of the present invention.
- a laminated ceramic capacitor can be produced by using the inorganic fine particle-dispersed slurry composition and the inorganic fine particle-dispersed molded product of the present invention for dielectric green sheets and electrode pastes.
- a magnetic material can be produced by using the inorganic fine particle-dispersed slurry composition and the inorganic fine particle-dispersed molding of the present invention.
- the method for producing the laminated ceramic capacitor includes the steps of printing a conductive paste on the inorganic fine particle-dispersed molding of the present invention and drying it to produce a dielectric sheet, and laminating the dielectric sheet. method.
- the conductive paste contains conductive powder.
- the material of the conductive powder is not particularly limited as long as it has conductivity, and examples thereof include nickel, palladium, platinum, gold, silver, copper, molybdenum, tin, and alloys thereof. These conductive powders may be used alone or in combination of two or more.
- a method for printing the conductive paste is not particularly limited, and examples thereof include a screen printing method, a die coat printing method, an offset printing method, a gravure printing method, an inkjet printing method, and the like.
- the laminated ceramic capacitor is obtained by laminating the dielectric sheets printed with the conductive paste.
- the present invention it is possible to provide a (meth)acrylic resin composition that has excellent decomposability at low temperatures and that can improve the dispersibility of inorganic fine particles and the effect of suppressing aggregation. Further, an inorganic fine particle-dispersed slurry composition and an inorganic fine particle-dispersed molded product using the (meth)acrylic resin composition can be provided.
- MMA methyl methacrylate EMA: ethyl methacrylate nBMA: n-butyl methacrylate iBMA: isobutyl methacrylate 2EHMA: 2-ethylhexyl methacrylate HEMA: 2-hydroxyethyl methacrylate HPMA: 2-hydroxypropyl methacrylate HBMA: 2-hydroxybutyl methacrylate
- Ceramic powder and a plasticizer were added to the obtained (meth)acrylic resin composition so as to have the composition shown in Table 3, and the mixture was kneaded with a high-speed stirrer to obtain an inorganic powder.
- a microparticle-dispersed slurry composition was prepared.
- the ceramic powder copper powder (manufactured by Fujino Metal Co., Ltd., average particle size 0.1 ⁇ m), glass frit (manufactured by AGC, average particle size 0.8 ⁇ m), and as the plasticizer, di(butoxyethyl) adipate. was used.
- Weight concentration of OH groups contained in high molecular weight (meth)acrylic resin [weight of OH groups contained in all monomers/(weight of all monomers + weight of polymerization initiator)] ⁇ 100 Weight concentration of OH groups contained in the low molecular weight (meth) acrylic resin: [(weight of OH groups contained in all monomers + weight of OH groups contained in chain transfer agent) / (weight of all monomers + chain transfer Weight of agent + weight of polymerization initiator)] ⁇ 100 Weight concentration of OH groups contained in organic solvent: (weight of OH groups contained in all organic solvents/weight of all organic solvents) x 100
- Weight concentration of S atom contained in the (meth)acrylic resin [weight of S atoms contained in chain transfer agent/(weight of all monomers + weight of polymerization initiator + weight of chain transfer agent)] ⁇ 100
- the weight concentration of the S atoms is the weight concentration of the S atoms contained in each (meth)acrylic resin and each (meth)acrylic resin. ) calculated based on the mixing ratio of the acrylic resin.
- the inorganic fine particle dispersion slurry composition is printed in an environment of a temperature of 23 ° C. and a humidity of 50%, and the condition is 100 ° C. for 30 minutes. Solvent drying was performed in a blower oven. Using the obtained printed pattern, measurements were made at 10 points with a surface roughness meter (Surfcom, manufactured by Tokyo Seimitsu Co., Ltd.). In addition, the following were used as a screen printer, a screen plate, and a printing glass substrate.
- Screen printer (MT-320TV, manufactured by Microtec) Screen plate (manufactured by Tokyo Process Service Co., Ltd., ST500, emulsion 2 ⁇ m, 2012 pattern, screen frame 320 mm ⁇ 320 mm)
- Printed glass substrate (soda glass, 150 mm x 150 mm, thickness 1.5 mm) When the surface roughness is small, it can be said that the dispersibility of the inorganic fine particles is excellent.
- the present invention it is possible to provide a (meth)acrylic resin composition that has excellent decomposability at low temperatures and that can improve the dispersibility of inorganic fine particles and the effect of suppressing aggregation. Further, an inorganic fine particle-dispersed slurry composition and an inorganic fine particle-dispersed molded product using the (meth)acrylic resin composition can be provided.
Abstract
The present invention provides a (meth)acrylic resin composition which has excellent degradability at a low temperature and can improve the dispersibility and aggregation inhibitory effect of inorganic fine particles. Moreover, the present invention provides an inorganic fine particle-dispersed slurry composition and an inorganic fine particle-dispersed molded product which use said (meth)acrylic resin composition. The present invention is a (meth)acrylic resin composition containing a (meth)acrylic resin and an organic solvent, wherein the (meth)acrylic resin composition satisfies any of the following (1)-(3), and the weight concentration of the OH group contained in the organic solvent is 9.0-28.0 wt%: (1) the (meth)acrylic resin includes a high-molecular-weight (meth)acrylic resin (A) having a weight-average molecular weight of 120,000-300,000, and the weight concentration of the OH group contained in the high-molecular-weight (meth)acrylic resin (A) is 0.4-2.0 wt%; (2) the (meth)acrylic resin includes a high-molecular-weight (meth)acrylic resin (B) having a weight-average molecular weight of 300,000-500,000 (exclusive of 300,000), and the weight concentration of the OH group contained in the high-molecular-weight (meth)acrylic resin (B) is 1.3-3.5 wt%; and (3) the (meth)acrylic resin includes a low-molecular-weight (meth)acrylic resin (C) having a weight-average molecular weight of 5,000-100,000, the weight concentration of the OH group contained in the low-molecular-weight (meth)acrylic resin (C) is 1.3-3.5 wt%, and the weight concentration of the S atom contained in the (meth)acrylic resin is 250-20,000 ppm.
Description
本発明は、（メタ）アクリル樹脂組成物、無機微粒子分散スラリー組成物及び無機微粒子分散成形物に関する。
TECHNICAL FIELD The present invention relates to a (meth)acrylic resin composition, an inorganic fine particle-dispersed slurry composition, and an inorganic fine particle-dispersed molding.
セラミック粉末、ガラス粒子等の無機微粒子をバインダー樹脂に分散させた組成物が、積層セラミクスコンデンサ等の積層電子部品の生産に用いられている。
このような積層セラミクスコンデンサは、一般に、次のような方法を用いて製造される。まず、バインダー樹脂を有機溶剤に溶解した溶液に、可塑剤、分散剤等の添加剤を添加した後、セラミック原料粉末を加え、ボールミル等を用いて均一に混合して無機微粒子分散スラリー組成物を得る。
得られた無機微粒子分散スラリー組成物を、ドクターブレード、リバースロールコーター等を用いて、離型処理したポリエチレンテレフタレートフィルム、ＳＵＳプレート等の支持体表面に流延成形し、有機溶剤等の揮発分を溜去させた後、支持体から剥離してセラミックグリーンシートを得る。
次に、得られたセラミックグリーンシート上に内部電極となる導電ペーストをスクリーン印刷等により塗工し、これを複数枚積み重ね、加熱及び圧着して積層体を得る。得られた積層体を加熱して、バインダー樹脂等の成分を熱分解して除去する処理、いわゆる脱脂処理を行った後、焼成することによって、内部電極を備えたセラミック焼成体を得る。更に、得られたセラミック焼成体の端面に外部電極を塗布し、焼成することによって、積層セラミクスコンデンサが完成する。 A composition in which inorganic fine particles such as ceramic powder and glass particles are dispersed in a binder resin is used in the production of laminated electronic components such as laminated ceramic capacitors.
Such laminated ceramic capacitors are generally manufactured using the following method. First, after adding additives such as a plasticizer and a dispersant to a solution of a binder resin dissolved in an organic solvent, ceramic raw material powder is added and uniformly mixed using a ball mill or the like to obtain an inorganic fine particle dispersion slurry composition. obtain.
The resulting inorganic fine particle-dispersed slurry composition is cast on the surface of a support such as a release-treated polyethylene terephthalate film, SUS plate, or the like using a doctor blade, reverse roll coater, or the like, and volatile matter such as an organic solvent is removed. After evaporating, the ceramic green sheet is obtained by peeling off from the support.
Next, the resulting ceramic green sheets are coated with a conductive paste that will become internal electrodes by screen printing or the like, and a plurality of these sheets are stacked, heated and pressure-bonded to obtain a laminate. The resulting laminate is heated to thermally decompose and remove components such as the binder resin, ie, a so-called degreasing treatment, followed by firing to obtain a fired ceramic body having internal electrodes. Further, external electrodes are applied to the end faces of the fired ceramic body obtained, and fired to complete a laminated ceramic capacitor.
このような積層セラミクスコンデンサは、一般に、次のような方法を用いて製造される。まず、バインダー樹脂を有機溶剤に溶解した溶液に、可塑剤、分散剤等の添加剤を添加した後、セラミック原料粉末を加え、ボールミル等を用いて均一に混合して無機微粒子分散スラリー組成物を得る。
得られた無機微粒子分散スラリー組成物を、ドクターブレード、リバースロールコーター等を用いて、離型処理したポリエチレンテレフタレートフィルム、ＳＵＳプレート等の支持体表面に流延成形し、有機溶剤等の揮発分を溜去させた後、支持体から剥離してセラミックグリーンシートを得る。
次に、得られたセラミックグリーンシート上に内部電極となる導電ペーストをスクリーン印刷等により塗工し、これを複数枚積み重ね、加熱及び圧着して積層体を得る。得られた積層体を加熱して、バインダー樹脂等の成分を熱分解して除去する処理、いわゆる脱脂処理を行った後、焼成することによって、内部電極を備えたセラミック焼成体を得る。更に、得られたセラミック焼成体の端面に外部電極を塗布し、焼成することによって、積層セラミクスコンデンサが完成する。 A composition in which inorganic fine particles such as ceramic powder and glass particles are dispersed in a binder resin is used in the production of laminated electronic components such as laminated ceramic capacitors.
Such laminated ceramic capacitors are generally manufactured using the following method. First, after adding additives such as a plasticizer and a dispersant to a solution of a binder resin dissolved in an organic solvent, ceramic raw material powder is added and uniformly mixed using a ball mill or the like to obtain an inorganic fine particle dispersion slurry composition. obtain.
The resulting inorganic fine particle-dispersed slurry composition is cast on the surface of a support such as a release-treated polyethylene terephthalate film, SUS plate, or the like using a doctor blade, reverse roll coater, or the like, and volatile matter such as an organic solvent is removed. After evaporating, the ceramic green sheet is obtained by peeling off from the support.
Next, the resulting ceramic green sheets are coated with a conductive paste that will become internal electrodes by screen printing or the like, and a plurality of these sheets are stacked, heated and pressure-bonded to obtain a laminate. The resulting laminate is heated to thermally decompose and remove components such as the binder resin, ie, a so-called degreasing treatment, followed by firing to obtain a fired ceramic body having internal electrodes. Further, external electrodes are applied to the end faces of the fired ceramic body obtained, and fired to complete a laminated ceramic capacitor.
近年、積層セラミクスコンデンサの微細化に伴い、用いる無機微粒子の微細化も進んでいる。微細化した無機微粒子はペースト中で凝集しやすく、凝集が生じると脱脂工程及び焼成工程においてボイドが残りやすくなったり、積層セラミクスコンデンサとした際に、無機微粒子の分散性が低下した結果、製品の電気特性を低下させる原因となる。
In recent years, along with the miniaturization of multilayer ceramic capacitors, the miniaturization of inorganic fine particles to be used has also progressed. Fine inorganic particles tend to agglomerate in the paste, and if agglomeration occurs, voids tend to remain in the degreasing and firing processes. It causes deterioration of electrical characteristics.
バインダー樹脂としては、例えば、エチルセルロースやポリビニルアセタール樹脂（ＰＶＢ）が用いられることが一般的である。例えば、特許文献１には、これらのバインダーを用いる構成において、セラミック粉末を効率的に分散させる方法が開示されている。具体的には、チタン酸カルシウム等のセラミック粉末をエタノール等の溶剤中で一次解砕し、その後、ポリビニルブチラール樹脂、エチルセルロース樹脂等の樹脂を添加する方法が開示されている。
また、特許文献２には、ポリビニルブチラール、セルロース系高分子の他、アクリル樹脂等をバインダーとして用いる方法が開示されている。 As the binder resin, for example, ethyl cellulose and polyvinyl acetal resin (PVB) are generally used. For example, Patent Literature 1 discloses a method for efficiently dispersing ceramic powder in a configuration using these binders. Specifically, a method is disclosed in which ceramic powder such as calcium titanate is first pulverized in a solvent such as ethanol, and then a resin such as polyvinyl butyral resin or ethyl cellulose resin is added.
Further, Patent Document 2 discloses a method using polyvinyl butyral, cellulose-based polymer, acrylic resin, etc. as a binder.
また、特許文献２には、ポリビニルブチラール、セルロース系高分子の他、アクリル樹脂等をバインダーとして用いる方法が開示されている。 As the binder resin, for example, ethyl cellulose and polyvinyl acetal resin (PVB) are generally used. For example, Patent Literature 1 discloses a method for efficiently dispersing ceramic powder in a configuration using these binders. Specifically, a method is disclosed in which ceramic powder such as calcium titanate is first pulverized in a solvent such as ethanol, and then a resin such as polyvinyl butyral resin or ethyl cellulose resin is added.
Further, Patent Document 2 discloses a method using polyvinyl butyral, cellulose-based polymer, acrylic resin, etc. as a binder.
しかしながら、特許文献１に記載のポリビニルアセタール樹脂は、分解温度が高く、低温焼成が望ましい用途、例えば、酸化しやすい銅等の金属や低融点ガラス等を用いる用途に適用できないという問題がある。
また、特許文献２にはアクリル系樹脂を用いることが記載されているが、平均粒子径が１μｍを下回る微小な無機微粒子を用いる場合、分散性が悪化するという問題がある。更に、特許文献２に記載のアクリル樹脂では、高い焼成温度が必要となる脱脂中に酸化による劣化が生じるという問題がある。 However, the polyvinyl acetal resin described in Patent Document 1 has a problem that it has a high decomposition temperature and cannot be applied to applications where low-temperature firing is desirable, such as applications using easily oxidizable metals such as copper or low-melting-point glass.
Further, Patent Document 2 describes the use of an acrylic resin, but when fine inorganic fine particles having an average particle size of less than 1 μm are used, there is a problem that the dispersibility deteriorates. Furthermore, the acrylic resin described in Patent Document 2 has a problem that deterioration due to oxidation occurs during degreasing, which requires a high baking temperature.
また、特許文献２にはアクリル系樹脂を用いることが記載されているが、平均粒子径が１μｍを下回る微小な無機微粒子を用いる場合、分散性が悪化するという問題がある。更に、特許文献２に記載のアクリル樹脂では、高い焼成温度が必要となる脱脂中に酸化による劣化が生じるという問題がある。 However, the polyvinyl acetal resin described in Patent Document 1 has a problem that it has a high decomposition temperature and cannot be applied to applications where low-temperature firing is desirable, such as applications using easily oxidizable metals such as copper or low-melting-point glass.
Further, Patent Document 2 describes the use of an acrylic resin, but when fine inorganic fine particles having an average particle size of less than 1 μm are used, there is a problem that the dispersibility deteriorates. Furthermore, the acrylic resin described in Patent Document 2 has a problem that deterioration due to oxidation occurs during degreasing, which requires a high baking temperature.
本発明は、低温で優れた分解性を有するとともに、無機微粒子の分散性や凝集抑制効果を向上させることができる（メタ）アクリル樹脂組成物を提供することを目的とする。また、該（メタ）アクリル樹脂組成物を用いる無機微粒子分散スラリー組成物、無機微粒子分散成形物を提供することを目的とする。
An object of the present invention is to provide a (meth)acrylic resin composition that has excellent decomposability at low temperatures and that can improve the dispersibility of inorganic fine particles and the effect of suppressing aggregation. Another object of the present invention is to provide an inorganic fine particle-dispersed slurry composition and an inorganic fine particle-dispersed molding using the (meth)acrylic resin composition.
本開示（１）は、（メタ）アクリル樹脂、及び、有機溶剤を含有する（メタ）アクリル樹脂組成物であって、下記（１）～（３）の何れか１つを満たし、前記有機溶剤中に含まれるＯＨ基の重量濃度が９．０重量％以上２８．０重量％以下である（メタ）アクリル樹脂組成物である。
（１）前記（メタ）アクリル樹脂は、重量平均分子量が１２万以上３０万以下の高分子量（メタ）アクリル樹脂（Ａ）を含有し、前記高分子量（メタ）アクリル樹脂（Ａ）中に含まれるＯＨ基の重量濃度が０．４重量％以上２．０重量％以下である。
（２）前記（メタ）アクリル樹脂は、重量平均分子量が３０万を超え５０万以下である高分子量（メタ）アクリル樹脂（Ｂ）を含有し、前記高分子量（メタ）アクリル樹脂（Ｂ）中に含まれるＯＨ基の重量濃度が１．３重量％以上３．５重量％以下である。
（３）前記（メタ）アクリル樹脂は、重量平均分子量が０．５万以上１０万以下である低分子量（メタ）アクリル樹脂（Ｃ）を含有し、前記低分子量（メタ）アクリル樹脂（Ｃ）中に含まれるＯＨ基の重量濃度が１．３重量％以上３．５重量％以下であり、前記（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度が２５０ｐｐｍ以上２００００ｐｐｍ以下である。
本開示（２）は、（１）を満たし、かつ、重量平均分子量が０．５万以上１０万以下である低分子量（メタ）アクリル樹脂を含有し、前記低分子量（メタ）アクリル樹脂中に含まれるＯＨ基の重量濃度が１．３重量％以上３．５重量％以下であり、高分子量（メタ）アクリル樹脂（Ａ）１００重量部に対する前記低分子量（メタ）アクリル樹脂の含有量が０．１重量部以上１０重量部以下である本開示（１）の（メタ）アクリル樹脂組成物である。
本開示（３）は、（１）又は（２）を満たし、かつ、高分子量（メタ）アクリル樹脂（Ａ）又は（Ｂ）のエタノールへの溶解度が１０重量部／エタノール１００重量部以上である本開示（１）の（メタ）アクリル樹脂組成物である。
本開示（４）は、（１）又は（２）を満たし、かつ、高分子量（メタ）アクリル樹脂（Ａ）又は（Ｂ）は、全構成単位に対して、下記式（ａ）で表される構成単位を７９重量％以上９６重量％以下、下記式（ｂ）で表される構成単位を３．１重量％以上１７重量％以下含有する本開示（１）又は（３）の（メタ）アクリル樹脂組成物である。
式（ａ）中、Ｒ１は炭素数１～８の直鎖状又は分岐状アルキル基を表し、式（ｂ）中、Ｒ２は、水素原子の少なくとも１つがＯＨ基で置換された炭素数２～４の直鎖状又は分岐状アルキル基を表す。
本開示（５）は、（１）又は（２）を満たし、かつ、高分子量（メタ）アクリル樹脂（Ａ）又は（Ｂ）中に含まれるＯＨ基の重量濃度に対する有機溶剤中に含まれるＯＨ基の重量濃度の比（有機溶剤中に含まれるＯＨ基の重量濃度／高分子量（メタ）アクリル樹脂（Ａ）又は（Ｂ）中に含まれるＯＨ基の重量濃度）が４．５以上４６．２以下である本開示（１）、（３）又は（４）の（メタ）アクリル樹脂組成物である。
本開示（６）は、（２）を満たし、かつ、（メタ）アクリル樹脂は、高分子量（メタ）アクリル樹脂（Ｂ）のみからなるものであり、前記（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度が２５０ｐｐｍ以上２００００ｐｐｍ以下である本開示（１）、（３）、（４）又は（５）の（メタ）アクリル樹脂組成物である。
本開示（７）は、本開示（１）～（６）の何れかの（メタ）アクリル樹脂組成物、無機微粒子、及び、可塑剤を含有する無機微粒子分散スラリー組成物である。
本開示（８）は、本開示（７）の無機微粒子分散スラリー組成物を用いてなる無機微粒子分散成形物である。
以下に本発明を詳述する。 The present disclosure (1) is a (meth) acrylic resin and a (meth) acrylic resin composition containing an organic solvent, satisfying any one of the following (1) to (3), the organic solvent A (meth)acrylic resin composition having a weight concentration of OH groups contained therein of 9.0% by weight or more and 28.0% by weight or less.
(1) The (meth)acrylic resin contains a high molecular weight (meth)acrylic resin (A) having a weight average molecular weight of 120,000 or more and 300,000 or less, and is contained in the high molecular weight (meth)acrylic resin (A). The weight concentration of the OH group contained in the polymer is 0.4% by weight or more and 2.0% by weight or less.
(2) The (meth)acrylic resin contains a high molecular weight (meth)acrylic resin (B) having a weight average molecular weight of more than 300,000 and 500,000 or less, and the high molecular weight (meth)acrylic resin (B) contains The weight concentration of OH groups contained in is 1.3% by weight or more and 3.5% by weight or less.
(3) The (meth)acrylic resin contains a low-molecular-weight (meth)acrylic resin (C) having a weight-average molecular weight of 5,000 to 100,000, and the low-molecular-weight (meth)acrylic resin (C) The weight concentration of OH groups contained therein is 1.3% by weight or more and 3.5% by weight or less, and the weight concentration of S atoms contained in the (meth)acrylic resin is 250 ppm or more and 20000 ppm or less.
(2) of the present disclosure satisfies (1) and contains a low-molecular-weight (meth)acrylic resin having a weight average molecular weight of 5,000 to 100,000, wherein the low-molecular-weight (meth)acrylic resin contains The weight concentration of the OH group contained is 1.3% by weight or more and 3.5% by weight or less, and the content of the low molecular weight (meth)acrylic resin with respect to 100 parts by weight of the high molecular weight (meth)acrylic resin (A) is 0 (1) The (meth)acrylic resin composition of the present disclosure (1), which is 1 part by weight or more and 10 parts by weight or less.
The present disclosure (3) satisfies (1) or (2), and the solubility of the high-molecular-weight (meth)acrylic resin (A) or (B) in ethanol is 10 parts by weight/100 parts by weight or more of ethanol. It is a (meth)acrylic resin composition of the present disclosure (1).
The present disclosure (4) satisfies (1) or (2), and the high molecular weight (meth)acrylic resin (A) or (B) is represented by the following formula (a) for all structural units (Meta) of (1) or (3) of the present disclosure containing 79% by weight or more and 96% by weight or less of the structural unit represented by the following formula (b) and 3.1% by weight or more and 17% by weight or less of the structural unit represented by the following formula (b) It is an acrylic resin composition.
In formula (a), R 1 represents a linear or branched alkyl group having 1 to 8 carbon atoms, and in formula (b), R 2 represents the number of carbon atoms in which at least one hydrogen atom is substituted with an OH group It represents 2 to 4 linear or branched alkyl groups.
The present disclosure (5) satisfies (1) or (2), and the OH contained in the organic solvent with respect to the weight concentration of OH groups contained in the high molecular weight (meth)acrylic resin (A) or (B) The ratio of the weight concentration of groups (the weight concentration of OH groups contained in the organic solvent/the weight concentration of OH groups contained in the high-molecular-weight (meth)acrylic resin (A) or (B)) is 4.5 or more.46. The (meth)acrylic resin composition according to (1), (3) or (4) of the present disclosure, which is 2 or less.
The present disclosure (6) satisfies (2), and the (meth)acrylic resin consists only of a high-molecular-weight (meth)acrylic resin (B), and S contained in the (meth)acrylic resin The (meth)acrylic resin composition according to (1), (3), (4) or (5) of the present disclosure, wherein the weight concentration of atoms is 250 ppm or more and 20000 ppm or less.
The present disclosure (7) is an inorganic fine particle-dispersed slurry composition containing the (meth)acrylic resin composition according to any one of the present disclosures (1) to (6), inorganic fine particles, and a plasticizer.
The present disclosure (8) is an inorganic fine particle-dispersed molded product obtained by using the inorganic fine particle-dispersed slurry composition of the present disclosure (7).
The present invention will be described in detail below.
（１）前記（メタ）アクリル樹脂は、重量平均分子量が１２万以上３０万以下の高分子量（メタ）アクリル樹脂（Ａ）を含有し、前記高分子量（メタ）アクリル樹脂（Ａ）中に含まれるＯＨ基の重量濃度が０．４重量％以上２．０重量％以下である。
（２）前記（メタ）アクリル樹脂は、重量平均分子量が３０万を超え５０万以下である高分子量（メタ）アクリル樹脂（Ｂ）を含有し、前記高分子量（メタ）アクリル樹脂（Ｂ）中に含まれるＯＨ基の重量濃度が１．３重量％以上３．５重量％以下である。
（３）前記（メタ）アクリル樹脂は、重量平均分子量が０．５万以上１０万以下である低分子量（メタ）アクリル樹脂（Ｃ）を含有し、前記低分子量（メタ）アクリル樹脂（Ｃ）中に含まれるＯＨ基の重量濃度が１．３重量％以上３．５重量％以下であり、前記（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度が２５０ｐｐｍ以上２００００ｐｐｍ以下である。
本開示（２）は、（１）を満たし、かつ、重量平均分子量が０．５万以上１０万以下である低分子量（メタ）アクリル樹脂を含有し、前記低分子量（メタ）アクリル樹脂中に含まれるＯＨ基の重量濃度が１．３重量％以上３．５重量％以下であり、高分子量（メタ）アクリル樹脂（Ａ）１００重量部に対する前記低分子量（メタ）アクリル樹脂の含有量が０．１重量部以上１０重量部以下である本開示（１）の（メタ）アクリル樹脂組成物である。
本開示（３）は、（１）又は（２）を満たし、かつ、高分子量（メタ）アクリル樹脂（Ａ）又は（Ｂ）のエタノールへの溶解度が１０重量部／エタノール１００重量部以上である本開示（１）の（メタ）アクリル樹脂組成物である。
本開示（４）は、（１）又は（２）を満たし、かつ、高分子量（メタ）アクリル樹脂（Ａ）又は（Ｂ）は、全構成単位に対して、下記式（ａ）で表される構成単位を７９重量％以上９６重量％以下、下記式（ｂ）で表される構成単位を３．１重量％以上１７重量％以下含有する本開示（１）又は（３）の（メタ）アクリル樹脂組成物である。
本開示（５）は、（１）又は（２）を満たし、かつ、高分子量（メタ）アクリル樹脂（Ａ）又は（Ｂ）中に含まれるＯＨ基の重量濃度に対する有機溶剤中に含まれるＯＨ基の重量濃度の比（有機溶剤中に含まれるＯＨ基の重量濃度／高分子量（メタ）アクリル樹脂（Ａ）又は（Ｂ）中に含まれるＯＨ基の重量濃度）が４．５以上４６．２以下である本開示（１）、（３）又は（４）の（メタ）アクリル樹脂組成物である。
本開示（６）は、（２）を満たし、かつ、（メタ）アクリル樹脂は、高分子量（メタ）アクリル樹脂（Ｂ）のみからなるものであり、前記（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度が２５０ｐｐｍ以上２００００ｐｐｍ以下である本開示（１）、（３）、（４）又は（５）の（メタ）アクリル樹脂組成物である。
本開示（７）は、本開示（１）～（６）の何れかの（メタ）アクリル樹脂組成物、無機微粒子、及び、可塑剤を含有する無機微粒子分散スラリー組成物である。
本開示（８）は、本開示（７）の無機微粒子分散スラリー組成物を用いてなる無機微粒子分散成形物である。
以下に本発明を詳述する。 The present disclosure (1) is a (meth) acrylic resin and a (meth) acrylic resin composition containing an organic solvent, satisfying any one of the following (1) to (3), the organic solvent A (meth)acrylic resin composition having a weight concentration of OH groups contained therein of 9.0% by weight or more and 28.0% by weight or less.
(1) The (meth)acrylic resin contains a high molecular weight (meth)acrylic resin (A) having a weight average molecular weight of 120,000 or more and 300,000 or less, and is contained in the high molecular weight (meth)acrylic resin (A). The weight concentration of the OH group contained in the polymer is 0.4% by weight or more and 2.0% by weight or less.
(2) The (meth)acrylic resin contains a high molecular weight (meth)acrylic resin (B) having a weight average molecular weight of more than 300,000 and 500,000 or less, and the high molecular weight (meth)acrylic resin (B) contains The weight concentration of OH groups contained in is 1.3% by weight or more and 3.5% by weight or less.
(3) The (meth)acrylic resin contains a low-molecular-weight (meth)acrylic resin (C) having a weight-average molecular weight of 5,000 to 100,000, and the low-molecular-weight (meth)acrylic resin (C) The weight concentration of OH groups contained therein is 1.3% by weight or more and 3.5% by weight or less, and the weight concentration of S atoms contained in the (meth)acrylic resin is 250 ppm or more and 20000 ppm or less.
(2) of the present disclosure satisfies (1) and contains a low-molecular-weight (meth)acrylic resin having a weight average molecular weight of 5,000 to 100,000, wherein the low-molecular-weight (meth)acrylic resin contains The weight concentration of the OH group contained is 1.3% by weight or more and 3.5% by weight or less, and the content of the low molecular weight (meth)acrylic resin with respect to 100 parts by weight of the high molecular weight (meth)acrylic resin (A) is 0 (1) The (meth)acrylic resin composition of the present disclosure (1), which is 1 part by weight or more and 10 parts by weight or less.
The present disclosure (3) satisfies (1) or (2), and the solubility of the high-molecular-weight (meth)acrylic resin (A) or (B) in ethanol is 10 parts by weight/100 parts by weight or more of ethanol. It is a (meth)acrylic resin composition of the present disclosure (1).
The present disclosure (4) satisfies (1) or (2), and the high molecular weight (meth)acrylic resin (A) or (B) is represented by the following formula (a) for all structural units (Meta) of (1) or (3) of the present disclosure containing 79% by weight or more and 96% by weight or less of the structural unit represented by the following formula (b) and 3.1% by weight or more and 17% by weight or less of the structural unit represented by the following formula (b) It is an acrylic resin composition.
The present disclosure (5) satisfies (1) or (2), and the OH contained in the organic solvent with respect to the weight concentration of OH groups contained in the high molecular weight (meth)acrylic resin (A) or (B) The ratio of the weight concentration of groups (the weight concentration of OH groups contained in the organic solvent/the weight concentration of OH groups contained in the high-molecular-weight (meth)acrylic resin (A) or (B)) is 4.5 or more.46. The (meth)acrylic resin composition according to (1), (3) or (4) of the present disclosure, which is 2 or less.
The present disclosure (6) satisfies (2), and the (meth)acrylic resin consists only of a high-molecular-weight (meth)acrylic resin (B), and S contained in the (meth)acrylic resin The (meth)acrylic resin composition according to (1), (3), (4) or (5) of the present disclosure, wherein the weight concentration of atoms is 250 ppm or more and 20000 ppm or less.
The present disclosure (7) is an inorganic fine particle-dispersed slurry composition containing the (meth)acrylic resin composition according to any one of the present disclosures (1) to (6), inorganic fine particles, and a plasticizer.
The present disclosure (8) is an inorganic fine particle-dispersed molded product obtained by using the inorganic fine particle-dispersed slurry composition of the present disclosure (7).
The present invention will be described in detail below.
本発明者らは、所定の重量平均分子量、ＯＨ基の重量濃度、Ｓ原子の重量濃度を有する（メタ）アクリル樹脂と、ＯＨ基の重量濃度が９．０重量％以上２８．０重量％以下である有機溶剤とを組み合わせて用いることにより、バインダー樹脂が低温でも極めて優れた分解性を発現しつつ、更に、無機微粒子の分散性、凝集抑制効果を向上できることを見出し、本発明を完成するに至った。
The present inventors have prepared a (meth)acrylic resin having a predetermined weight average molecular weight, OH group weight concentration, and S atom weight concentration, and By using it in combination with an organic solvent, the binder resin exhibits extremely excellent degradability even at low temperatures, and furthermore, the dispersibility of inorganic fine particles and the effect of suppressing aggregation can be improved. Arrived.
本発明の（メタ）アクリル樹脂組成物は、（メタ）アクリル樹脂を含有する。
上記（メタ）アクリル樹脂は、下記（１）～（３）の何れか１つを満たす。
（１）前記（メタ）アクリル樹脂は、重量平均分子量が１２万以上３０万以下の高分子量（メタ）アクリル樹脂（Ａ）を含有し、前記高分子量（メタ）アクリル樹脂（Ａ）中に含まれるＯＨ基の重量濃度が０．４重量％以上２．０重量％以下である。
（２）前記（メタ）アクリル樹脂は、重量平均分子量が３０万を超え５０万以下である高分子量（メタ）アクリル樹脂（Ｂ）を含有し、前記高分子量（メタ）アクリル樹脂（Ｂ）中に含まれるＯＨ基の重量濃度が１．３重量％以上３．５重量％以下である。
（３）前記（メタ）アクリル樹脂は、重量平均分子量が０．５万以上１０万以下である低分子量（メタ）アクリル樹脂（Ｃ）を含有し、前記低分子量（メタ）アクリル樹脂中に含まれるＯＨ基の重量濃度が１．３重量％以上３．５重量％以下であり、前記（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度が２５０ｐｐｍ以上２００００ｐｐｍ以下である。上記構成を満たすことで、無機微粒子分散スラリー組成物とした際、無機微粒子の分散性を充分向上させることができる。また、無機微粒子の凝集を抑制することができる。 The (meth)acrylic resin composition of the present invention contains a (meth)acrylic resin.
The (meth)acrylic resin satisfies any one of the following (1) to (3).
(1) The (meth)acrylic resin contains a high molecular weight (meth)acrylic resin (A) having a weight average molecular weight of 120,000 or more and 300,000 or less, and is contained in the high molecular weight (meth)acrylic resin (A). The weight concentration of the OH group contained in the polymer is 0.4% by weight or more and 2.0% by weight or less.
(2) The (meth)acrylic resin contains a high molecular weight (meth)acrylic resin (B) having a weight average molecular weight of more than 300,000 and 500,000 or less, and the high molecular weight (meth)acrylic resin (B) contains The weight concentration of OH groups contained in is 1.3% by weight or more and 3.5% by weight or less.
(3) The (meth)acrylic resin contains a low-molecular-weight (meth)acrylic resin (C) having a weight-average molecular weight of 5,000 to 100,000, and is included in the low-molecular-weight (meth)acrylic resin. The weight concentration of OH groups contained in the (meth)acrylic resin is 1.3 wt % or more and 3.5 wt % or less, and the weight concentration of S atoms contained in the (meth)acrylic resin is 250 ppm or more and 20000 ppm or less. By satisfying the above configuration, the dispersibility of the inorganic fine particles can be sufficiently improved when an inorganic fine particle-dispersed slurry composition is prepared. In addition, aggregation of inorganic fine particles can be suppressed.
上記（メタ）アクリル樹脂は、下記（１）～（３）の何れか１つを満たす。
（１）前記（メタ）アクリル樹脂は、重量平均分子量が１２万以上３０万以下の高分子量（メタ）アクリル樹脂（Ａ）を含有し、前記高分子量（メタ）アクリル樹脂（Ａ）中に含まれるＯＨ基の重量濃度が０．４重量％以上２．０重量％以下である。
（２）前記（メタ）アクリル樹脂は、重量平均分子量が３０万を超え５０万以下である高分子量（メタ）アクリル樹脂（Ｂ）を含有し、前記高分子量（メタ）アクリル樹脂（Ｂ）中に含まれるＯＨ基の重量濃度が１．３重量％以上３．５重量％以下である。
（３）前記（メタ）アクリル樹脂は、重量平均分子量が０．５万以上１０万以下である低分子量（メタ）アクリル樹脂（Ｃ）を含有し、前記低分子量（メタ）アクリル樹脂中に含まれるＯＨ基の重量濃度が１．３重量％以上３．５重量％以下であり、前記（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度が２５０ｐｐｍ以上２００００ｐｐｍ以下である。上記構成を満たすことで、無機微粒子分散スラリー組成物とした際、無機微粒子の分散性を充分向上させることができる。また、無機微粒子の凝集を抑制することができる。 The (meth)acrylic resin composition of the present invention contains a (meth)acrylic resin.
The (meth)acrylic resin satisfies any one of the following (1) to (3).
(1) The (meth)acrylic resin contains a high molecular weight (meth)acrylic resin (A) having a weight average molecular weight of 120,000 or more and 300,000 or less, and is contained in the high molecular weight (meth)acrylic resin (A). The weight concentration of the OH group contained in the polymer is 0.4% by weight or more and 2.0% by weight or less.
(2) The (meth)acrylic resin contains a high molecular weight (meth)acrylic resin (B) having a weight average molecular weight of more than 300,000 and 500,000 or less, and the high molecular weight (meth)acrylic resin (B) contains The weight concentration of OH groups contained in is 1.3% by weight or more and 3.5% by weight or less.
(3) The (meth)acrylic resin contains a low-molecular-weight (meth)acrylic resin (C) having a weight-average molecular weight of 5,000 to 100,000, and is included in the low-molecular-weight (meth)acrylic resin. The weight concentration of OH groups contained in the (meth)acrylic resin is 1.3 wt % or more and 3.5 wt % or less, and the weight concentration of S atoms contained in the (meth)acrylic resin is 250 ppm or more and 20000 ppm or less. By satisfying the above configuration, the dispersibility of the inorganic fine particles can be sufficiently improved when an inorganic fine particle-dispersed slurry composition is prepared. In addition, aggregation of inorganic fine particles can be suppressed.
＜高分子量（メタ）アクリル樹脂（Ａ）＞
上記（１）を満たす本発明の（メタ）アクリル樹脂組成物において、上記（メタ）アクリル樹脂は、高分子量（メタ）アクリル樹脂（Ａ）を含有する。
上記高分子量（メタ）アクリル樹脂（Ａ）は、重量平均分子量が１２万以上３０万以下である。
上記範囲とすることで、無機微粒子分散スラリー組成物とした際、無機微粒子の分散性を充分向上させることができる。また、無機微粒子の凝集を抑制することができる。
上記重量平均分子量は、１５万以上であることが好ましく、１８万以上であることがより好ましく、２５万以下であることが好ましく、２２万以下であることがより好ましい。
上記範囲とすることで、無機微粒子分散スラリー組成物とした際、充分な粘度を有するものとなり、また、印刷性に向上できる。
また、上記高分子量（メタ）アクリル樹脂（Ａ）の重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）は、２以上であることが好ましく、８以下であることが好ましい。
上記範囲内とすることで、低重合度の成分が適度に含有されるため、無機微粒子分散スラリー組成物の粘度が好適な範囲となり、生産性を高めることができる。また、得られる無機微粒子分散シートのシート強度を適度なものとできる。更に、得られるセラミックグリーンシートの表面平滑性を充分に向上させることができる。
上記Ｍｗ／Ｍｎは３以上であることがより好ましく、６以下であることがより好ましい。
なお、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）は、ポリスチレン換算による平均分子量であり、カラムとして例えばカラムＬＦ－８０４（昭和電工社製）を用いてＧＰＣ測定を行うことで得ることができる。 <High molecular weight (meth)acrylic resin (A)>
In the (meth)acrylic resin composition of the present invention satisfying the above (1), the (meth)acrylic resin contains a high molecular weight (meth)acrylic resin (A).
The high molecular weight (meth)acrylic resin (A) has a weight average molecular weight of 120,000 or more and 300,000 or less.
Within the above range, the dispersibility of the inorganic fine particles can be sufficiently improved when the inorganic fine particle-dispersed slurry composition is prepared. In addition, aggregation of inorganic fine particles can be suppressed.
The weight average molecular weight is preferably 150,000 or more, more preferably 180,000 or more, preferably 250,000 or less, and more preferably 220,000 or less.
Within the above range, the inorganic fine particle-dispersed slurry composition has a sufficient viscosity, and the printability can be improved.
In addition, the ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the high molecular weight (meth)acrylic resin (A) is preferably 2 or more, and 8 or less. is preferred.
When the content is within the above range, the component having a low degree of polymerization is appropriately contained, so that the viscosity of the inorganic fine particle-dispersed slurry composition is within a suitable range, and the productivity can be enhanced. In addition, the sheet strength of the obtained inorganic fine particle-dispersed sheet can be made moderate. Furthermore, the surface smoothness of the resulting ceramic green sheet can be sufficiently improved.
The above Mw/Mn is more preferably 3 or more, and more preferably 6 or less.
The weight average molecular weight (Mw) and number average molecular weight (Mn) are average molecular weights in terms of polystyrene, and can be obtained by performing GPC measurement using, for example, a column LF-804 (manufactured by Showa Denko KK) as a column. can.
上記（１）を満たす本発明の（メタ）アクリル樹脂組成物において、上記（メタ）アクリル樹脂は、高分子量（メタ）アクリル樹脂（Ａ）を含有する。
上記高分子量（メタ）アクリル樹脂（Ａ）は、重量平均分子量が１２万以上３０万以下である。
上記範囲とすることで、無機微粒子分散スラリー組成物とした際、無機微粒子の分散性を充分向上させることができる。また、無機微粒子の凝集を抑制することができる。
上記重量平均分子量は、１５万以上であることが好ましく、１８万以上であることがより好ましく、２５万以下であることが好ましく、２２万以下であることがより好ましい。
上記範囲とすることで、無機微粒子分散スラリー組成物とした際、充分な粘度を有するものとなり、また、印刷性に向上できる。
また、上記高分子量（メタ）アクリル樹脂（Ａ）の重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）は、２以上であることが好ましく、８以下であることが好ましい。
上記範囲内とすることで、低重合度の成分が適度に含有されるため、無機微粒子分散スラリー組成物の粘度が好適な範囲となり、生産性を高めることができる。また、得られる無機微粒子分散シートのシート強度を適度なものとできる。更に、得られるセラミックグリーンシートの表面平滑性を充分に向上させることができる。
上記Ｍｗ／Ｍｎは３以上であることがより好ましく、６以下であることがより好ましい。
なお、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）は、ポリスチレン換算による平均分子量であり、カラムとして例えばカラムＬＦ－８０４（昭和電工社製）を用いてＧＰＣ測定を行うことで得ることができる。 <High molecular weight (meth)acrylic resin (A)>
In the (meth)acrylic resin composition of the present invention satisfying the above (1), the (meth)acrylic resin contains a high molecular weight (meth)acrylic resin (A).
The high molecular weight (meth)acrylic resin (A) has a weight average molecular weight of 120,000 or more and 300,000 or less.
Within the above range, the dispersibility of the inorganic fine particles can be sufficiently improved when the inorganic fine particle-dispersed slurry composition is prepared. In addition, aggregation of inorganic fine particles can be suppressed.
The weight average molecular weight is preferably 150,000 or more, more preferably 180,000 or more, preferably 250,000 or less, and more preferably 220,000 or less.
Within the above range, the inorganic fine particle-dispersed slurry composition has a sufficient viscosity, and the printability can be improved.
In addition, the ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the high molecular weight (meth)acrylic resin (A) is preferably 2 or more, and 8 or less. is preferred.
When the content is within the above range, the component having a low degree of polymerization is appropriately contained, so that the viscosity of the inorganic fine particle-dispersed slurry composition is within a suitable range, and the productivity can be enhanced. In addition, the sheet strength of the obtained inorganic fine particle-dispersed sheet can be made moderate. Furthermore, the surface smoothness of the resulting ceramic green sheet can be sufficiently improved.
The above Mw/Mn is more preferably 3 or more, and more preferably 6 or less.
The weight average molecular weight (Mw) and number average molecular weight (Mn) are average molecular weights in terms of polystyrene, and can be obtained by performing GPC measurement using, for example, a column LF-804 (manufactured by Showa Denko KK) as a column. can.
上記高分子量（メタ）アクリル樹脂（Ａ）中に含まれるＯＨ基の重量濃度が０．４重量％以上２．０重量％以下である。
上記範囲とすることで、バインダー樹脂が低温でも極めて優れた分解性を発現しつつ、更に、無機微粒子の分散性、凝集抑制効果を向上させることができる。
上記ＯＨ基の重量濃度は、０．５重量％以上であることが好ましく、０．６重量％以上であることがより好ましく、１．６重量％以下であることが好ましく、１．４重量％以下であることがより好ましい。
上記ＯＨ基の重量濃度は、高分子量（メタ）アクリル樹脂（Ａ）全体の重量に対するＯＨ基の重量の割合を意味し、以下の式に基づいて算出することができる。
高分子量（メタ）アクリル樹脂（Ａ）中に含まれるＯＨ基の重量濃度＝［全モノマー中に含まれるＯＨ基の重量／（全モノマーの重量＋重合開始剤の重量）］×１００ The weight concentration of OH groups contained in the high molecular weight (meth)acrylic resin (A) is 0.4% by weight or more and 2.0% by weight or less.
By setting the amount within the above range, the binder resin exhibits extremely excellent decomposability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
The weight concentration of the OH group is preferably 0.5% by weight or more, more preferably 0.6% by weight or more, preferably 1.6% by weight or less, and 1.4% by weight. The following are more preferable.
The weight concentration of the OH group means the ratio of the weight of the OH group to the total weight of the high-molecular-weight (meth)acrylic resin (A), and can be calculated based on the following formula.
Weight concentration of OH groups contained in high molecular weight (meth)acrylic resin (A) = [weight of OH groups contained in all monomers/(weight of all monomers + weight of polymerization initiator)] x 100
上記範囲とすることで、バインダー樹脂が低温でも極めて優れた分解性を発現しつつ、更に、無機微粒子の分散性、凝集抑制効果を向上させることができる。
上記ＯＨ基の重量濃度は、０．５重量％以上であることが好ましく、０．６重量％以上であることがより好ましく、１．６重量％以下であることが好ましく、１．４重量％以下であることがより好ましい。
上記ＯＨ基の重量濃度は、高分子量（メタ）アクリル樹脂（Ａ）全体の重量に対するＯＨ基の重量の割合を意味し、以下の式に基づいて算出することができる。
高分子量（メタ）アクリル樹脂（Ａ）中に含まれるＯＨ基の重量濃度＝［全モノマー中に含まれるＯＨ基の重量／（全モノマーの重量＋重合開始剤の重量）］×１００ The weight concentration of OH groups contained in the high molecular weight (meth)acrylic resin (A) is 0.4% by weight or more and 2.0% by weight or less.
By setting the amount within the above range, the binder resin exhibits extremely excellent decomposability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
The weight concentration of the OH group is preferably 0.5% by weight or more, more preferably 0.6% by weight or more, preferably 1.6% by weight or less, and 1.4% by weight. The following are more preferable.
The weight concentration of the OH group means the ratio of the weight of the OH group to the total weight of the high-molecular-weight (meth)acrylic resin (A), and can be calculated based on the following formula.
Weight concentration of OH groups contained in high molecular weight (meth)acrylic resin (A) = [weight of OH groups contained in all monomers/(weight of all monomers + weight of polymerization initiator)] x 100
＜高分子量（メタ）アクリル樹脂（Ｂ）＞
上記（２）を満たす本発明の（メタ）アクリル樹脂組成物において、上記（メタ）アクリル樹脂は、高分子量（メタ）アクリル樹脂（Ｂ）を含有する。
上記高分子量（メタ）アクリル樹脂（Ａ）は、重量平均分子量が３０万を超え５０万以下である。
上記範囲とすることで、無機微粒子分散スラリー組成物とした際、無機微粒子の分散性を充分向上させることができる。また、無機微粒子の凝集を抑制することができる。
上記重量平均分子量は、３２万以上であることが好ましく、３３万以上であることがより好ましく、４８万以下であることが好ましく、４５万以下であることがより好ましい。
上記範囲とすることで、無機微粒子分散スラリー組成物とした際、充分な粘度を有するものとなり、また、印刷性に向上できる。
また、上記高分子量（メタ）アクリル樹脂（Ｂ）の重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）は、２以上であることが好ましく、８以下であることが好ましい。
上記範囲内とすることで、低重合度の成分が適度に含有されるため、無機微粒子分散スラリー組成物の粘度が好適な範囲となり、生産性を高めることができる。また、得られる無機微粒子分散シートのシート強度を適度なものとできる。更に、得られるセラミックグリーンシートの表面平滑性を充分に向上させることができる。
上記Ｍｗ／Ｍｎは３以上であることがより好ましく、６以下であることがより好ましい。 <High molecular weight (meth)acrylic resin (B)>
In the (meth)acrylic resin composition of the present invention satisfying the above (2), the (meth)acrylic resin contains a high-molecular-weight (meth)acrylic resin (B).
The high molecular weight (meth)acrylic resin (A) has a weight average molecular weight of more than 300,000 and 500,000 or less.
Within the above range, the dispersibility of the inorganic fine particles can be sufficiently improved when the inorganic fine particle-dispersed slurry composition is prepared. In addition, aggregation of inorganic fine particles can be suppressed.
The weight average molecular weight is preferably 320,000 or more, more preferably 330,000 or more, preferably 480,000 or less, and more preferably 450,000 or less.
Within the above range, the inorganic fine particle-dispersed slurry composition has a sufficient viscosity, and the printability can be improved.
Further, the ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the high molecular weight (meth)acrylic resin (B) is preferably 2 or more, and 8 or less. is preferred.
When the content is within the above range, the component having a low degree of polymerization is appropriately contained, so that the viscosity of the inorganic fine particle-dispersed slurry composition is within a suitable range, and the productivity can be enhanced. In addition, the sheet strength of the obtained inorganic fine particle-dispersed sheet can be made moderate. Furthermore, the surface smoothness of the resulting ceramic green sheet can be sufficiently improved.
The above Mw/Mn is more preferably 3 or more, and more preferably 6 or less.
上記（２）を満たす本発明の（メタ）アクリル樹脂組成物において、上記（メタ）アクリル樹脂は、高分子量（メタ）アクリル樹脂（Ｂ）を含有する。
上記高分子量（メタ）アクリル樹脂（Ａ）は、重量平均分子量が３０万を超え５０万以下である。
上記範囲とすることで、無機微粒子分散スラリー組成物とした際、無機微粒子の分散性を充分向上させることができる。また、無機微粒子の凝集を抑制することができる。
上記重量平均分子量は、３２万以上であることが好ましく、３３万以上であることがより好ましく、４８万以下であることが好ましく、４５万以下であることがより好ましい。
上記範囲とすることで、無機微粒子分散スラリー組成物とした際、充分な粘度を有するものとなり、また、印刷性に向上できる。
また、上記高分子量（メタ）アクリル樹脂（Ｂ）の重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）は、２以上であることが好ましく、８以下であることが好ましい。
上記範囲内とすることで、低重合度の成分が適度に含有されるため、無機微粒子分散スラリー組成物の粘度が好適な範囲となり、生産性を高めることができる。また、得られる無機微粒子分散シートのシート強度を適度なものとできる。更に、得られるセラミックグリーンシートの表面平滑性を充分に向上させることができる。
上記Ｍｗ／Ｍｎは３以上であることがより好ましく、６以下であることがより好ましい。 <High molecular weight (meth)acrylic resin (B)>
In the (meth)acrylic resin composition of the present invention satisfying the above (2), the (meth)acrylic resin contains a high-molecular-weight (meth)acrylic resin (B).
The high molecular weight (meth)acrylic resin (A) has a weight average molecular weight of more than 300,000 and 500,000 or less.
Within the above range, the dispersibility of the inorganic fine particles can be sufficiently improved when the inorganic fine particle-dispersed slurry composition is prepared. In addition, aggregation of inorganic fine particles can be suppressed.
The weight average molecular weight is preferably 320,000 or more, more preferably 330,000 or more, preferably 480,000 or less, and more preferably 450,000 or less.
Within the above range, the inorganic fine particle-dispersed slurry composition has a sufficient viscosity, and the printability can be improved.
Further, the ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the high molecular weight (meth)acrylic resin (B) is preferably 2 or more, and 8 or less. is preferred.
When the content is within the above range, the component having a low degree of polymerization is appropriately contained, so that the viscosity of the inorganic fine particle-dispersed slurry composition is within a suitable range, and the productivity can be enhanced. In addition, the sheet strength of the obtained inorganic fine particle-dispersed sheet can be made moderate. Furthermore, the surface smoothness of the resulting ceramic green sheet can be sufficiently improved.
The above Mw/Mn is more preferably 3 or more, and more preferably 6 or less.
上記高分子量（メタ）アクリル樹脂（Ｂ）中に含まれるＯＨ基の重量濃度が１．３重量％以上３．５重量％以下である。
上記範囲とすることで、バインダー樹脂が低温でも極めて優れた分解性を発現しつつ、更に、無機微粒子の分散性、凝集抑制効果を向上させることができる。
上記ＯＨ基の重量濃度は、１．５重量％以上であることが好ましく、２重量％以上であることがより好ましく、３．３重量％以下であることが好ましく、３重量％以下であることがより好ましい。
上記ＯＨ基の重量濃度は、高分子量（メタ）アクリル樹脂（Ｂ）全体の重量に対するＯＨ基の重量の割合を意味し、以下の式に基づいて算出することができる。
高分子量（メタ）アクリル樹脂（Ｂ）中に含まれるＯＨ基の重量濃度＝［全モノマー中に含まれるＯＨ基の重量／（全モノマーの重量＋重合開始剤の重量）］×１００ The weight concentration of OH groups contained in the high molecular weight (meth)acrylic resin (B) is 1.3% by weight or more and 3.5% by weight or less.
By setting the amount within the above range, the binder resin exhibits extremely excellent decomposability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
The weight concentration of the OH group is preferably 1.5% by weight or more, more preferably 2% by weight or more, preferably 3.3% by weight or less, and 3% by weight or less. is more preferred.
The weight concentration of the OH group means the ratio of the weight of the OH group to the total weight of the high-molecular-weight (meth)acrylic resin (B), and can be calculated based on the following formula.
Weight concentration of OH groups contained in high molecular weight (meth)acrylic resin (B) = [weight of OH groups contained in all monomers/(weight of all monomers + weight of polymerization initiator)] x 100
上記範囲とすることで、バインダー樹脂が低温でも極めて優れた分解性を発現しつつ、更に、無機微粒子の分散性、凝集抑制効果を向上させることができる。
上記ＯＨ基の重量濃度は、１．５重量％以上であることが好ましく、２重量％以上であることがより好ましく、３．３重量％以下であることが好ましく、３重量％以下であることがより好ましい。
上記ＯＨ基の重量濃度は、高分子量（メタ）アクリル樹脂（Ｂ）全体の重量に対するＯＨ基の重量の割合を意味し、以下の式に基づいて算出することができる。
高分子量（メタ）アクリル樹脂（Ｂ）中に含まれるＯＨ基の重量濃度＝［全モノマー中に含まれるＯＨ基の重量／（全モノマーの重量＋重合開始剤の重量）］×１００ The weight concentration of OH groups contained in the high molecular weight (meth)acrylic resin (B) is 1.3% by weight or more and 3.5% by weight or less.
By setting the amount within the above range, the binder resin exhibits extremely excellent decomposability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
The weight concentration of the OH group is preferably 1.5% by weight or more, more preferably 2% by weight or more, preferably 3.3% by weight or less, and 3% by weight or less. is more preferred.
The weight concentration of the OH group means the ratio of the weight of the OH group to the total weight of the high-molecular-weight (meth)acrylic resin (B), and can be calculated based on the following formula.
Weight concentration of OH groups contained in high molecular weight (meth)acrylic resin (B) = [weight of OH groups contained in all monomers/(weight of all monomers + weight of polymerization initiator)] x 100
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）は、下記式（ａ）で表される構成単位を有することが好ましく、下記式（ｂ）で表される構成単位を有することが好ましい。
The high molecular weight (meth)acrylic resins (A) and (B) preferably have a structural unit represented by the following formula (a), and preferably have a structural unit represented by the following formula (b). .
式（ａ）中、Ｒ１は炭素数１～８の直鎖状又は分岐状アルキル基を表し、式（ｂ）中、Ｒ２は、水素原子の少なくとも１つがＯＨ基で置換された炭素数２～４の直鎖状又は分岐状アルキル基を表す。
上記Ｒ１としては、炭素数１～４の直鎖状又は分岐状アルキル基であることがより好ましく、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基等が挙げられる。
上記Ｒ２としては、水素原子の少なくとも１つがＯＨ基で置換された炭素数２～４の直鎖状又は分岐状アルキル基が好ましく、例えば、２－ヒドロキシエチル基、２－ヒドロキシプロピル基、２－ヒドロキシブチル基等が挙げられる。 In formula (a), R 1 represents a linear or branched alkyl group having 1 to 8 carbon atoms, and in formula (b), R 2 represents the number of carbon atoms in which at least one hydrogen atom is substituted with an OH group It represents 2 to 4 linear or branched alkyl groups.
R 1 above is more preferably a linear or branched alkyl group having 1 to 4 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group. etc.
R 2 is preferably a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one hydrogen atom is substituted with an OH group. -hydroxybutyl group and the like.
上記Ｒ１としては、炭素数１～４の直鎖状又は分岐状アルキル基であることがより好ましく、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基等が挙げられる。
上記Ｒ２としては、水素原子の少なくとも１つがＯＨ基で置換された炭素数２～４の直鎖状又は分岐状アルキル基が好ましく、例えば、２－ヒドロキシエチル基、２－ヒドロキシプロピル基、２－ヒドロキシブチル基等が挙げられる。 In formula (a), R 1 represents a linear or branched alkyl group having 1 to 8 carbon atoms, and in formula (b), R 2 represents the number of carbon atoms in which at least one hydrogen atom is substituted with an OH group It represents 2 to 4 linear or branched alkyl groups.
R 1 above is more preferably a linear or branched alkyl group having 1 to 4 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group. etc.
R 2 is preferably a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one hydrogen atom is substituted with an OH group. -hydroxybutyl group and the like.
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）における上記式（ａ）で表される構成単位の含有量は、７９重量％以上であることが好ましく、９６重量％以下であることが好ましい。
上記範囲とすることで、低温分解性を充分に高めることができる。
上記式（ａ）で表される構成単位の含有量は、８５重量％以上であることがより好ましく、９５重量％以下であることがより好ましい。 The content of the structural unit represented by the formula (a) in the high-molecular-weight (meth)acrylic resins (A) and (B) is preferably 79% by weight or more and 96% by weight or less. preferable.
By setting it as the said range, low-temperature decomposability can fully be improved.
The content of the structural unit represented by the above formula (a) is more preferably 85% by weight or more, and more preferably 95% by weight or less.
上記範囲とすることで、低温分解性を充分に高めることができる。
上記式（ａ）で表される構成単位の含有量は、８５重量％以上であることがより好ましく、９５重量％以下であることがより好ましい。 The content of the structural unit represented by the formula (a) in the high-molecular-weight (meth)acrylic resins (A) and (B) is preferably 79% by weight or more and 96% by weight or less. preferable.
By setting it as the said range, low-temperature decomposability can fully be improved.
The content of the structural unit represented by the above formula (a) is more preferably 85% by weight or more, and more preferably 95% by weight or less.
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）における上記式（ｂ）で表される構成単位の含有量は、３．１重量％以上であることが好ましく、１７重量％以下であることが好ましい。
バインダー樹脂に対する溶媒としてはエタノールがよく用いられるが、一般的にアクリル樹脂はポリビニルアセタール樹脂よりもエタノールに対する溶解性が低く、一次解砕後にアクリル樹脂を添加すると無機微粒子が凝集してしまうという問題があるが、上記範囲とすることで、無機微粒子の分散性や凝集抑制効果を向上させることができる。
また、エタノールに対する溶解性をより高めることができる。
上記式（２）で表される構成単位の含有量は、４重量％以上であることがより好ましく、１５重量％以下であることがより好ましい。 The content of the structural unit represented by the formula (b) in the high molecular weight (meth)acrylic resins (A) and (B) is preferably 3.1% by weight or more and 17% by weight or less. is preferred.
Ethanol is often used as a solvent for binder resins, but acrylic resins generally have lower solubility in ethanol than polyvinyl acetal resins. However, by setting the amount in the above range, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
Moreover, the solubility in ethanol can be further enhanced.
The content of the structural unit represented by the above formula (2) is more preferably 4% by weight or more, and more preferably 15% by weight or less.
バインダー樹脂に対する溶媒としてはエタノールがよく用いられるが、一般的にアクリル樹脂はポリビニルアセタール樹脂よりもエタノールに対する溶解性が低く、一次解砕後にアクリル樹脂を添加すると無機微粒子が凝集してしまうという問題があるが、上記範囲とすることで、無機微粒子の分散性や凝集抑制効果を向上させることができる。
また、エタノールに対する溶解性をより高めることができる。
上記式（２）で表される構成単位の含有量は、４重量％以上であることがより好ましく、１５重量％以下であることがより好ましい。 The content of the structural unit represented by the formula (b) in the high molecular weight (meth)acrylic resins (A) and (B) is preferably 3.1% by weight or more and 17% by weight or less. is preferred.
Ethanol is often used as a solvent for binder resins, but acrylic resins generally have lower solubility in ethanol than polyvinyl acetal resins. However, by setting the amount in the above range, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
Moreover, the solubility in ethanol can be further enhanced.
The content of the structural unit represented by the above formula (2) is more preferably 4% by weight or more, and more preferably 15% by weight or less.
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）は、炭素数３～４の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルに由来するセグメントを有することが好ましい。
上記セグメントを有することで、低温分解性により優れたものとできる。
上記炭素数３～４の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル等が挙げられる。なかでも、（メタ）アクリル酸イソブチルが好ましい。 The high-molecular-weight (meth)acrylic resins (A) and (B) preferably have segments derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 3 to 4 carbon atoms.
By having the above segment, the low-temperature decomposability can be made more excellent.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 3 to 4 carbon atoms include n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-(meth)acrylate. -butyl, isobutyl (meth)acrylate and the like. Among them, isobutyl (meth)acrylate is preferred.
上記セグメントを有することで、低温分解性により優れたものとできる。
上記炭素数３～４の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル等が挙げられる。なかでも、（メタ）アクリル酸イソブチルが好ましい。 The high-molecular-weight (meth)acrylic resins (A) and (B) preferably have segments derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 3 to 4 carbon atoms.
By having the above segment, the low-temperature decomposability can be made more excellent.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 3 to 4 carbon atoms include n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-(meth)acrylate. -butyl, isobutyl (meth)acrylate and the like. Among them, isobutyl (meth)acrylate is preferred.
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）における炭素数３～４の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルに由来するセグメントの含有量は、３０重量％以上であることが好ましく、４０重量％以上であることがより好ましく、９５重量％以下であることが好ましく、８８重量％以下であることがより好ましい。
The content of the segment derived from the (meth)acrylic acid ester having a linear or branched alkyl group having 3 to 4 carbon atoms in the high-molecular-weight (meth)acrylic resins (A) and (B) is 30% by weight. It is preferably 40% by weight or more, more preferably 40% by weight or more, preferably 95% by weight or less, and more preferably 88% by weight or less.
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）は、炭素数１～２のアルキル基を有する（メタ）アクリル酸エステルに由来するセグメントを有していてもよい。
上記炭素数１～２のアルキル基を有する（メタ）アクリル酸エステルとしては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチルが挙げられる。 The high-molecular-weight (meth)acrylic resins (A) and (B) may have segments derived from (meth)acrylic acid esters having alkyl groups of 1 to 2 carbon atoms.
Examples of the (meth)acrylic acid ester having an alkyl group having 1 to 2 carbon atoms include methyl (meth)acrylate and ethyl (meth)acrylate.
上記炭素数１～２のアルキル基を有する（メタ）アクリル酸エステルとしては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチルが挙げられる。 The high-molecular-weight (meth)acrylic resins (A) and (B) may have segments derived from (meth)acrylic acid esters having alkyl groups of 1 to 2 carbon atoms.
Examples of the (meth)acrylic acid ester having an alkyl group having 1 to 2 carbon atoms include methyl (meth)acrylate and ethyl (meth)acrylate.
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）における炭素数１～２のアルキル基を有する（メタ）アクリル酸エステルに由来するセグメントの含有量は、０重量％以上であることが好ましく、１０重量％以上であることがより好ましく、６６．８重量％以下であることが好ましく、４６重量％以下であることがより好ましい。
The content of the segment derived from the (meth)acrylic acid ester having an alkyl group having 1 to 2 carbon atoms in the high-molecular-weight (meth)acrylic resins (A) and (B) is preferably 0% by weight or more. , more preferably 10% by weight or more, preferably 66.8% by weight or less, and more preferably 46% by weight or less.
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）は、炭素数５～８の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルに由来するセグメントを有していてもよい。
上記炭素数５～８の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルとしては、（メタ）アクリル酸ｎ－ペンチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸ネオペンチル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸ｎ－ヘプチル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸２－エチルヘキシル等が挙げられる。なかでも、炭素数６～８の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルが好ましく、（メタ）アクリル酸２－エチルヘキシルがより好ましい。 The high-molecular-weight (meth)acrylic resins (A) and (B) may have a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 5 to 8 carbon atoms. good.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 5 to 8 carbon atoms include n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, Examples include n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate and 2-ethylhexyl (meth)acrylate. Among them, (meth)acrylic acid esters having a linear or branched alkyl group having 6 to 8 carbon atoms are preferred, and 2-ethylhexyl (meth)acrylate is more preferred.
上記炭素数５～８の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルとしては、（メタ）アクリル酸ｎ－ペンチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸ネオペンチル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸ｎ－ヘプチル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸２－エチルヘキシル等が挙げられる。なかでも、炭素数６～８の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルが好ましく、（メタ）アクリル酸２－エチルヘキシルがより好ましい。 The high-molecular-weight (meth)acrylic resins (A) and (B) may have a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 5 to 8 carbon atoms. good.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 5 to 8 carbon atoms include n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, Examples include n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate and 2-ethylhexyl (meth)acrylate. Among them, (meth)acrylic acid esters having a linear or branched alkyl group having 6 to 8 carbon atoms are preferred, and 2-ethylhexyl (meth)acrylate is more preferred.
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）における炭素数５～８の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルに由来するセグメントの含有量は、０重量％以上であることが好ましく、９重量％以上であることがより好ましく、２５重量％以下であることが好ましく、２０重量％以下であることがより好ましい。
The content of the segment derived from the (meth)acrylic acid ester having a linear or branched alkyl group having 5 to 8 carbon atoms in the high molecular weight (meth)acrylic resins (A) and (B) is 0 weight. % or more, more preferably 9 wt % or more, preferably 25 wt % or less, and more preferably 20 wt % or less.
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）は、炭素数９以上の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルに由来するセグメントを有していてもよい。
上記炭素数９以上の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸ｎ－ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸ｎ－デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ｎ－ラウリル、（メタ）アクリル酸イソラウリル、（メタ）アクリル酸ｎ－ステアリル、（メタ）アクリル酸イソステアリル等が挙げられる。 The high-molecular-weight (meth)acrylic resins (A) and (B) may have a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 9 or more carbon atoms. .
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 9 or more carbon atoms include n-nonyl (meth)acrylate, isononyl (meth)acrylate, and n (meth)acrylate. -decyl, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, isolauryl (meth)acrylate, n-stearyl (meth)acrylate, isostearyl (meth)acrylate and the like.
上記炭素数９以上の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸ｎ－ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸ｎ－デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ｎ－ラウリル、（メタ）アクリル酸イソラウリル、（メタ）アクリル酸ｎ－ステアリル、（メタ）アクリル酸イソステアリル等が挙げられる。 The high-molecular-weight (meth)acrylic resins (A) and (B) may have a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 9 or more carbon atoms. .
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 9 or more carbon atoms include n-nonyl (meth)acrylate, isononyl (meth)acrylate, and n (meth)acrylate. -decyl, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, isolauryl (meth)acrylate, n-stearyl (meth)acrylate, isostearyl (meth)acrylate and the like.
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）は、水素原子の少なくとも１つがＯＨ基で置換された直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルに由来するセグメントを有することが好ましい。
上記セグメントを有することにより、バインダー樹脂が低温でも極めて優れた分解性を発現しつつ、更に、無機微粒子の分散性、凝集抑制効果を向上させることができる。 The high-molecular-weight (meth)acrylic resins (A) and (B) contain segments derived from (meth)acrylic acid esters having linear or branched alkyl groups in which at least one of the hydrogen atoms is substituted with an OH group. It is preferable to have
By having the above segment, the binder resin exhibits extremely excellent degradability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
上記セグメントを有することにより、バインダー樹脂が低温でも極めて優れた分解性を発現しつつ、更に、無機微粒子の分散性、凝集抑制効果を向上させることができる。 The high-molecular-weight (meth)acrylic resins (A) and (B) contain segments derived from (meth)acrylic acid esters having linear or branched alkyl groups in which at least one of the hydrogen atoms is substituted with an OH group. It is preferable to have
By having the above segment, the binder resin exhibits extremely excellent degradability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
上記水素原子の少なくとも１つがＯＨ基で置換された直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルとしては、ＯＨ基の重量の割合が１０．５重量％以上であるものが好ましく、１１．５重量％以上であるものがより好ましく、１３．１重量％以下であるものが好ましい。
The (meth)acrylic acid ester having a linear or branched alkyl group in which at least one of the hydrogen atoms is substituted with an OH group preferably has an OH group weight ratio of 10.5% by weight or more. , more preferably 11.5% by weight or more, and preferably 13.1% by weight or less.
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）は、水素原子の少なくとも１つがＯＨ基で置換された炭素数２～４の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルに由来するセグメントを有することが好ましい。
上記水素原子の少なくとも１つがＯＨ基で置換された炭素数２～４の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシブチル、（メタ）アクリル酸４－ヒドロキシブチル等が挙げられる。なかでも、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチルが好ましい。 The high-molecular-weight (meth)acrylic resins (A) and (B) are (meth)acrylic acid having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group. It is preferred to have segments derived from esters.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. is mentioned. Among them, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate are preferred.
上記水素原子の少なくとも１つがＯＨ基で置換された炭素数２～４の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシブチル、（メタ）アクリル酸４－ヒドロキシブチル等が挙げられる。なかでも、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチルが好ましい。 The high-molecular-weight (meth)acrylic resins (A) and (B) are (meth)acrylic acid having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group. It is preferred to have segments derived from esters.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. is mentioned. Among them, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate are preferred.
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）における水素原子の少なくとも１つがＯＨ基で置換された炭素数２～４の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルに由来するセグメントの含有量は、３．１重量％以上であることが好ましく、５．０重量％以上であることがより好ましく、１７．０重量％以下であることが好ましく、１２．２重量％以下であることがより好ましい。
(Meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one hydrogen atom in the high-molecular-weight (meth)acrylic resins (A) and (B) is substituted with an OH group The content of the segment derived from is preferably 3.1% by weight or more, more preferably 5.0% by weight or more, preferably 17.0% by weight or less, and 12.2% by weight % or less.
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）は、水素原子の少なくとも１つがＯＨ基で置換された炭素数５以上の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルに由来するセグメントを有することが好ましい。
上記水素原子の少なくとも１つがＯＨ基で置換された炭素数５以上の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸ヒドロキシペンチル、（メタ）アクリル酸ヒドロキシヘキシル、（メタ）アクリル酸ヒドロキシヘプチル、（メタ）アクリル酸ヒドロキシオクチル等が挙げられる。 The high-molecular-weight (meth)acrylic resins (A) and (B) are (meth)acrylic acid esters having a linear or branched alkyl group having 5 or more carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group. It is preferred to have a segment derived from
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 5 or more carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group include hydroxypentyl (meth)acrylate, (meth) hydroxyhexyl acrylate, hydroxyheptyl (meth)acrylate, hydroxyoctyl (meth)acrylate and the like.
上記水素原子の少なくとも１つがＯＨ基で置換された炭素数５以上の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸ヒドロキシペンチル、（メタ）アクリル酸ヒドロキシヘキシル、（メタ）アクリル酸ヒドロキシヘプチル、（メタ）アクリル酸ヒドロキシオクチル等が挙げられる。 The high-molecular-weight (meth)acrylic resins (A) and (B) are (meth)acrylic acid esters having a linear or branched alkyl group having 5 or more carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group. It is preferred to have a segment derived from
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 5 or more carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group include hydroxypentyl (meth)acrylate, (meth) hydroxyhexyl acrylate, hydroxyheptyl (meth)acrylate, hydroxyoctyl (meth)acrylate and the like.
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）は、上記（メタ）アクリル酸エステルに由来するセグメントの他、（メタ）アクリル酸に由来するセグメント、グリシジル基を有する（メタ）アクリル酸エステル等の他の（メタ）アクリル酸エステルに由来するセグメントを有していてもよい。
The high-molecular weight (meth)acrylic resins (A) and (B) include segments derived from the (meth)acrylic acid ester, segments derived from (meth)acrylic acid, and (meth)acrylic acid having a glycidyl group. It may have segments derived from other (meth)acrylic acid esters such as esters.
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）のガラス転移温度（Ｔｇ）は３０℃以上８５℃以下であることが好ましい。
上記範囲とすることで、可塑剤の添加量を少なくすることができ、また、低温分解性を向上させることができる。
上記Ｔｇは３２℃以上であることがより好ましく、４２℃以上であることが更に好ましく、４５℃以上であることが更により好ましく、５０℃以上であることが特に好ましく、８０℃以下であることがより好ましく、７５℃以下であることが更に好ましい。
なお、上記ガラス転移温度（Ｔｇ）は、例えば、示差走査熱量計（ＤＳＣ）等を用いて測定することができる。 The glass transition temperature (Tg) of the high molecular weight (meth)acrylic resins (A) and (B) is preferably 30° C. or higher and 85° C. or lower.
By setting the amount within the above range, the amount of the plasticizer to be added can be reduced, and the low-temperature decomposability can be improved.
The Tg is more preferably 32° C. or higher, still more preferably 42° C. or higher, even more preferably 45° C. or higher, particularly preferably 50° C. or higher, and 80° C. or lower. is more preferable, and 75° C. or less is even more preferable.
The glass transition temperature (Tg) can be measured using, for example, a differential scanning calorimeter (DSC).
上記範囲とすることで、可塑剤の添加量を少なくすることができ、また、低温分解性を向上させることができる。
上記Ｔｇは３２℃以上であることがより好ましく、４２℃以上であることが更に好ましく、４５℃以上であることが更により好ましく、５０℃以上であることが特に好ましく、８０℃以下であることがより好ましく、７５℃以下であることが更に好ましい。
なお、上記ガラス転移温度（Ｔｇ）は、例えば、示差走査熱量計（ＤＳＣ）等を用いて測定することができる。 The glass transition temperature (Tg) of the high molecular weight (meth)acrylic resins (A) and (B) is preferably 30° C. or higher and 85° C. or lower.
By setting the amount within the above range, the amount of the plasticizer to be added can be reduced, and the low-temperature decomposability can be improved.
The Tg is more preferably 32° C. or higher, still more preferably 42° C. or higher, even more preferably 45° C. or higher, particularly preferably 50° C. or higher, and 80° C. or lower. is more preferable, and 75° C. or less is even more preferable.
The glass transition temperature (Tg) can be measured using, for example, a differential scanning calorimeter (DSC).
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）は、エタノールへの溶解度が１０重量部／エタノール１００重量部以上であることが好ましい。
上記範囲とすることで、無機微粒子の分散性、凝集抑制効果を向上させることができる。また、有機溶剤への溶解度を充分に高めることができる。
上記エタノールへの溶解度は、５０重量部以上であることがより好ましく、１００重量部以上であること更に好ましい。
上記エタノールへの溶解度は、２５℃の環境下でエタノール１００重量部に溶解させた際、析出物が生じるまでに要した樹脂の添加量を意味する。 The above high molecular weight (meth)acrylic resins (A) and (B) preferably have a solubility in ethanol of 10 parts by weight/100 parts by weight or more of ethanol.
By setting it as the said range, the dispersibility of an inorganic fine particle and the aggregation inhibitory effect can be improved. In addition, the solubility in organic solvents can be sufficiently increased.
The solubility in ethanol is more preferably 50 parts by weight or more, and even more preferably 100 parts by weight or more.
The above-mentioned solubility in ethanol means the amount of resin added required until precipitation occurs when dissolved in 100 parts by weight of ethanol in an environment of 25°C.
上記範囲とすることで、無機微粒子の分散性、凝集抑制効果を向上させることができる。また、有機溶剤への溶解度を充分に高めることができる。
上記エタノールへの溶解度は、５０重量部以上であることがより好ましく、１００重量部以上であること更に好ましい。
上記エタノールへの溶解度は、２５℃の環境下でエタノール１００重量部に溶解させた際、析出物が生じるまでに要した樹脂の添加量を意味する。 The above high molecular weight (meth)acrylic resins (A) and (B) preferably have a solubility in ethanol of 10 parts by weight/100 parts by weight or more of ethanol.
By setting it as the said range, the dispersibility of an inorganic fine particle and the aggregation inhibitory effect can be improved. In addition, the solubility in organic solvents can be sufficiently increased.
The solubility in ethanol is more preferably 50 parts by weight or more, and even more preferably 100 parts by weight or more.
The above-mentioned solubility in ethanol means the amount of resin added required until precipitation occurs when dissolved in 100 parts by weight of ethanol in an environment of 25°C.
本発明の（メタ）アクリル樹脂組成物における上記高分子量（メタ）アクリル樹脂（Ａ）の含有量は、５重量％以上であることが好ましく、１０重量％以上であることがより好ましく、３０重量％以上であることが更に好ましく、７０重量％以下であることが好ましく、６０重量％以下であることがより好ましい。
The content of the high molecular weight (meth)acrylic resin (A) in the (meth)acrylic resin composition of the present invention is preferably 5% by weight or more, more preferably 10% by weight or more, and 30% by weight. % or more, preferably 70% by weight or less, and more preferably 60% by weight or less.
本発明の（メタ）アクリル樹脂組成物における上記高分子量（メタ）アクリル樹脂（Ｂ）の含有量は、５重量％以上であることが好ましく、１０重量％以上であることがより好ましく、３０重量％以上であることが更に好ましく、７０重量％以下であることが好ましく、６０重量％以下であることがより好ましい。
The content of the high molecular weight (meth)acrylic resin (B) in the (meth)acrylic resin composition of the present invention is preferably 5% by weight or more, more preferably 10% by weight or more, and 30% by weight. % or more, preferably 70% by weight or less, and more preferably 60% by weight or less.
また、上記（２）を満たす本発明の（メタ）アクリル樹脂組成物において、上記（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度は２５０ｐｐｍ以上であることが好ましく、２００００ｐｐｍ以下であることが好ましい。
上記範囲とすることで、バインダー樹脂が低温でも極めて優れた分解性を発現しつつ、更に、無機微粒子の分散性、凝集抑制効果を向上させることができる。
上記Ｓ原子の重量濃度は、４００ｐｐｍ以上であることがより好ましく、１５０００ｐｐｍ以下であることがより好ましい。
上記Ｓ原子の重量濃度は、（メタ）アクリル樹脂の重量に対するＳ原子の重量の割合を意味し、以下の式に基づいて算出することができる。
（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度＝［連鎖移動剤に含まれるＳ原子の重量／（全モノマーの重量＋重合開始剤の重量＋連鎖移動剤の重量）］×１００
なお、上記（メタ）アクリル樹脂組成物が複数の（メタ）アクリル樹脂を含有する場合、上記Ｓ原子の重量濃度は、各（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度及び各（メタ）アクリル樹脂の配合割合に基づいて算出することができる。
また、上記Ｓ原子の重量濃度は、ＩＣＰ－ＡＥＳ（誘導結合プラズマ発光分光分析法）によっても求めることができる。 In the (meth)acrylic resin composition of the present invention satisfying the above (2), the weight concentration of S atoms contained in the (meth)acrylic resin is preferably 250 ppm or more, and preferably 20000 ppm or less. preferable.
By setting the amount within the above range, the binder resin exhibits extremely excellent decomposability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
The weight concentration of the S atoms is more preferably 400 ppm or more, and more preferably 15000 ppm or less.
The weight concentration of S atoms means the ratio of the weight of S atoms to the weight of the (meth)acrylic resin, and can be calculated based on the following formula.
Weight concentration of S atoms contained in (meth)acrylic resin = [weight of S atoms contained in chain transfer agent/(weight of all monomers + weight of polymerization initiator + weight of chain transfer agent)] × 100
When the (meth)acrylic resin composition contains a plurality of (meth)acrylic resins, the weight concentration of the S atoms is the weight concentration of the S atoms contained in each (meth)acrylic resin and each (meth)acrylic resin. ) can be calculated based on the mixing ratio of the acrylic resin.
The weight concentration of S atoms can also be determined by ICP-AES (inductively coupled plasma atomic emission spectrometry).
上記範囲とすることで、バインダー樹脂が低温でも極めて優れた分解性を発現しつつ、更に、無機微粒子の分散性、凝集抑制効果を向上させることができる。
上記Ｓ原子の重量濃度は、４００ｐｐｍ以上であることがより好ましく、１５０００ｐｐｍ以下であることがより好ましい。
上記Ｓ原子の重量濃度は、（メタ）アクリル樹脂の重量に対するＳ原子の重量の割合を意味し、以下の式に基づいて算出することができる。
（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度＝［連鎖移動剤に含まれるＳ原子の重量／（全モノマーの重量＋重合開始剤の重量＋連鎖移動剤の重量）］×１００
なお、上記（メタ）アクリル樹脂組成物が複数の（メタ）アクリル樹脂を含有する場合、上記Ｓ原子の重量濃度は、各（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度及び各（メタ）アクリル樹脂の配合割合に基づいて算出することができる。
また、上記Ｓ原子の重量濃度は、ＩＣＰ－ＡＥＳ（誘導結合プラズマ発光分光分析法）によっても求めることができる。 In the (meth)acrylic resin composition of the present invention satisfying the above (2), the weight concentration of S atoms contained in the (meth)acrylic resin is preferably 250 ppm or more, and preferably 20000 ppm or less. preferable.
By setting the amount within the above range, the binder resin exhibits extremely excellent decomposability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
The weight concentration of the S atoms is more preferably 400 ppm or more, and more preferably 15000 ppm or less.
The weight concentration of S atoms means the ratio of the weight of S atoms to the weight of the (meth)acrylic resin, and can be calculated based on the following formula.
Weight concentration of S atoms contained in (meth)acrylic resin = [weight of S atoms contained in chain transfer agent/(weight of all monomers + weight of polymerization initiator + weight of chain transfer agent)] × 100
When the (meth)acrylic resin composition contains a plurality of (meth)acrylic resins, the weight concentration of the S atoms is the weight concentration of the S atoms contained in each (meth)acrylic resin and each (meth)acrylic resin. ) can be calculated based on the mixing ratio of the acrylic resin.
The weight concentration of S atoms can also be determined by ICP-AES (inductively coupled plasma atomic emission spectrometry).
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）を製造する方法は特に限定されない。例えば、（メタ）アクリル酸エステル等を含む原料モノマー混合物に有機溶剤等を加えてモノマー混合液を調整し、更に、得られたモノマー混合液に重合開始剤、連鎖移動剤を添加して、上記原料モノマーを共重合させる方法が挙げられる。
重合させる方法は特に限定されず、乳化重合、懸濁重合、塊状重合、界面重合、溶液重合等が挙げられる。なかでも、溶液重合が好ましい。 The method for producing the high molecular weight (meth)acrylic resins (A) and (B) is not particularly limited. For example, an organic solvent or the like is added to a raw material monomer mixture containing (meth) acrylic acid ester or the like to prepare a monomer mixture, and a polymerization initiator and a chain transfer agent are added to the obtained monomer mixture, and the above A method of copolymerizing raw material monomers may be mentioned.
The polymerization method is not particularly limited, and examples thereof include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, and solution polymerization. Among them, solution polymerization is preferred.
重合させる方法は特に限定されず、乳化重合、懸濁重合、塊状重合、界面重合、溶液重合等が挙げられる。なかでも、溶液重合が好ましい。 The method for producing the high molecular weight (meth)acrylic resins (A) and (B) is not particularly limited. For example, an organic solvent or the like is added to a raw material monomer mixture containing (meth) acrylic acid ester or the like to prepare a monomer mixture, and a polymerization initiator and a chain transfer agent are added to the obtained monomer mixture, and the above A method of copolymerizing raw material monomers may be mentioned.
The polymerization method is not particularly limited, and examples thereof include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, and solution polymerization. Among them, solution polymerization is preferred.
上記重合開始剤としては、例えば、ｔ－ブチルパーオキシピバレート、Ｐ－メンタンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、１，１，３，３－テトラメチルブチルハイドロパーオキサイド、クメンハイドロキシパーオキサイド、ｔ－ブチルハイドロキシパーオキサイド、過酸化シクロヘキサノン、ジコハク酸パーオキサイド等が挙げられる。
上記連鎖移動剤としては、例えば、３－メルカプト－１，２－プロパンジオール、３－メルカプト－１－プロパノール、３－メルカプト－２－ブタノール、８－メルカプト－１－オクタノール、メルカプトコハク酸、メルカプト酢酸等が挙げられる。 Examples of the polymerization initiator include t-butyl peroxypivalate, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroxyperoxide, t-butyl hydroxyperoxide, cyclohexanone peroxide, disuccinic acid peroxide and the like.
Examples of the chain transfer agent include 3-mercapto-1,2-propanediol, 3-mercapto-1-propanol, 3-mercapto-2-butanol, 8-mercapto-1-octanol, mercaptosuccinic acid, and mercaptoacetic acid. etc.
上記連鎖移動剤としては、例えば、３－メルカプト－１，２－プロパンジオール、３－メルカプト－１－プロパノール、３－メルカプト－２－ブタノール、８－メルカプト－１－オクタノール、メルカプトコハク酸、メルカプト酢酸等が挙げられる。 Examples of the polymerization initiator include t-butyl peroxypivalate, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroxyperoxide, t-butyl hydroxyperoxide, cyclohexanone peroxide, disuccinic acid peroxide and the like.
Examples of the chain transfer agent include 3-mercapto-1,2-propanediol, 3-mercapto-1-propanol, 3-mercapto-2-butanol, 8-mercapto-1-octanol, mercaptosuccinic acid, and mercaptoacetic acid. etc.
＜低分子量（メタ）アクリル樹脂（Ｃ）＞
上記（３）を満たす本発明の（メタ）アクリル樹脂組成物において、上記（メタ）アクリル樹脂は、低分子量（メタ）アクリル樹脂（Ｃ）を含有する。
本明細書において、上記低分子量（メタ）アクリル樹脂（Ｃ）は、重量平均分子量が０．５万以上１０万以下である。
上記低分子量（メタ）アクリル樹脂（Ｃ）を含有することで、無機微粒子に分散性を向上させることができる。
上記重量平均分子量は、０．６万以上であることがより好ましく、０．８万以上であることが更に好ましく、９万以下であることがより好ましく、３万以下であることが更に好ましい。
また、上記低分子量（メタ）アクリル樹脂（Ｃ）の重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）は、１．３以上であることが好ましく、２以上であることがより好ましく、８以下であることが好ましい。
上記範囲内とすることで、低重合度の成分が適度に含有されるため、無機微粒子分散スラリー組成物の粘度が好適な範囲となり、生産性を高めることができる。また、得られる無機微粒子分散シートのシート強度を適度なものとできる。更に、得られるセラミックグリーンシートの表面平滑性を充分に向上できる。
上記Ｍｗ／Ｍｎは３以上であることがより好ましく、６以下であることがより好ましい。
なお、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）は、ポリスチレン換算による平均分子量であり、カラムとして例えばカラムＬＦ－８０４（昭和電工社製）を用いてＧＰＣ測定を行うことで得ることができる。 <Low molecular weight (meth)acrylic resin (C)>
In the (meth)acrylic resin composition of the present invention satisfying the above (3), the (meth)acrylic resin contains a low molecular weight (meth)acrylic resin (C).
In this specification, the low molecular weight (meth)acrylic resin (C) has a weight average molecular weight of 5,000 or more and 100,000 or less.
By containing the low-molecular-weight (meth)acrylic resin (C), the dispersibility of the inorganic fine particles can be improved.
The weight average molecular weight is more preferably 6,000 or more, still more preferably 8,000 or more, more preferably 90,000 or less, and even more preferably 30,000 or less.
Further, the ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the low molecular weight (meth)acrylic resin (C) is preferably 1.3 or more, and 2 or more. It is more preferable that there is one, and it is preferable that it is 8 or less.
When the content is within the above range, the component having a low degree of polymerization is appropriately contained, so that the viscosity of the inorganic fine particle-dispersed slurry composition is within a suitable range, and the productivity can be enhanced. In addition, the sheet strength of the obtained inorganic fine particle-dispersed sheet can be made moderate. Furthermore, the surface smoothness of the resulting ceramic green sheet can be sufficiently improved.
The above Mw/Mn is more preferably 3 or more, and more preferably 6 or less.
The weight average molecular weight (Mw) and number average molecular weight (Mn) are average molecular weights in terms of polystyrene, and can be obtained by performing GPC measurement using, for example, a column LF-804 (manufactured by Showa Denko KK) as a column. can.
上記（３）を満たす本発明の（メタ）アクリル樹脂組成物において、上記（メタ）アクリル樹脂は、低分子量（メタ）アクリル樹脂（Ｃ）を含有する。
本明細書において、上記低分子量（メタ）アクリル樹脂（Ｃ）は、重量平均分子量が０．５万以上１０万以下である。
上記低分子量（メタ）アクリル樹脂（Ｃ）を含有することで、無機微粒子に分散性を向上させることができる。
上記重量平均分子量は、０．６万以上であることがより好ましく、０．８万以上であることが更に好ましく、９万以下であることがより好ましく、３万以下であることが更に好ましい。
また、上記低分子量（メタ）アクリル樹脂（Ｃ）の重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）は、１．３以上であることが好ましく、２以上であることがより好ましく、８以下であることが好ましい。
上記範囲内とすることで、低重合度の成分が適度に含有されるため、無機微粒子分散スラリー組成物の粘度が好適な範囲となり、生産性を高めることができる。また、得られる無機微粒子分散シートのシート強度を適度なものとできる。更に、得られるセラミックグリーンシートの表面平滑性を充分に向上できる。
上記Ｍｗ／Ｍｎは３以上であることがより好ましく、６以下であることがより好ましい。
なお、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）は、ポリスチレン換算による平均分子量であり、カラムとして例えばカラムＬＦ－８０４（昭和電工社製）を用いてＧＰＣ測定を行うことで得ることができる。 <Low molecular weight (meth)acrylic resin (C)>
In the (meth)acrylic resin composition of the present invention satisfying the above (3), the (meth)acrylic resin contains a low molecular weight (meth)acrylic resin (C).
In this specification, the low molecular weight (meth)acrylic resin (C) has a weight average molecular weight of 5,000 or more and 100,000 or less.
By containing the low-molecular-weight (meth)acrylic resin (C), the dispersibility of the inorganic fine particles can be improved.
The weight average molecular weight is more preferably 6,000 or more, still more preferably 8,000 or more, more preferably 90,000 or less, and even more preferably 30,000 or less.
Further, the ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the low molecular weight (meth)acrylic resin (C) is preferably 1.3 or more, and 2 or more. It is more preferable that there is one, and it is preferable that it is 8 or less.
When the content is within the above range, the component having a low degree of polymerization is appropriately contained, so that the viscosity of the inorganic fine particle-dispersed slurry composition is within a suitable range, and the productivity can be enhanced. In addition, the sheet strength of the obtained inorganic fine particle-dispersed sheet can be made moderate. Furthermore, the surface smoothness of the resulting ceramic green sheet can be sufficiently improved.
The above Mw/Mn is more preferably 3 or more, and more preferably 6 or less.
The weight average molecular weight (Mw) and number average molecular weight (Mn) are average molecular weights in terms of polystyrene, and can be obtained by performing GPC measurement using, for example, a column LF-804 (manufactured by Showa Denko KK) as a column. can.
上記低分子量（メタ）アクリル樹脂（Ｃ）中に含まれるＯＨ基の重量濃度は、１．３重量％以上３．５重量％以下である。
上記範囲とすることで、バインダー樹脂が低温でも極めて優れた分解性を発現しつつ、更に、無機微粒子の分散性、凝集抑制効果を向上させることができる。
上記ＯＨ基の重量濃度は、１．４重量％以上であることが好ましく、３．３重量％以下であることが好ましく、３．２重量％以下であることがより好ましい。
上記ＯＨ基の重量濃度は、低分子量（メタ）アクリル樹脂（Ｃ）全体の重量に対するＯＨ基の重量の割合を意味し、以下の式に基づいて算出することができる。
低分子量（メタ）アクリル樹脂（Ｃ）中に含まれるＯＨ基の重量濃度＝［（全モノマー中に含まれるＯＨ基の重量＋連鎖移動剤に含まれるＯＨ基の重量）／（全モノマーの重量＋重合開始剤の重量＋連鎖移動剤の重量）］×１００ The weight concentration of OH groups contained in the low molecular weight (meth)acrylic resin (C) is 1.3% by weight or more and 3.5% by weight or less.
By setting the amount within the above range, the binder resin exhibits extremely excellent decomposability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
The weight concentration of the OH groups is preferably 1.4% by weight or more, preferably 3.3% by weight or less, and more preferably 3.2% by weight or less.
The weight concentration of OH groups means the ratio of the weight of OH groups to the total weight of the low-molecular-weight (meth)acrylic resin (C), and can be calculated based on the following formula.
Weight concentration of OH groups contained in the low molecular weight (meth) acrylic resin (C) = [(weight of OH groups contained in all monomers + weight of OH groups contained in chain transfer agent) / (weight of all monomers + weight of polymerization initiator + weight of chain transfer agent)] × 100
上記範囲とすることで、バインダー樹脂が低温でも極めて優れた分解性を発現しつつ、更に、無機微粒子の分散性、凝集抑制効果を向上させることができる。
上記ＯＨ基の重量濃度は、１．４重量％以上であることが好ましく、３．３重量％以下であることが好ましく、３．２重量％以下であることがより好ましい。
上記ＯＨ基の重量濃度は、低分子量（メタ）アクリル樹脂（Ｃ）全体の重量に対するＯＨ基の重量の割合を意味し、以下の式に基づいて算出することができる。
低分子量（メタ）アクリル樹脂（Ｃ）中に含まれるＯＨ基の重量濃度＝［（全モノマー中に含まれるＯＨ基の重量＋連鎖移動剤に含まれるＯＨ基の重量）／（全モノマーの重量＋重合開始剤の重量＋連鎖移動剤の重量）］×１００ The weight concentration of OH groups contained in the low molecular weight (meth)acrylic resin (C) is 1.3% by weight or more and 3.5% by weight or less.
By setting the amount within the above range, the binder resin exhibits extremely excellent decomposability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
The weight concentration of the OH groups is preferably 1.4% by weight or more, preferably 3.3% by weight or less, and more preferably 3.2% by weight or less.
The weight concentration of OH groups means the ratio of the weight of OH groups to the total weight of the low-molecular-weight (meth)acrylic resin (C), and can be calculated based on the following formula.
Weight concentration of OH groups contained in the low molecular weight (meth) acrylic resin (C) = [(weight of OH groups contained in all monomers + weight of OH groups contained in chain transfer agent) / (weight of all monomers + weight of polymerization initiator + weight of chain transfer agent)] × 100
上記低分子量（メタ）アクリル樹脂（Ｃ）は、炭素数３～４の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルに由来するセグメントを有することが好ましい。
上記セグメントを有することで、低温分解性により優れたものとできる。
上記炭素数３～４の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル等が挙げられる。なかでも、（メタ）アクリル酸イソブチルが好ましい。 The low-molecular-weight (meth)acrylic resin (C) preferably has a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group with 3 to 4 carbon atoms.
By having the above segment, the low-temperature decomposability can be made more excellent.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 3 to 4 carbon atoms include n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-(meth)acrylate. -butyl, isobutyl (meth)acrylate and the like. Among them, isobutyl (meth)acrylate is preferred.
上記セグメントを有することで、低温分解性により優れたものとできる。
上記炭素数３～４の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル等が挙げられる。なかでも、（メタ）アクリル酸イソブチルが好ましい。 The low-molecular-weight (meth)acrylic resin (C) preferably has a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group with 3 to 4 carbon atoms.
By having the above segment, the low-temperature decomposability can be made more excellent.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 3 to 4 carbon atoms include n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-(meth)acrylate. -butyl, isobutyl (meth)acrylate and the like. Among them, isobutyl (meth)acrylate is preferred.
上記低分子量（メタ）アクリル樹脂（Ｃ）における炭素数３～４の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルに由来するセグメントの含有量は、３８重量％以上であることが好ましく、５０重量％以上であることがより好ましく、８０重量％以下であることが好ましく、７５重量％以下であることがより好ましい。
The content of the segment derived from the (meth)acrylic acid ester having a linear or branched alkyl group having 3 to 4 carbon atoms in the low molecular weight (meth)acrylic resin (C) is 38% by weight or more. , more preferably 50% by weight or more, preferably 80% by weight or less, and more preferably 75% by weight or less.
上記低分子量（メタ）アクリル樹脂（Ｃ）は、炭素数１～２のアルキル基を有する（メタ）アクリル酸エステルに由来するセグメントを有していてもよい。
上記炭素数１～２のアルキル基を有する（メタ）アクリル酸エステルとしては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチルが挙げられる。 The low-molecular-weight (meth)acrylic resin (C) may have a segment derived from a (meth)acrylic acid ester having an alkyl group having 1 to 2 carbon atoms.
Examples of the (meth)acrylic acid ester having an alkyl group having 1 to 2 carbon atoms include methyl (meth)acrylate and ethyl (meth)acrylate.
上記炭素数１～２のアルキル基を有する（メタ）アクリル酸エステルとしては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチルが挙げられる。 The low-molecular-weight (meth)acrylic resin (C) may have a segment derived from a (meth)acrylic acid ester having an alkyl group having 1 to 2 carbon atoms.
Examples of the (meth)acrylic acid ester having an alkyl group having 1 to 2 carbon atoms include methyl (meth)acrylate and ethyl (meth)acrylate.
上記低分子量（メタ）アクリル樹脂（Ｃ）における炭素数１～２のアルキル基を有する（メタ）アクリル酸エステルに由来するセグメントの含有量は、０重量％以上であることが好ましく、７重量％以上であることがより好ましく、３３重量％以下であることが好ましく、２０．５重量％以下であることがより好ましい。
The content of the segment derived from the (meth)acrylic acid ester having an alkyl group having 1 to 2 carbon atoms in the low molecular weight (meth)acrylic resin (C) is preferably 0% by weight or more, and 7% by weight. It is more preferably 33% by weight or less, and more preferably 20.5% by weight or less.
上記低分子量（メタ）アクリル樹脂（Ｃ）は、炭素数５～８の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルに由来するセグメントを有していてもよい。
上記炭素数５～８の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルとしては、（メタ）アクリル酸ｎ－ペンチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸ネオペンチル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸ｎ－ヘプチル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸２－エチルヘキシル等が挙げられる。なかでも、炭素数６～８の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルが好ましく、（メタ）アクリル酸２－エチルヘキシルがより好ましい。 The low-molecular-weight (meth)acrylic resin (C) may have a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group with 5 to 8 carbon atoms.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 5 to 8 carbon atoms include n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, Examples include n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate and 2-ethylhexyl (meth)acrylate. Among them, (meth)acrylic acid esters having a linear or branched alkyl group having 6 to 8 carbon atoms are preferred, and 2-ethylhexyl (meth)acrylate is more preferred.
上記炭素数５～８の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルとしては、（メタ）アクリル酸ｎ－ペンチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸ネオペンチル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸ｎ－ヘプチル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸２－エチルヘキシル等が挙げられる。なかでも、炭素数６～８の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルが好ましく、（メタ）アクリル酸２－エチルヘキシルがより好ましい。 The low-molecular-weight (meth)acrylic resin (C) may have a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group with 5 to 8 carbon atoms.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 5 to 8 carbon atoms include n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, Examples include n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate and 2-ethylhexyl (meth)acrylate. Among them, (meth)acrylic acid esters having a linear or branched alkyl group having 6 to 8 carbon atoms are preferred, and 2-ethylhexyl (meth)acrylate is more preferred.
上記低分子量（メタ）アクリル樹脂（Ｃ）における炭素数５～８の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルに由来するセグメントの含有量は、０重量％以上であることが好ましく、１０重量％以上であることがより好ましく、４０重量％以下であることが好ましく、３０重量％以下であることがより好ましい。
The content of the segment derived from the (meth)acrylic acid ester having a linear or branched alkyl group having 5 to 8 carbon atoms in the low molecular weight (meth)acrylic resin (C) is 0% by weight or more. It is preferably 10% by weight or more, more preferably 40% by weight or less, and more preferably 30% by weight or less.
上記低分子量（メタ）アクリル樹脂（Ｃ）は、炭素数９以上の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルに由来するセグメントを有していてもよい。
上記炭素数９以上の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸ｎ－ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸ｎ－デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ｎ－ラウリル、（メタ）アクリル酸イソラウリル、（メタ）アクリル酸ｎ－ステアリル、（メタ）アクリル酸イソステアリル等が挙げられる。 The low-molecular-weight (meth)acrylic resin (C) may have a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group with 9 or more carbon atoms.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 9 or more carbon atoms include n-nonyl (meth)acrylate, isononyl (meth)acrylate, and n (meth)acrylate. -decyl, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, isolauryl (meth)acrylate, n-stearyl (meth)acrylate, isostearyl (meth)acrylate and the like.
上記炭素数９以上の直鎖状又は分岐状のアルキル基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸ｎ－ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸ｎ－デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ｎ－ラウリル、（メタ）アクリル酸イソラウリル、（メタ）アクリル酸ｎ－ステアリル、（メタ）アクリル酸イソステアリル等が挙げられる。 The low-molecular-weight (meth)acrylic resin (C) may have a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group with 9 or more carbon atoms.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 9 or more carbon atoms include n-nonyl (meth)acrylate, isononyl (meth)acrylate, and n (meth)acrylate. -decyl, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, isolauryl (meth)acrylate, n-stearyl (meth)acrylate, isostearyl (meth)acrylate and the like.
上記低分子量（メタ）アクリル樹脂（Ｃ）は、水素原子の少なくとも１つがＯＨ基で置換された直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルに由来するセグメントを有することが好ましい。
上記セグメントを有することにより、バインダー樹脂が低温でも極めて優れた分解性を発現しつつ、更に、無機微粒子の分散性、凝集抑制効果を向上させることができる。 The low-molecular-weight (meth)acrylic resin (C) preferably has a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group in which at least one of the hydrogen atoms is substituted with an OH group. .
By having the above segment, the binder resin exhibits extremely excellent degradability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
上記セグメントを有することにより、バインダー樹脂が低温でも極めて優れた分解性を発現しつつ、更に、無機微粒子の分散性、凝集抑制効果を向上させることができる。 The low-molecular-weight (meth)acrylic resin (C) preferably has a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group in which at least one of the hydrogen atoms is substituted with an OH group. .
By having the above segment, the binder resin exhibits extremely excellent degradability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
上記水素原子の少なくとも１つがＯＨ基で置換された直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルとしては、ＯＨ基の重量の割合が１０．５重量％以上であるものが好ましく、１１．５重量％以上であるものがより好ましく、１３．１重量％以下であるものが好ましい。
The (meth)acrylic acid ester having a linear or branched alkyl group in which at least one of the hydrogen atoms is substituted with an OH group preferably has an OH group weight ratio of 10.5% by weight or more. , more preferably 11.5% by weight or more, and preferably 13.1% by weight or less.
上記低分子量（メタ）アクリル樹脂（Ｃ）は、水素原子の少なくとも１つがＯＨ基で置換された炭素数２～４の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルに由来するセグメントを有することが好ましい。
上記水素原子の少なくとも１つがＯＨ基で置換された炭素数２～４の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシブチル、（メタ）アクリル酸４－ヒドロキシブチル等が挙げられる。なかでも、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチルが好ましい。 The low-molecular-weight (meth)acrylic resin (C) is derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group. It is preferred to have segments.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. is mentioned. Among them, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate are preferred.
上記水素原子の少なくとも１つがＯＨ基で置換された炭素数２～４の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシブチル、（メタ）アクリル酸４－ヒドロキシブチル等が挙げられる。なかでも、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチルが好ましい。 The low-molecular-weight (meth)acrylic resin (C) is derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group. It is preferred to have segments.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. is mentioned. Among them, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate are preferred.
上記低分子量（メタ）アクリル樹脂（Ｃ）における水素原子の少なくとも１つがＯＨ基で置換された炭素数２～４の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルに由来するセグメントの含有量は、７重量％以上であることが好ましく、１０重量％以上であることがより好ましく、２０重量％以下であることが好ましく、１６重量％以下であることがより好ましい。
A segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one of the hydrogen atoms in the low molecular weight (meth)acrylic resin (C) is substituted with an OH group is preferably 7% by weight or more, more preferably 10% by weight or more, preferably 20% by weight or less, and more preferably 16% by weight or less.
上記低分子量（メタ）アクリル樹脂（Ｃ）は、水素原子の少なくとも１つがＯＨ基で置換された炭素数５以上の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルに由来するセグメントを有することが好ましい。
上記水素原子の少なくとも１つがＯＨ基で置換された炭素数５以上の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸ヒドロキシペンチル、（メタ）アクリル酸ヒドロキシヘキシル、（メタ）アクリル酸ヒドロキシヘプチル、（メタ）アクリル酸ヒドロキシオクチル等が挙げられる。 The low-molecular-weight (meth)acrylic resin (C) is a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 5 or more carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group. It is preferred to have
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 5 or more carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group include hydroxypentyl (meth)acrylate, (meth) hydroxyhexyl acrylate, hydroxyheptyl (meth)acrylate, hydroxyoctyl (meth)acrylate and the like.
上記水素原子の少なくとも１つがＯＨ基で置換された炭素数５以上の直鎖状又は分岐状アルキル基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸ヒドロキシペンチル、（メタ）アクリル酸ヒドロキシヘキシル、（メタ）アクリル酸ヒドロキシヘプチル、（メタ）アクリル酸ヒドロキシオクチル等が挙げられる。 The low-molecular-weight (meth)acrylic resin (C) is a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 5 or more carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group. It is preferred to have
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 5 or more carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group include hydroxypentyl (meth)acrylate, (meth) hydroxyhexyl acrylate, hydroxyheptyl (meth)acrylate, hydroxyoctyl (meth)acrylate and the like.
上記低分子量（メタ）アクリル樹脂（Ｃ）は、上記（メタ）アクリル酸エステルに由来するセグメントの他、（メタ）アクリル酸に由来するセグメント、グリシジル基を有する（メタ）アクリル酸エステル等の他の（メタ）アクリル酸エステルに由来するセグメントを有していてもよい。
The low-molecular-weight (meth)acrylic resin (C) includes segments derived from the (meth)acrylic acid ester, segments derived from (meth)acrylic acid, glycidyl group-containing (meth)acrylic acid esters, and the like. may have a segment derived from the (meth)acrylic acid ester of.
また、上記（３）を満たす本発明の（メタ）アクリル樹脂組成物において、上記（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度は２５０ｐｐｍ以上２００００ｐｐｍ以下である。
上記範囲とすることで、バインダー樹脂が低温でも極めて優れた分解性を発現しつつ、更に、無機微粒子の分散性、凝集抑制効果を向上させることができる。
上記Ｓ原子の重量濃度は、１５００ｐｐｍ以上であることが好ましく、３０００ｐｐｍ以上であることがより好ましく、１８０００ｐｐｍ以下であることが好ましく、１００００ｐｐｍ以下であることがより好ましい。
上記Ｓ原子の重量濃度は、（メタ）アクリル樹脂の重量に対するＳ原子の重量の割合を意味し、以下の式に基づいて算出することができる。
（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度＝［連鎖移動剤に含まれるＳ原子の重量／（全モノマーの重量＋重合開始剤の重量＋連鎖移動剤の重量）］×１００
なお、上記（メタ）アクリル樹脂組成物が複数の（メタ）アクリル樹脂を含有する場合、上記Ｓ原子の重量濃度は、各（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度及び各（メタ）アクリル樹脂の配合割合に基づいて算出することができる。
また、上記Ｓ原子の重量濃度は、ＩＣＰ－ＡＥＳ（誘導結合プラズマ発光分光分析法）によっても求めることができる。 In the (meth)acrylic resin composition of the present invention satisfying the above (3), the weight concentration of S atoms contained in the (meth)acrylic resin is 250 ppm or more and 20000 ppm or less.
By setting the amount within the above range, the binder resin exhibits extremely excellent decomposability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
The weight concentration of the S atoms is preferably 1500 ppm or more, more preferably 3000 ppm or more, preferably 18000 ppm or less, and more preferably 10000 ppm or less.
The weight concentration of S atoms means the ratio of the weight of S atoms to the weight of the (meth)acrylic resin, and can be calculated based on the following formula.
Weight concentration of S atoms contained in (meth)acrylic resin = [weight of S atoms contained in chain transfer agent/(weight of all monomers + weight of polymerization initiator + weight of chain transfer agent)] × 100
When the (meth)acrylic resin composition contains a plurality of (meth)acrylic resins, the weight concentration of the S atoms is the weight concentration of the S atoms contained in each (meth)acrylic resin and each (meth)acrylic resin. ) can be calculated based on the mixing ratio of the acrylic resin.
The weight concentration of S atoms can also be determined by ICP-AES (inductively coupled plasma atomic emission spectrometry).
上記範囲とすることで、バインダー樹脂が低温でも極めて優れた分解性を発現しつつ、更に、無機微粒子の分散性、凝集抑制効果を向上させることができる。
上記Ｓ原子の重量濃度は、１５００ｐｐｍ以上であることが好ましく、３０００ｐｐｍ以上であることがより好ましく、１８０００ｐｐｍ以下であることが好ましく、１００００ｐｐｍ以下であることがより好ましい。
上記Ｓ原子の重量濃度は、（メタ）アクリル樹脂の重量に対するＳ原子の重量の割合を意味し、以下の式に基づいて算出することができる。
（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度＝［連鎖移動剤に含まれるＳ原子の重量／（全モノマーの重量＋重合開始剤の重量＋連鎖移動剤の重量）］×１００
なお、上記（メタ）アクリル樹脂組成物が複数の（メタ）アクリル樹脂を含有する場合、上記Ｓ原子の重量濃度は、各（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度及び各（メタ）アクリル樹脂の配合割合に基づいて算出することができる。
また、上記Ｓ原子の重量濃度は、ＩＣＰ－ＡＥＳ（誘導結合プラズマ発光分光分析法）によっても求めることができる。 In the (meth)acrylic resin composition of the present invention satisfying the above (3), the weight concentration of S atoms contained in the (meth)acrylic resin is 250 ppm or more and 20000 ppm or less.
By setting the amount within the above range, the binder resin exhibits extremely excellent decomposability even at low temperatures, and furthermore, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
The weight concentration of the S atoms is preferably 1500 ppm or more, more preferably 3000 ppm or more, preferably 18000 ppm or less, and more preferably 10000 ppm or less.
The weight concentration of S atoms means the ratio of the weight of S atoms to the weight of the (meth)acrylic resin, and can be calculated based on the following formula.
Weight concentration of S atoms contained in (meth)acrylic resin = [weight of S atoms contained in chain transfer agent/(weight of all monomers + weight of polymerization initiator + weight of chain transfer agent)] × 100
When the (meth)acrylic resin composition contains a plurality of (meth)acrylic resins, the weight concentration of the S atoms is the weight concentration of the S atoms contained in each (meth)acrylic resin and each (meth)acrylic resin. ) can be calculated based on the mixing ratio of the acrylic resin.
The weight concentration of S atoms can also be determined by ICP-AES (inductively coupled plasma atomic emission spectrometry).
上記低分子量（メタ）アクリル樹脂（Ｃ）のガラス転移温度（Ｔｇ）は３０℃以上６０℃以下である。
上記範囲とすることで、可塑剤の添加量を少なくすることができ、また、低温分解性を向上させることができる。
上記Ｔｇは３２℃以上であることが好ましく、４２℃以上であることがより好ましく、４５℃以上であることが更により好ましく、５８℃以下であることが好ましく、５０℃以下であることがより好ましい。
なお、上記ガラス転移温度（Ｔｇ）は、例えば、示差走査熱量計（ＤＳＣ）等を用いて測定することができる。 The glass transition temperature (Tg) of the low molecular weight (meth)acrylic resin (C) is 30°C or higher and 60°C or lower.
By setting the amount within the above range, the amount of the plasticizer to be added can be reduced, and the low-temperature decomposability can be improved.
The Tg is preferably 32° C. or higher, more preferably 42° C. or higher, even more preferably 45° C. or higher, preferably 58° C. or lower, and more preferably 50° C. or lower. preferable.
The glass transition temperature (Tg) can be measured using, for example, a differential scanning calorimeter (DSC).
上記範囲とすることで、可塑剤の添加量を少なくすることができ、また、低温分解性を向上させることができる。
上記Ｔｇは３２℃以上であることが好ましく、４２℃以上であることがより好ましく、４５℃以上であることが更により好ましく、５８℃以下であることが好ましく、５０℃以下であることがより好ましい。
なお、上記ガラス転移温度（Ｔｇ）は、例えば、示差走査熱量計（ＤＳＣ）等を用いて測定することができる。 The glass transition temperature (Tg) of the low molecular weight (meth)acrylic resin (C) is 30°C or higher and 60°C or lower.
By setting the amount within the above range, the amount of the plasticizer to be added can be reduced, and the low-temperature decomposability can be improved.
The Tg is preferably 32° C. or higher, more preferably 42° C. or higher, even more preferably 45° C. or higher, preferably 58° C. or lower, and more preferably 50° C. or lower. preferable.
The glass transition temperature (Tg) can be measured using, for example, a differential scanning calorimeter (DSC).
本発明の（メタ）アクリル樹脂組成物における上記低分子量（メタ）アクリル樹脂（Ｃ）の含有量は、０．００６重量％以上であることが好ましく、０．０１重量％以上であることがより好ましく、１０重量％以下であることが好ましく、８重量％以下であることがより好ましい。
The content of the low molecular weight (meth)acrylic resin (C) in the (meth)acrylic resin composition of the present invention is preferably 0.006% by weight or more, more preferably 0.01% by weight or more. It is preferably 10% by weight or less, more preferably 8% by weight or less.
また、上記（１）を満たす本発明の（メタ）アクリル樹脂組成物において、上記（メタ）アクリル樹脂は、上記高分子量（メタ）アクリル樹脂（Ａ）に加えて、更に、上記低分子量（メタ）アクリル樹脂（Ｂ）を含有することが好ましい。
更に、上記低分子量（メタ）アクリル樹脂（Ｃ）を含有することで、無機微粒子の分散性をより向上させることができる。 Further, in the (meth)acrylic resin composition of the present invention satisfying the above (1), the (meth)acrylic resin is, in addition to the high molecular weight (meth)acrylic resin (A), further the low molecular weight (meth) ) It is preferable to contain an acrylic resin (B).
Further, by containing the low-molecular-weight (meth)acrylic resin (C), the dispersibility of the inorganic fine particles can be further improved.
更に、上記低分子量（メタ）アクリル樹脂（Ｃ）を含有することで、無機微粒子の分散性をより向上させることができる。 Further, in the (meth)acrylic resin composition of the present invention satisfying the above (1), the (meth)acrylic resin is, in addition to the high molecular weight (meth)acrylic resin (A), further the low molecular weight (meth) ) It is preferable to contain an acrylic resin (B).
Further, by containing the low-molecular-weight (meth)acrylic resin (C), the dispersibility of the inorganic fine particles can be further improved.
上記（１）を満たす本発明の（メタ）アクリル樹脂組成物において、上記低分子量（メタ）アクリル樹脂（Ｃ）の含有量は、上記高分子量（メタ）アクリル樹脂（Ａ）１００重量部に対して、０．１重量部以上であることが好ましく、１０重量部以下であることが好ましい。
上記範囲とすることで、無機微粒子の分散性をより向上させることができる。
上記高分子量（メタ）アクリル樹脂１００重量部に対する低分子量（メタ）アクリル樹脂（Ｃ）の含有量は、０．３重量部以上であることがより好ましく、７．５重量部以下であることがより好ましい。 In the (meth)acrylic resin composition of the present invention that satisfies the above (1), the content of the low molecular weight (meth)acrylic resin (C) is based on 100 parts by weight of the high molecular weight (meth)acrylic resin (A). Therefore, it is preferably 0.1 parts by weight or more, and preferably 10 parts by weight or less.
By setting it as the said range, the dispersibility of an inorganic fine particle can be improved more.
The content of the low-molecular-weight (meth)acrylic resin (C) with respect to 100 parts by weight of the high-molecular-weight (meth)acrylic resin is more preferably 0.3 parts by weight or more, and is preferably 7.5 parts by weight or less. more preferred.
上記範囲とすることで、無機微粒子の分散性をより向上させることができる。
上記高分子量（メタ）アクリル樹脂１００重量部に対する低分子量（メタ）アクリル樹脂（Ｃ）の含有量は、０．３重量部以上であることがより好ましく、７．５重量部以下であることがより好ましい。 In the (meth)acrylic resin composition of the present invention that satisfies the above (1), the content of the low molecular weight (meth)acrylic resin (C) is based on 100 parts by weight of the high molecular weight (meth)acrylic resin (A). Therefore, it is preferably 0.1 parts by weight or more, and preferably 10 parts by weight or less.
By setting it as the said range, the dispersibility of an inorganic fine particle can be improved more.
The content of the low-molecular-weight (meth)acrylic resin (C) with respect to 100 parts by weight of the high-molecular-weight (meth)acrylic resin is more preferably 0.3 parts by weight or more, and is preferably 7.5 parts by weight or less. more preferred.
上記低分子量（メタ）アクリル樹脂（Ｃ）を製造する方法は特に限定されない。例えば、（メタ）アクリル酸エステル等を含む原料モノマー混合物に有機溶剤等を加えてモノマー混合液を調整し、更に、得られたモノマー混合液に重合開始剤、連鎖移動剤を添加して、上記原料モノマーを共重合させる方法が挙げられる。
重合させる方法は特に限定されず、乳化重合、懸濁重合、塊状重合、界面重合、溶液重合等が挙げられる。なかでも、溶液重合が好ましい。 The method for producing the low molecular weight (meth)acrylic resin (C) is not particularly limited. For example, an organic solvent or the like is added to a raw material monomer mixture containing (meth) acrylic acid ester or the like to prepare a monomer mixture, and a polymerization initiator and a chain transfer agent are added to the obtained monomer mixture, and the above A method of copolymerizing raw material monomers may be mentioned.
The polymerization method is not particularly limited, and examples thereof include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, and solution polymerization. Among them, solution polymerization is preferred.
重合させる方法は特に限定されず、乳化重合、懸濁重合、塊状重合、界面重合、溶液重合等が挙げられる。なかでも、溶液重合が好ましい。 The method for producing the low molecular weight (meth)acrylic resin (C) is not particularly limited. For example, an organic solvent or the like is added to a raw material monomer mixture containing (meth) acrylic acid ester or the like to prepare a monomer mixture, and a polymerization initiator and a chain transfer agent are added to the obtained monomer mixture, and the above A method of copolymerizing raw material monomers may be mentioned.
The polymerization method is not particularly limited, and examples thereof include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, and solution polymerization. Among them, solution polymerization is preferred.
上記重合開始剤としては、例えば、ｔ－ブチルパーオキシピバレート、Ｐ－メンタンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、１，１，３，３－テトラメチルブチルハイドロパーオキサイド、クメンハイドロキシパーオキサイド、ｔ－ブチルハイドロキシパーオキサイド、過酸化シクロヘキサノン、ジコハク酸パーオキサイド等が挙げられる。
Examples of the polymerization initiator include t-butyl peroxypivalate, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroxyperoxide, t-butyl hydroxyperoxide, cyclohexanone peroxide, disuccinic acid peroxide and the like.
上記連鎖移動剤としては、例えば、３－メルカプト－１，２－プロパンジオール、３－メルカプト－１－プロパノール、３－メルカプト－２－ブタノール、８－メルカプト－１－オクタノール、メルカプトコハク酸、メルカプト酢酸等が挙げられる。
Examples of the chain transfer agent include 3-mercapto-1,2-propanediol, 3-mercapto-1-propanol, 3-mercapto-2-butanol, 8-mercapto-1-octanol, mercaptosuccinic acid, and mercaptoacetic acid. etc.
＜有機溶剤＞
本発明の（メタ）アクリル樹脂組成物は、有機溶剤を含有する。
上記有機溶剤中に含まれるＯＨ基の重量濃度は、９．０重量％以上２８．０重量％以下である。
上記有機溶剤を含有することにより、無機微粒子の分散性、凝集抑制効果を向上させることができる。
上記ＯＨ基の重量濃度は、１１．０重量％以上であることが好ましく、１３．０重量％以上であることがより好ましく、２６．０重量％以下であることが好ましく、２４重量％以下であることがより好ましく、２２．５重量％以下であることが更に好ましい。
上記ＯＨ基の重量濃度は、有機溶剤全体の重量に対するＯＨ基の重量の割合を意味し、以下の式に基づいて算出することができる。
有機溶剤中に含まれるＯＨ基の重量濃度＝（全有機溶剤中に含まれるＯＨ基の重量／全有機溶剤の重量）×１００ <Organic solvent>
The (meth)acrylic resin composition of the present invention contains an organic solvent.
The weight concentration of OH groups contained in the organic solvent is 9.0% by weight or more and 28.0% by weight or less.
By containing the above organic solvent, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
The weight concentration of the OH group is preferably 11.0% by weight or more, more preferably 13.0% by weight or more, preferably 26.0% by weight or less, and 24% by weight or less. more preferably 22.5% by weight or less.
The weight concentration of the OH group means the ratio of the weight of the OH group to the weight of the entire organic solvent, and can be calculated based on the following formula.
Weight concentration of OH groups contained in organic solvent = (weight of OH groups contained in all organic solvents/weight of all organic solvents) x 100
本発明の（メタ）アクリル樹脂組成物は、有機溶剤を含有する。
上記有機溶剤中に含まれるＯＨ基の重量濃度は、９．０重量％以上２８．０重量％以下である。
上記有機溶剤を含有することにより、無機微粒子の分散性、凝集抑制効果を向上させることができる。
上記ＯＨ基の重量濃度は、１１．０重量％以上であることが好ましく、１３．０重量％以上であることがより好ましく、２６．０重量％以下であることが好ましく、２４重量％以下であることがより好ましく、２２．５重量％以下であることが更に好ましい。
上記ＯＨ基の重量濃度は、有機溶剤全体の重量に対するＯＨ基の重量の割合を意味し、以下の式に基づいて算出することができる。
有機溶剤中に含まれるＯＨ基の重量濃度＝（全有機溶剤中に含まれるＯＨ基の重量／全有機溶剤の重量）×１００ <Organic solvent>
The (meth)acrylic resin composition of the present invention contains an organic solvent.
The weight concentration of OH groups contained in the organic solvent is 9.0% by weight or more and 28.0% by weight or less.
By containing the above organic solvent, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be improved.
The weight concentration of the OH group is preferably 11.0% by weight or more, more preferably 13.0% by weight or more, preferably 26.0% by weight or less, and 24% by weight or less. more preferably 22.5% by weight or less.
The weight concentration of the OH group means the ratio of the weight of the OH group to the weight of the entire organic solvent, and can be calculated based on the following formula.
Weight concentration of OH groups contained in organic solvent = (weight of OH groups contained in all organic solvents/weight of all organic solvents) x 100
上記高分子量（メタ）アクリル樹脂（Ａ）及び（Ｂ）中に含まれるＯＨ基の重量濃度に対する上記有機溶剤中に含まれるＯＨ基の重量濃度の比（有機溶剤中に含まれるＯＨ基の重量濃度／高分子量（メタ）アクリル樹脂中に含まれるＯＨ基の重量濃度）は、４．５以上であることが好ましく、４６．２以下であることが好ましい。
上記範囲とすることで、無機微粒子の分散性、凝集抑制効果をより向上させることができる。
上記比は、８．１以上であることがより好ましく、１０以上であることが更に好ましく、４０以下であることがより好ましく、３０以下であることが更に好ましく、２５以下であることが更により好ましく、２０以下であることが特に好ましい。 Ratio of weight concentration of OH groups contained in the organic solvent to weight concentration of OH groups contained in the high molecular weight (meth)acrylic resins (A) and (B) (weight of OH groups contained in the organic solvent The concentration/weight concentration of OH groups contained in the high molecular weight (meth)acrylic resin) is preferably 4.5 or more and preferably 46.2 or less.
By setting the amount within the above range, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be further improved.
The above ratio is more preferably 8.1 or more, more preferably 10 or more, more preferably 40 or less, still more preferably 30 or less, and even more preferably 25 or less. It is preferably 20 or less, and particularly preferably 20 or less.
上記範囲とすることで、無機微粒子の分散性、凝集抑制効果をより向上させることができる。
上記比は、８．１以上であることがより好ましく、１０以上であることが更に好ましく、４０以下であることがより好ましく、３０以下であることが更に好ましく、２５以下であることが更により好ましく、２０以下であることが特に好ましい。 Ratio of weight concentration of OH groups contained in the organic solvent to weight concentration of OH groups contained in the high molecular weight (meth)acrylic resins (A) and (B) (weight of OH groups contained in the organic solvent The concentration/weight concentration of OH groups contained in the high molecular weight (meth)acrylic resin) is preferably 4.5 or more and preferably 46.2 or less.
By setting the amount within the above range, the dispersibility of the inorganic fine particles and the effect of suppressing aggregation can be further improved.
The above ratio is more preferably 8.1 or more, more preferably 10 or more, more preferably 40 or less, still more preferably 30 or less, and even more preferably 25 or less. It is preferably 20 or less, and particularly preferably 20 or less.
上記有機溶剤は、ＯＨ基を有する有機溶剤を含有する。
上記ＯＨ基を有する有機溶剤としては、例えば、脂肪族アルコール、環状アルコール、脂環式アルコール等が挙げられる。
上記脂肪族アルコールとしては、例えば、エタノール、プロパノール、イソプロパノール、ヘプタノール、オクタノール、デカノール、トリデカノール、ラウリルアルコール、テトラデシルアルコール、セチルアルコール、２－エチル－１－ヘキサノール、オクタデシルアルコール、ヘキサデセノール、オレイルアルコール、テキサノール、２－ブチル－２－エチル－１，３－プロパンジオール、ネオペンチルグリコール等が挙げられる。
上記環状アルコールとしては、例えば、クレゾール、オイゲノール等が挙げられる。
上記脂環式アルコールとしては、例えば、シクロヘキサノール等のシクロアルカノール、テルピネオール、ジヒドロテルピネオール等のテルペンアルコール等が挙げられる。
なかでも、脂肪族アルコールが好ましく、エタノール、イソプロパノール、２－ブチル－２－エチル－１，３－プロパンジオール、ネオペンチルグリコール、テキサノールが好ましい。 The organic solvent contains an organic solvent having an OH group.
Examples of organic solvents having an OH group include aliphatic alcohols, cyclic alcohols, and alicyclic alcohols.
Examples of the aliphatic alcohol include ethanol, propanol, isopropanol, heptanol, octanol, decanol, tridecanol, lauryl alcohol, tetradecyl alcohol, cetyl alcohol, 2-ethyl-1-hexanol, octadecyl alcohol, hexadecenol, oleyl alcohol, texanol. , 2-butyl-2-ethyl-1,3-propanediol, neopentyl glycol and the like.
Examples of the cyclic alcohol include cresol and eugenol.
Examples of the alicyclic alcohols include cycloalkanols such as cyclohexanol, terpene alcohols such as terpineol and dihydroterpineol, and the like.
Among them, aliphatic alcohols are preferred, and ethanol, isopropanol, 2-butyl-2-ethyl-1,3-propanediol, neopentyl glycol and texanol are preferred.
上記ＯＨ基を有する有機溶剤としては、例えば、脂肪族アルコール、環状アルコール、脂環式アルコール等が挙げられる。
上記脂肪族アルコールとしては、例えば、エタノール、プロパノール、イソプロパノール、ヘプタノール、オクタノール、デカノール、トリデカノール、ラウリルアルコール、テトラデシルアルコール、セチルアルコール、２－エチル－１－ヘキサノール、オクタデシルアルコール、ヘキサデセノール、オレイルアルコール、テキサノール、２－ブチル－２－エチル－１，３－プロパンジオール、ネオペンチルグリコール等が挙げられる。
上記環状アルコールとしては、例えば、クレゾール、オイゲノール等が挙げられる。
上記脂環式アルコールとしては、例えば、シクロヘキサノール等のシクロアルカノール、テルピネオール、ジヒドロテルピネオール等のテルペンアルコール等が挙げられる。
なかでも、脂肪族アルコールが好ましく、エタノール、イソプロパノール、２－ブチル－２－エチル－１，３－プロパンジオール、ネオペンチルグリコール、テキサノールが好ましい。 The organic solvent contains an organic solvent having an OH group.
Examples of organic solvents having an OH group include aliphatic alcohols, cyclic alcohols, and alicyclic alcohols.
Examples of the aliphatic alcohol include ethanol, propanol, isopropanol, heptanol, octanol, decanol, tridecanol, lauryl alcohol, tetradecyl alcohol, cetyl alcohol, 2-ethyl-1-hexanol, octadecyl alcohol, hexadecenol, oleyl alcohol, texanol. , 2-butyl-2-ethyl-1,3-propanediol, neopentyl glycol and the like.
Examples of the cyclic alcohol include cresol and eugenol.
Examples of the alicyclic alcohols include cycloalkanols such as cyclohexanol, terpene alcohols such as terpineol and dihydroterpineol, and the like.
Among them, aliphatic alcohols are preferred, and ethanol, isopropanol, 2-butyl-2-ethyl-1,3-propanediol, neopentyl glycol and texanol are preferred.
上記ＯＨ基を有する有機溶剤は、分子量が４６以上であることが好ましく、６０以上であることがより好ましく、２２０以下であることが好ましく、１６０以下であることがより好ましい。
また、上記ＯＨ基を有する有機溶剤は、炭素数が２以上であることが好ましく、３以上であることがより好ましく、１２以下であることが好ましく、１０以下であることがより好ましい。 The organic solvent having an OH group preferably has a molecular weight of 46 or more, more preferably 60 or more, preferably 220 or less, and more preferably 160 or less.
The organic solvent having an OH group preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms, preferably 12 or less carbon atoms, and more preferably 10 or less carbon atoms.
また、上記ＯＨ基を有する有機溶剤は、炭素数が２以上であることが好ましく、３以上であることがより好ましく、１２以下であることが好ましく、１０以下であることがより好ましい。 The organic solvent having an OH group preferably has a molecular weight of 46 or more, more preferably 60 or more, preferably 220 or less, and more preferably 160 or less.
The organic solvent having an OH group preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms, preferably 12 or less carbon atoms, and more preferably 10 or less carbon atoms.
上記ＯＨ基を有する有機溶剤中に含まれるＯＨ基の重量の割合は、７．５重量％以上であることが好ましく、１５重量％以上であることがより好ましく、２１重量％以上であることが更に好ましく、３７重量％以下であることが好ましい。
The weight ratio of OH groups contained in the organic solvent having OH groups is preferably 7.5% by weight or more, more preferably 15% by weight or more, and is preferably 21% by weight or more. More preferably, it is 37% by weight or less.
上記有機溶剤全体に対するＯＨ基を有する有機溶剤の含有量は、２９重量％以上であることが好ましく、４３重量％以上であることがより好ましく、７９重量％以下であることが好ましく、６１重量％以下であることがより好ましい。
The content of the organic solvent having an OH group with respect to the entire organic solvent is preferably 29% by weight or more, more preferably 43% by weight or more, preferably 79% by weight or less, and 61% by weight. The following are more preferable.
上記有機溶剤は、ＯＨ基を有する有機溶剤以外の他の有機溶剤を含有していてもよい。
上記他の有機溶剤としては、例えば、アセトン、メチルエチルケトン、ジプロピルケトン、ジイソブチルケトン等のケトン類、トルエン、キシレン等の芳香族炭化水素類、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸ブチル、ブタン酸メチル、ブタン酸エチル、ブタン酸ブチル、ペンタン酸メチル、ペンタン酸エチル、ペンタン酸ブチル、ヘキサン酸メチル、ヘキサン酸エチル、ヘキサン酸ブチル、酢酸エチル、酢酸ブチル、酢酸ヘキシル、酢酸２－エチルヘキシル、酪酸２－エチルヘキシル等のエステル類等が挙げられる。
なかでも、トルエン、酢酸ブチル、メチルエチルケトンが好ましい。 The organic solvent may contain an organic solvent other than the organic solvent having an OH group.
Examples of the other organic solvents include ketones such as acetone, methyl ethyl ketone, dipropyl ketone and diisobutyl ketone, aromatic hydrocarbons such as toluene and xylene, methyl propionate, ethyl propionate, butyl propionate, and butanoic acid. Methyl, ethyl butanoate, butyl butanoate, methyl pentanoate, ethyl pentanoate, butyl pentanoate, methyl hexanoate, ethyl hexanoate, butyl hexanoate, ethyl acetate, butyl acetate, hexyl acetate, 2-ethylhexyl acetate, butyric acid 2 - Esters such as ethylhexyl.
Among them, toluene, butyl acetate and methyl ethyl ketone are preferred.
上記他の有機溶剤としては、例えば、アセトン、メチルエチルケトン、ジプロピルケトン、ジイソブチルケトン等のケトン類、トルエン、キシレン等の芳香族炭化水素類、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸ブチル、ブタン酸メチル、ブタン酸エチル、ブタン酸ブチル、ペンタン酸メチル、ペンタン酸エチル、ペンタン酸ブチル、ヘキサン酸メチル、ヘキサン酸エチル、ヘキサン酸ブチル、酢酸エチル、酢酸ブチル、酢酸ヘキシル、酢酸２－エチルヘキシル、酪酸２－エチルヘキシル等のエステル類等が挙げられる。
なかでも、トルエン、酢酸ブチル、メチルエチルケトンが好ましい。 The organic solvent may contain an organic solvent other than the organic solvent having an OH group.
Examples of the other organic solvents include ketones such as acetone, methyl ethyl ketone, dipropyl ketone and diisobutyl ketone, aromatic hydrocarbons such as toluene and xylene, methyl propionate, ethyl propionate, butyl propionate, and butanoic acid. Methyl, ethyl butanoate, butyl butanoate, methyl pentanoate, ethyl pentanoate, butyl pentanoate, methyl hexanoate, ethyl hexanoate, butyl hexanoate, ethyl acetate, butyl acetate, hexyl acetate, 2-ethylhexyl acetate, butyric acid 2 - Esters such as ethylhexyl.
Among them, toluene, butyl acetate and methyl ethyl ketone are preferred.
上記有機溶剤全体に対する上記他の有機溶剤の含有量は、２１重量％以上であることが好ましく、３９重量％以上であることがより好ましく、７１重量％以下であることが好ましく、５７重量％以下であることがより好ましい。
The content of the other organic solvent relative to the total organic solvent is preferably 21% by weight or more, more preferably 39% by weight or more, preferably 71% by weight or less, and 57% by weight or less. is more preferable.
本発明の（メタ）アクリル樹脂組成物における上記有機溶剤の含有量は、２０重量％以上であることが好ましく、３０重量％以上であることがより好ましく、９５重量％以下であることが好ましく、７０重量％以下であることがより好ましく、６０重量％以下であることが更に好ましい。
The content of the organic solvent in the (meth)acrylic resin composition of the present invention is preferably 20% by weight or more, more preferably 30% by weight or more, and preferably 95% by weight or less, It is more preferably 70% by weight or less, and even more preferably 60% by weight or less.
本発明の（メタ）アクリル樹脂組成物における上記有機溶剤の含有量は、上記（メタ）アクリル樹脂１００重量部に対して、２５重量部以上であることが好ましく、１００重量部以上であることがより好ましく、２０００重量部以下であることが好ましく、１５００重量部以下であることがより好ましい。
The content of the organic solvent in the (meth)acrylic resin composition of the present invention is preferably 25 parts by weight or more, more preferably 100 parts by weight or more, relative to 100 parts by weight of the (meth)acrylic resin. More preferably, it is 2000 parts by weight or less, and more preferably 1500 parts by weight or less.
本発明の（メタ）アクリル樹脂組成物における上記有機溶剤の含有量は、上記高分子量（メタ）アクリル樹脂（Ａ）１００重量部に対して、２５重量部以上であることが好ましく、４２．９重量部以上であることがより好ましく、１９００重量部以下であることが好ましく、２３３．３重量部以下であることがより好ましく、１５０重量部以下であることがより好ましい。
The content of the organic solvent in the (meth)acrylic resin composition of the present invention is preferably 25 parts by weight or more with respect to 100 parts by weight of the high molecular weight (meth)acrylic resin (A), and is 42.9 parts by weight. It is more preferably 1900 parts by weight or less, more preferably 233.3 parts by weight or less, and more preferably 150 parts by weight or less.
本発明の（メタ）アクリル樹脂組成物における上記有機溶剤の含有量は、上記高分子量（メタ）アクリル樹脂（Ｂ）１００重量部に対して、２５重量部以上であることが好ましく、１００重量部以上であることがより好ましく、２０００重量部以下であることが好ましく、１５００重量部以下であることがより好ましい。
The content of the organic solvent in the (meth)acrylic resin composition of the present invention is preferably 25 parts by weight or more and 100 parts by weight with respect to 100 parts by weight of the high molecular weight (meth)acrylic resin (B). It is more preferably 2000 parts by weight or less, and more preferably 1500 parts by weight or less.
本発明の（メタ）アクリル樹脂組成物における上記有機溶剤の含有量は、上記低分子量（メタ）アクリル樹脂（Ｃ）１００重量部に対して、２５重量部以上であることが好ましく、１０００重量部以上であることがより好ましく、１，５００，０００重量部以下であることが好ましく、１，０００，０００重量部以下であることがより好ましい。
The content of the organic solvent in the (meth)acrylic resin composition of the present invention is preferably 25 parts by weight or more and 1000 parts by weight with respect to 100 parts by weight of the low molecular weight (meth)acrylic resin (C). It is more preferably 1,500,000 parts by weight or less, and more preferably 1,000,000 parts by weight or less.
上記有機溶剤の沸点は９０～１６０℃であることが好ましい。上記沸点が９０℃以上であることで、蒸発が早くなりすぎず、取り扱い性に優れる。上記沸点を１６０℃以下とすることで、無機微粒子分散シートの強度を向上させることが可能となる。
The boiling point of the organic solvent is preferably 90 to 160°C. When the boiling point is 90° C. or higher, the evaporation does not become too fast and the handleability is excellent. By setting the boiling point to 160° C. or lower, it is possible to improve the strength of the inorganic fine particle dispersed sheet.
本発明の（メタ）アクリル樹脂組成物を作製する方法は特に限定されないが、例えば、上記高分子量（メタ）アクリル樹脂（Ａ）、上記高分子量（メタ）アクリル樹脂（Ｂ）、上記高分子量（メタ）アクリル樹脂（Ｃ）のうちの少なくとも１つを含む（メタ）アクリル樹脂、上記有機溶剤、必要に応じて添加されるその他の添加剤を混合する方法が挙げられる。
The method for producing the (meth)acrylic resin composition of the present invention is not particularly limited. A method of mixing a (meth)acrylic resin containing at least one of the meth)acrylic resins (C), the above organic solvent, and other additives added as necessary.
本発明の（メタ）アクリル樹脂組成物は、低温分解性に優れるとともに、無機微粒子の分散性、凝集抑制効果に優れることから、無機微粒子及び可塑剤を組み合わせて、無機微粒子分散スラリー組成物として好適に用いることができる。
The (meth)acrylic resin composition of the present invention has excellent low-temperature decomposability, excellent dispersibility of inorganic fine particles, and excellent aggregation-inhibiting effect. can be used for
本発明の（メタ）アクリル樹脂組成物、無機微粒子及び可塑剤を含有する無機微粒子分散スラリー組成物もまた本発明の１つである。
An inorganic fine particle-dispersed slurry composition containing the (meth)acrylic resin composition of the present invention, inorganic fine particles and a plasticizer is also one aspect of the present invention.
＜無機微粒子＞
本発明の無機微粒子分散スラリー組成物は、無機微粒子を含有する。
上記無機微粒子は特に限定されず、例えば、ガラス粉末、セラミック粉末、蛍光体微粒子、珪素酸化物等、金属微粒子等が挙げられる。 <Inorganic fine particles>
The inorganic fine particle-dispersed slurry composition of the present invention contains inorganic fine particles.
The inorganic fine particles are not particularly limited, and examples thereof include glass powder, ceramic powder, phosphor fine particles, silicon oxide, and metal fine particles.
本発明の無機微粒子分散スラリー組成物は、無機微粒子を含有する。
上記無機微粒子は特に限定されず、例えば、ガラス粉末、セラミック粉末、蛍光体微粒子、珪素酸化物等、金属微粒子等が挙げられる。 <Inorganic fine particles>
The inorganic fine particle-dispersed slurry composition of the present invention contains inorganic fine particles.
The inorganic fine particles are not particularly limited, and examples thereof include glass powder, ceramic powder, phosphor fine particles, silicon oxide, and metal fine particles.
上記ガラス粉末は特に限定されず、例えば、酸化ビスマスガラス、ケイ酸塩ガラス、鉛ガラス、亜鉛ガラス、ボロンガラス等のガラス粉末や、ＣａＯ－Ａｌ２Ｏ３－ＳｉＯ２系、ＭｇＯ－Ａｌ２Ｏ３－ＳｉＯ２系、ＬｉＯ２－Ａｌ２Ｏ３－ＳｉＯ２系等の各種ケイ素酸化物のガラス粉末等が挙げられる。
また、上記ガラス粉末として、ＳｎＯ－Ｂ２Ｏ３－Ｐ２Ｏ５－Ａｌ２Ｏ３混合物、ＰｂＯ－Ｂ２Ｏ３－ＳｉＯ２混合物、ＢａＯ－ＺｎＯ－Ｂ２Ｏ３－ＳｉＯ２混合物、ＺｎＯ－Ｂｉ２Ｏ３－Ｂ２Ｏ３－ＳｉＯ２混合物、Ｂｉ２Ｏ３－Ｂ２Ｏ３－ＢａＯ－ＣｕＯ混合物、Ｂｉ２Ｏ３－ＺｎＯ－Ｂ２Ｏ３－Ａｌ２Ｏ３－ＳｒＯ混合物、ＺｎＯ－Ｂｉ２Ｏ３－Ｂ２Ｏ３混合物、Ｂｉ２Ｏ３－ＳｉＯ２混合物、Ｐ２Ｏ５－Ｎａ２Ｏ－ＣａＯ－ＢａＯ－Ａｌ２Ｏ３－Ｂ２Ｏ３混合物、Ｐ２Ｏ５－ＳｎＯ混合物、Ｐ２Ｏ５－ＳｎＯ－Ｂ２Ｏ３混合物、Ｐ２Ｏ５－ＳｎＯ－ＳｉＯ２混合物、ＣｕＯ－Ｐ２Ｏ５－ＲＯ混合物、ＳｉＯ２－Ｂ２Ｏ３－ＺｎＯ－Ｎａ２Ｏ－Ｌｉ２Ｏ－ＮａＦ－Ｖ２Ｏ５混合物、Ｐ２Ｏ５－ＺｎＯ－ＳｎＯ－Ｒ２Ｏ－ＲＯ混合物、Ｂ２Ｏ３－ＳｉＯ２－ＺｎＯ混合物、Ｂ２Ｏ３－ＳｉＯ２－Ａｌ２Ｏ３－ＺｒＯ２混合物、ＳｉＯ２－Ｂ２Ｏ３－ＺｎＯ－Ｒ２Ｏ－ＲＯ混合物、ＳｉＯ２－Ｂ２Ｏ３－Ａｌ２Ｏ３－ＲＯ－Ｒ２Ｏ混合物、ＳｒＯ－ＺｎＯ－Ｐ２Ｏ５混合物、ＳｒＯ－ＺｎＯ－Ｐ２Ｏ５混合物、ＢａＯ－ＺｎＯ－Ｂ２Ｏ３－ＳｉＯ２混合物等のガラス粉末も用いることができる。なお、Ｒは、Ｚｎ、Ｂａ、Ｃａ、Ｍｇ、Ｓｒ、Ｓｎ、Ｎｉ、Ｆｅ及びＭｎからなる群より選択される元素である。
特に、ＰｂＯ－Ｂ２Ｏ３－ＳｉＯ２混合物のガラス粉末や、鉛を含有しないＢａＯ－ＺｎＯ－Ｂ２Ｏ３－ＳｉＯ２混合物又はＺｎＯ－Ｂｉ２Ｏ３－Ｂ２Ｏ３－ＳｉＯ２混合物等の無鉛ガラス粉末が好ましい。 The glass powder is not particularly limited. Examples include glass powders of various silicon oxides such as 3 -SiO 2 system and LiO 2 -Al 2 O 3 -SiO 2 system.
Further, as the glass powder, SnO--B 2 O 3 --P 2 O 5 --Al 2 O 3 mixture, PbO--B 2 O 3 --SiO 2 mixture, BaO--ZnO--B 2 O 3 ---SiO 2 mixture, ZnO -Bi 2 O 3 -B 2 O 3 -SiO 2 mixture, Bi 2 O 3 -B 2 O 3 -BaO-CuO mixture, Bi 2 O 3 -ZnO-B 2 O 3 -Al 2 O 3 -SrO mixture, ZnO - Bi2O3 - B2O3 mixture, Bi2O3 - SiO2 mixture , P2O5 - Na2O - CaO - BaO - Al2O3 - B2O3 mixture , P2O5 -SnO mixture, P2O5 - SnO - B2O3 mixture, P2O5 - SnO - SiO2 mixture, CuO - P2O5 - RO mixture , SiO2 - B2O3 - ZnO - Na2 O—Li 2 O—NaF—V 2 O 5 mixture, P 2 O 5 —ZnO—SnO—R 2 O—RO mixture, B 2 O 3 —SiO 2 —ZnO mixture, B 2 O 3 —SiO 2 —Al 2O3 - ZrO2 mixture, SiO2 - B2O3 - ZnO - R2O - RO mixture, SiO2 - B2O3 - Al2O3 - RO - R2O mixture, SrO-ZnO-P 2 O 5 mixtures, SrO--ZnO--P 2 O 5 mixtures, BaO--ZnO--B 2 O 3 --SiO 2 mixtures, and other glass powders can also be used. R is an element selected from the group consisting of Zn, Ba, Ca, Mg, Sr, Sn, Ni, Fe and Mn.
In particular, glass powders of PbO-B 2 O 3 -SiO 2 mixtures, lead-free BaO-ZnO-B 2 O 3 -SiO 2 mixtures or ZnO-Bi 2 O 3 -B 2 O 3 -SiO 2 mixtures, etc. of lead-free glass powder is preferred.
また、上記ガラス粉末として、ＳｎＯ－Ｂ２Ｏ３－Ｐ２Ｏ５－Ａｌ２Ｏ３混合物、ＰｂＯ－Ｂ２Ｏ３－ＳｉＯ２混合物、ＢａＯ－ＺｎＯ－Ｂ２Ｏ３－ＳｉＯ２混合物、ＺｎＯ－Ｂｉ２Ｏ３－Ｂ２Ｏ３－ＳｉＯ２混合物、Ｂｉ２Ｏ３－Ｂ２Ｏ３－ＢａＯ－ＣｕＯ混合物、Ｂｉ２Ｏ３－ＺｎＯ－Ｂ２Ｏ３－Ａｌ２Ｏ３－ＳｒＯ混合物、ＺｎＯ－Ｂｉ２Ｏ３－Ｂ２Ｏ３混合物、Ｂｉ２Ｏ３－ＳｉＯ２混合物、Ｐ２Ｏ５－Ｎａ２Ｏ－ＣａＯ－ＢａＯ－Ａｌ２Ｏ３－Ｂ２Ｏ３混合物、Ｐ２Ｏ５－ＳｎＯ混合物、Ｐ２Ｏ５－ＳｎＯ－Ｂ２Ｏ３混合物、Ｐ２Ｏ５－ＳｎＯ－ＳｉＯ２混合物、ＣｕＯ－Ｐ２Ｏ５－ＲＯ混合物、ＳｉＯ２－Ｂ２Ｏ３－ＺｎＯ－Ｎａ２Ｏ－Ｌｉ２Ｏ－ＮａＦ－Ｖ２Ｏ５混合物、Ｐ２Ｏ５－ＺｎＯ－ＳｎＯ－Ｒ２Ｏ－ＲＯ混合物、Ｂ２Ｏ３－ＳｉＯ２－ＺｎＯ混合物、Ｂ２Ｏ３－ＳｉＯ２－Ａｌ２Ｏ３－ＺｒＯ２混合物、ＳｉＯ２－Ｂ２Ｏ３－ＺｎＯ－Ｒ２Ｏ－ＲＯ混合物、ＳｉＯ２－Ｂ２Ｏ３－Ａｌ２Ｏ３－ＲＯ－Ｒ２Ｏ混合物、ＳｒＯ－ＺｎＯ－Ｐ２Ｏ５混合物、ＳｒＯ－ＺｎＯ－Ｐ２Ｏ５混合物、ＢａＯ－ＺｎＯ－Ｂ２Ｏ３－ＳｉＯ２混合物等のガラス粉末も用いることができる。なお、Ｒは、Ｚｎ、Ｂａ、Ｃａ、Ｍｇ、Ｓｒ、Ｓｎ、Ｎｉ、Ｆｅ及びＭｎからなる群より選択される元素である。
特に、ＰｂＯ－Ｂ２Ｏ３－ＳｉＯ２混合物のガラス粉末や、鉛を含有しないＢａＯ－ＺｎＯ－Ｂ２Ｏ３－ＳｉＯ２混合物又はＺｎＯ－Ｂｉ２Ｏ３－Ｂ２Ｏ３－ＳｉＯ２混合物等の無鉛ガラス粉末が好ましい。 The glass powder is not particularly limited. Examples include glass powders of various silicon oxides such as 3 -SiO 2 system and LiO 2 -Al 2 O 3 -SiO 2 system.
Further, as the glass powder, SnO--B 2 O 3 --P 2 O 5 --Al 2 O 3 mixture, PbO--B 2 O 3 --SiO 2 mixture, BaO--ZnO--B 2 O 3 ---SiO 2 mixture, ZnO -Bi 2 O 3 -B 2 O 3 -SiO 2 mixture, Bi 2 O 3 -B 2 O 3 -BaO-CuO mixture, Bi 2 O 3 -ZnO-B 2 O 3 -Al 2 O 3 -SrO mixture, ZnO - Bi2O3 - B2O3 mixture, Bi2O3 - SiO2 mixture , P2O5 - Na2O - CaO - BaO - Al2O3 - B2O3 mixture , P2O5 -SnO mixture, P2O5 - SnO - B2O3 mixture, P2O5 - SnO - SiO2 mixture, CuO - P2O5 - RO mixture , SiO2 - B2O3 - ZnO - Na2 O—Li 2 O—NaF—V 2 O 5 mixture, P 2 O 5 —ZnO—SnO—R 2 O—RO mixture, B 2 O 3 —SiO 2 —ZnO mixture, B 2 O 3 —SiO 2 —Al 2O3 - ZrO2 mixture, SiO2 - B2O3 - ZnO - R2O - RO mixture, SiO2 - B2O3 - Al2O3 - RO - R2O mixture, SrO-ZnO-P 2 O 5 mixtures, SrO--ZnO--P 2 O 5 mixtures, BaO--ZnO--B 2 O 3 --SiO 2 mixtures, and other glass powders can also be used. R is an element selected from the group consisting of Zn, Ba, Ca, Mg, Sr, Sn, Ni, Fe and Mn.
In particular, glass powders of PbO-B 2 O 3 -SiO 2 mixtures, lead-free BaO-ZnO-B 2 O 3 -SiO 2 mixtures or ZnO-Bi 2 O 3 -B 2 O 3 -SiO 2 mixtures, etc. of lead-free glass powder is preferred.
上記セラミック粉末は特に限定されず、例えば、アルミナ、フェライト、ジルコニア、ジルコン、ジルコン酸バリウム、ジルコン酸カルシウム、酸化チタン、チタン酸バリウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸マグネシウム、チタン酸亜鉛、チタン酸ランタン、チタン酸ネオジウム、チタン酸ジルコン鉛、窒化アルミナ、窒化ケイ素、窒化ホウ素、炭化ホウ素、錫酸バリウム、錫酸カルシウム、珪酸マグネシウム、ムライト、ステアタイト、コーディエライト、フォルステライト等が挙げられる。
また、ＩＴＯ、ＦＴＯ、酸化ニオブ、酸化バナジウム、酸化タングステン、ランタンストロンチウムマンガナイト、ランタンストロンチウムコバルトフェライト、イットリウム安定化ジルコニア、ガドリニウムドープセリア、酸化ニッケル、ランタンクロマイト等も使用することができる。
上記蛍光体微粒子は特に限定されず、例えば、蛍光体物質としては、ディスプレイ用の蛍光体物質として従来知られている青色蛍光体物質、赤色蛍光体物質、緑色蛍光体物質などが用いられる。青色蛍光体物質としては、例えば、ＭｇＡｌ１０Ｏ１７：Ｅｕ、Ｙ２ＳｉＯ５：Ｃｅ系、ＣａＷＯ４：Ｐｂ系、ＢａＭｇＡｌ１４Ｏ２３：Ｅｕ系、ＢａＭｇＡｌ１６Ｏ２７：Ｅｕ系、ＢａＭｇ２Ａｌ１４Ｏ２３：Ｅｕ系、ＢａＭｇ２Ａｌ１４Ｏ２７：Ｅｕ系、ＺｎＳ：（Ａｇ，Ｃｄ）系のものが用いられる。赤色蛍光体物質としては、例えば、Ｙ２Ｏ３：Ｅｕ系、Ｙ２ＳｉＯ５：Ｅｕ系、Ｙ３Ａｌ５Ｏ１２：Ｅｕ系、Ｚｎ３（ＰＯ４）２：Ｍｎ系、ＹＢＯ３：Ｅｕ系、（Ｙ，Ｇｄ）ＢＯ３：Ｅｕ系、ＧｄＢＯ３：Ｅｕ系、ＳｃＢＯ３：Ｅｕ系、ＬｕＢＯ３：Ｅｕ系のものが用いられる。緑色蛍光体物質としては、例えば、Ｚｎ２ＳｉＯ４：Ｍｎ系、ＢａＡｌ１２Ｏ１９：Ｍｎ系、ＳｒＡｌ１３Ｏ１９：Ｍｎ系、ＣａＡｌ１２Ｏ１９：Ｍｎ系、ＹＢＯ３：Ｔｂ系、ＢａＭｇＡｌ１４Ｏ２３：Ｍｎ系、ＬｕＢＯ３：Ｔｂ系、ＧｄＢＯ３：Ｔｂ系、ＳｃＢＯ３：Ｔｂ系、Ｓｒ６Ｓｉ３Ｏ３Ｃｌ４：Ｅｕ系のものが用いられる。その他、ＺｎＯ：Ｚｎ系、ＺｎＳ：（Ｃｕ，Ａｌ）系、ＺｎＳ：Ａｇ系、Ｙ２Ｏ２Ｓ：Ｅｕ系、ＺｎＳ：Ｚｎ系、（Ｙ，Ｃｄ）ＢＯ３：Ｅｕ系、ＢａＭｇＡｌ１２Ｏ２３：Ｅｕ系のものも用いることができる。 The ceramic powder is not particularly limited, and examples thereof include alumina, ferrite, zirconia, zircon, barium zirconate, calcium zirconate, titanium oxide, barium titanate, strontium titanate, calcium titanate, magnesium titanate, zinc titanate, Lanthanum titanate, neodymium titanate, lead zirconium titanate, alumina nitride, silicon nitride, boron nitride, boron carbide, barium stannate, calcium stannate, magnesium silicate, mullite, steatite, cordierite, forsterite, etc. be done.
ITO, FTO, niobium oxide, vanadium oxide, tungsten oxide, lanthanum strontium manganite, lanthanum strontium cobalt ferrite, yttrium-stabilized zirconia, gadolinium-doped ceria, nickel oxide, lanthanum chromite, and the like can also be used.
The phosphor fine particles are not particularly limited, and for example, blue phosphor substances, red phosphor substances, green phosphor substances, etc., which are conventionally known as phosphor substances for displays, are used. Blue phosphor materials include, for example, MgAl 10 O 17 :Eu, Y 2 SiO 5 :Ce system, CaWO 4 :Pb system, BaMgAl 14 O 23 :Eu system, BaMgAl 16 O 27 :Eu system, BaMg 2 Al 14 O 23 : Eu system, BaMg 2 Al 14 O 27 : Eu system, ZnS: (Ag, Cd) system is used. Examples of red phosphor materials include Y2O3 :Eu system, Y2SiO5 :Eu system, Y3Al5O12 :Eu system, Zn3 ( PO4 ) 2 : Mn system , YBO3 :Eu. (Y,Gd)BO 3 :Eu system, GdBO 3 :Eu system, ScBO 3 :Eu system, and LuBO 3 :Eu system. Green phosphor materials include, for example, Zn2SiO4 :Mn-based, BaAl12O19 :Mn-based, SrAl13O19 : Mn -based, CaAl12O19 : Mn -based, YBO3 : Tb - based, and BaMgAl14O . 23 :Mn system, LuBO3 :Tb system, GdBO3 :Tb system , ScBO3 : Tb system, and Sr6Si3O3Cl4 :Eu system. In addition, ZnO: Zn system, ZnS: (Cu, Al) system, ZnS: Ag system, Y 2 O 2 S: Eu system, ZnS: Zn system, (Y, Cd) BO 3 : Eu system, BaMgAl 12 O 23 : Eu-based ones can also be used.
また、ＩＴＯ、ＦＴＯ、酸化ニオブ、酸化バナジウム、酸化タングステン、ランタンストロンチウムマンガナイト、ランタンストロンチウムコバルトフェライト、イットリウム安定化ジルコニア、ガドリニウムドープセリア、酸化ニッケル、ランタンクロマイト等も使用することができる。
上記蛍光体微粒子は特に限定されず、例えば、蛍光体物質としては、ディスプレイ用の蛍光体物質として従来知られている青色蛍光体物質、赤色蛍光体物質、緑色蛍光体物質などが用いられる。青色蛍光体物質としては、例えば、ＭｇＡｌ１０Ｏ１７：Ｅｕ、Ｙ２ＳｉＯ５：Ｃｅ系、ＣａＷＯ４：Ｐｂ系、ＢａＭｇＡｌ１４Ｏ２３：Ｅｕ系、ＢａＭｇＡｌ１６Ｏ２７：Ｅｕ系、ＢａＭｇ２Ａｌ１４Ｏ２３：Ｅｕ系、ＢａＭｇ２Ａｌ１４Ｏ２７：Ｅｕ系、ＺｎＳ：（Ａｇ，Ｃｄ）系のものが用いられる。赤色蛍光体物質としては、例えば、Ｙ２Ｏ３：Ｅｕ系、Ｙ２ＳｉＯ５：Ｅｕ系、Ｙ３Ａｌ５Ｏ１２：Ｅｕ系、Ｚｎ３（ＰＯ４）２：Ｍｎ系、ＹＢＯ３：Ｅｕ系、（Ｙ，Ｇｄ）ＢＯ３：Ｅｕ系、ＧｄＢＯ３：Ｅｕ系、ＳｃＢＯ３：Ｅｕ系、ＬｕＢＯ３：Ｅｕ系のものが用いられる。緑色蛍光体物質としては、例えば、Ｚｎ２ＳｉＯ４：Ｍｎ系、ＢａＡｌ１２Ｏ１９：Ｍｎ系、ＳｒＡｌ１３Ｏ１９：Ｍｎ系、ＣａＡｌ１２Ｏ１９：Ｍｎ系、ＹＢＯ３：Ｔｂ系、ＢａＭｇＡｌ１４Ｏ２３：Ｍｎ系、ＬｕＢＯ３：Ｔｂ系、ＧｄＢＯ３：Ｔｂ系、ＳｃＢＯ３：Ｔｂ系、Ｓｒ６Ｓｉ３Ｏ３Ｃｌ４：Ｅｕ系のものが用いられる。その他、ＺｎＯ：Ｚｎ系、ＺｎＳ：（Ｃｕ，Ａｌ）系、ＺｎＳ：Ａｇ系、Ｙ２Ｏ２Ｓ：Ｅｕ系、ＺｎＳ：Ｚｎ系、（Ｙ，Ｃｄ）ＢＯ３：Ｅｕ系、ＢａＭｇＡｌ１２Ｏ２３：Ｅｕ系のものも用いることができる。 The ceramic powder is not particularly limited, and examples thereof include alumina, ferrite, zirconia, zircon, barium zirconate, calcium zirconate, titanium oxide, barium titanate, strontium titanate, calcium titanate, magnesium titanate, zinc titanate, Lanthanum titanate, neodymium titanate, lead zirconium titanate, alumina nitride, silicon nitride, boron nitride, boron carbide, barium stannate, calcium stannate, magnesium silicate, mullite, steatite, cordierite, forsterite, etc. be done.
ITO, FTO, niobium oxide, vanadium oxide, tungsten oxide, lanthanum strontium manganite, lanthanum strontium cobalt ferrite, yttrium-stabilized zirconia, gadolinium-doped ceria, nickel oxide, lanthanum chromite, and the like can also be used.
The phosphor fine particles are not particularly limited, and for example, blue phosphor substances, red phosphor substances, green phosphor substances, etc., which are conventionally known as phosphor substances for displays, are used. Blue phosphor materials include, for example, MgAl 10 O 17 :Eu, Y 2 SiO 5 :Ce system, CaWO 4 :Pb system, BaMgAl 14 O 23 :Eu system, BaMgAl 16 O 27 :Eu system, BaMg 2 Al 14 O 23 : Eu system, BaMg 2 Al 14 O 27 : Eu system, ZnS: (Ag, Cd) system is used. Examples of red phosphor materials include Y2O3 :Eu system, Y2SiO5 :Eu system, Y3Al5O12 :Eu system, Zn3 ( PO4 ) 2 : Mn system , YBO3 :Eu. (Y,Gd)BO 3 :Eu system, GdBO 3 :Eu system, ScBO 3 :Eu system, and LuBO 3 :Eu system. Green phosphor materials include, for example, Zn2SiO4 :Mn-based, BaAl12O19 :Mn-based, SrAl13O19 : Mn -based, CaAl12O19 : Mn -based, YBO3 : Tb - based, and BaMgAl14O . 23 :Mn system, LuBO3 :Tb system, GdBO3 :Tb system , ScBO3 : Tb system, and Sr6Si3O3Cl4 :Eu system. In addition, ZnO: Zn system, ZnS: (Cu, Al) system, ZnS: Ag system, Y 2 O 2 S: Eu system, ZnS: Zn system, (Y, Cd) BO 3 : Eu system, BaMgAl 12 O 23 : Eu-based ones can also be used.
上記金属微粒子は特に限定されず、例えば、鉄、銅、ニッケル、パラジウム、白金、金、銀、アルミニウム、タングステンやこれらの合金等からなる粉末等が挙げられる。
また、カルボキシル基、アミノ基、アミド基等との吸着特性が良好で酸化されやすい銅や鉄等の金属も好適に用いることができる。これらの金属粉末は、単独で用いてもよく、２種以上を併用してもよい。
また、上記金属微粒子は、金属錯体のほか、種々のカーボンブラック、カーボンナノチューブ等を使用してもよい。 The fine metal particles are not particularly limited, and examples thereof include powders of iron, copper, nickel, palladium, platinum, gold, silver, aluminum, tungsten, and alloys thereof.
In addition, metals such as copper and iron, which have good adsorption properties with carboxyl groups, amino groups, amide groups, etc. and are easily oxidized, can also be suitably used. These metal powders may be used alone or in combination of two or more.
In addition to metal complexes, various carbon blacks, carbon nanotubes, and the like may be used as the metal fine particles.
また、カルボキシル基、アミノ基、アミド基等との吸着特性が良好で酸化されやすい銅や鉄等の金属も好適に用いることができる。これらの金属粉末は、単独で用いてもよく、２種以上を併用してもよい。
また、上記金属微粒子は、金属錯体のほか、種々のカーボンブラック、カーボンナノチューブ等を使用してもよい。 The fine metal particles are not particularly limited, and examples thereof include powders of iron, copper, nickel, palladium, platinum, gold, silver, aluminum, tungsten, and alloys thereof.
In addition, metals such as copper and iron, which have good adsorption properties with carboxyl groups, amino groups, amide groups, etc. and are easily oxidized, can also be suitably used. These metal powders may be used alone or in combination of two or more.
In addition to metal complexes, various carbon blacks, carbon nanotubes, and the like may be used as the metal fine particles.
上記無機微粒子は、リチウム又はチタンを含有することが好ましい。具体的には例えば、ＬｉＯ２・Ａｌ２Ｏ３・ＳｉＯ２系無機ガラス等の低融点ガラス、Ｌｉ２Ｓ－ＭｘＳｙ（Ｍ＝Ｂ、Ｓｉ、Ｇｅ、Ｐ）等のリチウム硫黄系ガラス、ＬｉＣｅＯ２等のリチウムコバルト複合酸化物、ＬｉＭｎＯ４等のリチウムマンガン複合酸化物、リチウムニッケル複合酸化物、リチウムバナジウム複合酸化物、リチウムジルコニウム複合酸化物、リチウムハフニウム複合酸化物、ケイリン酸リチウム（Ｌｉ３．５Ｓｉ０．５Ｐ０．５Ｏ４）、リン酸チタンリチウム（ＬｉＴｉ２（ＰＯ４）３）、チタン酸リチウム（Ｌｉ４Ｔｉ５Ｏ１２）、Ｌｉ４／３Ｔｉ５／３Ｏ４、ＬｉＣｏＯ２、リン酸ゲルマニウムリチウム（ＬｉＧｅ２（ＰＯ４）３）、Ｌｉ２－ＳｉＳ系ガラス、Ｌｉ４ＧｅＳ４－Ｌｉ３ＰＳ４系ガラス、ＬｉＳｉＯ３、ＬｉＭｎ２Ｏ４、Ｌｉ２Ｓ－Ｐ２Ｓ５系ガラス・セラミクス、Ｌｉ２Ｏ－ＳｉＯ２、Ｌｉ２Ｏ－Ｖ２Ｏ５－ＳｉＯ２、ＬｉＳ－ＳｉＳ２－Ｌｉ４ＳｉＯ４系ガラス、ＬｉＰＯＮ等のイオン導電性酸化物、Ｌｉ２Ｏ－Ｐ２Ｏ５－Ｂ２Ｏ３、Ｌｉ２Ｏ－ＧｅＯ２Ｂａ等の酸化リチウム化合物、ＬｉｘＡｌｙＴｉｚ（ＰＯ４）３系ガラス、ＬａｘＬｉｙＴｉＯｚ系ガラス、ＬｉｘＧｅｙＰｚＯ４系ガラス、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２系ガラス、ＬｉｖＳｉｗＰｘＳｙＣｌｚ系ガラス、ＬｉＮｂＯ３等のリチウムニオブ酸化物、Ｌｉ－β－アルミナ等のリチウムアルミナ化合物、Ｌｉ１４Ｚｎ（ＧｅＯ４）４等のリチウム亜鉛酸化物等が挙げられる。
The inorganic fine particles preferably contain lithium or titanium. Specifically, for example, low-melting-point glass such as LiO 2 ·Al 2 O 3 ·SiO 2 -based inorganic glass, lithium sulfur-based glass such as Li 2 SM x Sy (M=B, Si, Ge, P) , Lithium cobalt composite oxides such as LiCeO2 , Lithium manganese composite oxides such as LiMnO4 , Lithium nickel composite oxides, Lithium vanadium composite oxides, Lithium zirconium composite oxides, Lithium hafnium composite oxides, Lithium silicate phosphate (Li 3.5Si0.5P0.5O4 ), lithium titanium phosphate ( LiTi2 ( PO4) 3 ) , lithium titanate ( Li4Ti5O12 ), Li4 / 3Ti5 / 3O 4 , LiCoO 2 , lithium germanium phosphate (LiGe 2 (PO 4 ) 3 ), Li 2 —SiS glass, Li 4 GeS 4 —Li 3 PS 4 glass, LiSiO 3 , LiMn 2 O 4 , Li 2 S— P 2 S 5 based glass/ceramics, Li 2 O—SiO 2 , Li 2 O—V 2 O 5 —SiO 2 , LiS—SiS 2 —Li 4 SiO 4 based glass, ion conductive oxides such as LiPON, Li Lithium oxide compounds such as 2 O—P 2 O 5 —B 2 O 3 and Li 2 O—GeO 2 Ba, Li x Aly Ti z ( PO 4 ) 3 -based glass, La x Li y TiO z -based glass, Li xGeyPzO4 - based glass , Li7La3Zr2O12 - based glass , LivSiwPxSyClz - based glass, lithium niobium oxides such as LiNbO3 , Li - β-alumina, etc. Examples include lithium alumina compounds and lithium zinc oxides such as Li 14 Zn(GeO 4 ) 4 .
本発明の無機微粒子分散スラリー組成物における上記無機微粒子の含有量としては特に限定されないが、好ましい下限が１０重量％、好ましい上限が９０重量％である。１０重量％以上とすることで、充分な粘度を有し、優れた塗工性を有するものとでき、９０重量％以下とすることで、無機微粒子の分散性に優れるものとできる。
The content of the inorganic fine particles in the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited, but the preferred lower limit is 10% by weight and the preferred upper limit is 90% by weight. When the amount is 10% by weight or more, sufficient viscosity and excellent coatability can be obtained.
＜その他＞
本発明の無機微粒子分散スラリー組成物は、更に、可塑剤を含有する。
上記可塑剤としては、例えば、アジピン酸ジ（ブトキシエチル）、アジピン酸ジブトキシエトキシエチル、トリエチレングリコールジブチル、トリエチレングリコールビス（２－エチルヘキサノエート）、トリエチレングリコールジヘキサノエート、アセチルクエン酸トリエチル、アセチルクエン酸トリブチル、アセチルクエン酸ジエチル、アセチルクエン酸ジブチル、セバシン酸ジブチル、トリアセチン、アセチルオキシマロン酸ジエチル、エトキシマロン酸ジエチル等が挙げられる。
これらの可塑剤を用いることで、通常の可塑剤を使用する場合と比較して可塑剤添加量を低減することが可能となる（バインダーに対して３０重量％程度添加されるところ、２５重量％以下、更に２０重量％以下に低減可能）。
なかでも、構造中にベンゼン環等の芳香環を含まない非芳香族の可塑剤を使用することが好ましく、アジピン酸、トリエチレングリコール、クエン酸又はコハク酸に由来する成分を含有することがより好ましい。なお、芳香環を有する可塑剤は、燃焼して煤になりやすいため好ましくない。 <Others>
The inorganic fine particle-dispersed slurry composition of the present invention further contains a plasticizer.
Examples of the plasticizer include di(butoxyethyl) adipate, dibutoxyethoxyethyl adipate, triethylene glycol dibutyl, triethylene glycol bis(2-ethylhexanoate), triethylene glycol dihexanoate, acetyl triethyl citrate, acetyl tributyl citrate, acetyl diethyl citrate, acetyl citrate dibutyl, dibutyl sebacate, triacetin, diethyl acetyloxymalonate, diethyl ethoxymalonate and the like.
By using these plasticizers, it is possible to reduce the amount of plasticizer added compared to the case of using a normal plasticizer (when about 30% by weight is added to the binder, 25% by weight hereinafter, it can be further reduced to 20% by weight or less).
Among them, it is preferable to use a non-aromatic plasticizer that does not contain an aromatic ring such as a benzene ring in its structure, and it is more preferable to use a component derived from adipic acid, triethylene glycol, citric acid or succinic acid. preferable. A plasticizer having an aromatic ring is not preferable because it is likely to burn and become soot.
本発明の無機微粒子分散スラリー組成物は、更に、可塑剤を含有する。
上記可塑剤としては、例えば、アジピン酸ジ（ブトキシエチル）、アジピン酸ジブトキシエトキシエチル、トリエチレングリコールジブチル、トリエチレングリコールビス（２－エチルヘキサノエート）、トリエチレングリコールジヘキサノエート、アセチルクエン酸トリエチル、アセチルクエン酸トリブチル、アセチルクエン酸ジエチル、アセチルクエン酸ジブチル、セバシン酸ジブチル、トリアセチン、アセチルオキシマロン酸ジエチル、エトキシマロン酸ジエチル等が挙げられる。
これらの可塑剤を用いることで、通常の可塑剤を使用する場合と比較して可塑剤添加量を低減することが可能となる（バインダーに対して３０重量％程度添加されるところ、２５重量％以下、更に２０重量％以下に低減可能）。
なかでも、構造中にベンゼン環等の芳香環を含まない非芳香族の可塑剤を使用することが好ましく、アジピン酸、トリエチレングリコール、クエン酸又はコハク酸に由来する成分を含有することがより好ましい。なお、芳香環を有する可塑剤は、燃焼して煤になりやすいため好ましくない。 <Others>
The inorganic fine particle-dispersed slurry composition of the present invention further contains a plasticizer.
Examples of the plasticizer include di(butoxyethyl) adipate, dibutoxyethoxyethyl adipate, triethylene glycol dibutyl, triethylene glycol bis(2-ethylhexanoate), triethylene glycol dihexanoate, acetyl triethyl citrate, acetyl tributyl citrate, acetyl diethyl citrate, acetyl citrate dibutyl, dibutyl sebacate, triacetin, diethyl acetyloxymalonate, diethyl ethoxymalonate and the like.
By using these plasticizers, it is possible to reduce the amount of plasticizer added compared to the case of using a normal plasticizer (when about 30% by weight is added to the binder, 25% by weight hereinafter, it can be further reduced to 20% by weight or less).
Among them, it is preferable to use a non-aromatic plasticizer that does not contain an aromatic ring such as a benzene ring in its structure, and it is more preferable to use a component derived from adipic acid, triethylene glycol, citric acid or succinic acid. preferable. A plasticizer having an aromatic ring is not preferable because it is likely to burn and become soot.
また、上記可塑剤としては、エチル基、ブチル基等の炭素数２以上のアルキル基を有するものが好ましく、炭素数４以上のアルキル基を有するものがより好ましい。
上記可塑剤は、炭素数が２以上のアルキル基を含有することで、可塑剤への水分の吸収を抑制して、得られる無機微粒子分散シートにボイドやふくれ等の不具合を発生することを防止することができる。特に、可塑剤のアルキル基は分子末端に位置していることが好ましい。
また、上記可塑剤は、エチル基等の炭素数が２の官能基、ブチル基等の炭素数が４の官能基、ブトキシエチル基等の官能基を有することが好ましい。上記官能基は末端分子鎖に存在することが好ましい。
末端分子鎖にエチル基等の炭素数が２の官能基を持つ可塑剤はメタクリル酸エチルに由来するセグメントとの相性がよく、末端分子にブチル基等の炭素数が４の官能基を持つ可塑剤はメタクリル酸ブチルに由来するセグメントとの相性が良い。炭素数が２又は４の官能基を持つ可塑剤は本発明にかかる高分子量（メタ）アクリル樹脂との相性が良く、樹脂の脆性を好ましく改善することができる。更には、ブトキシエチル基はメタクリル酸エチルに由来するセグメント及びメタクリル酸ブチルに由来するセグメントの両方の組成と相性がよく好ましく用いることができる。 The plasticizer preferably has an alkyl group with 2 or more carbon atoms such as ethyl or butyl, and more preferably has an alkyl group with 4 or more carbon atoms.
By containing an alkyl group having 2 or more carbon atoms, the plasticizer suppresses the absorption of water into the plasticizer and prevents defects such as voids and swelling in the obtained inorganic fine particle dispersion sheet. can do. In particular, the alkyl group of the plasticizer is preferably located at the molecular terminal.
Further, the plasticizer preferably has a functional group having 2 carbon atoms such as an ethyl group, a functional group having 4 carbon atoms such as a butyl group, and a functional group such as a butoxyethyl group. Preferably, the functional group is present at the terminal molecular chain.
A plasticizer with a functional group with 2 carbon atoms such as an ethyl group in the terminal molecular chain has good compatibility with a segment derived from ethyl methacrylate, and a plasticizer with a functional group with 4 carbon atoms such as a butyl group in the terminal molecule. The agent is compatible with segments derived from butyl methacrylate. A plasticizer having a functional group with 2 or 4 carbon atoms has good compatibility with the high-molecular-weight (meth)acrylic resin according to the present invention, and can preferably improve the brittleness of the resin. Furthermore, a butoxyethyl group is compatible with the composition of both the segment derived from ethyl methacrylate and the segment derived from butyl methacrylate, and can be preferably used.
上記可塑剤は、炭素数が２以上のアルキル基を含有することで、可塑剤への水分の吸収を抑制して、得られる無機微粒子分散シートにボイドやふくれ等の不具合を発生することを防止することができる。特に、可塑剤のアルキル基は分子末端に位置していることが好ましい。
また、上記可塑剤は、エチル基等の炭素数が２の官能基、ブチル基等の炭素数が４の官能基、ブトキシエチル基等の官能基を有することが好ましい。上記官能基は末端分子鎖に存在することが好ましい。
末端分子鎖にエチル基等の炭素数が２の官能基を持つ可塑剤はメタクリル酸エチルに由来するセグメントとの相性がよく、末端分子にブチル基等の炭素数が４の官能基を持つ可塑剤はメタクリル酸ブチルに由来するセグメントとの相性が良い。炭素数が２又は４の官能基を持つ可塑剤は本発明にかかる高分子量（メタ）アクリル樹脂との相性が良く、樹脂の脆性を好ましく改善することができる。更には、ブトキシエチル基はメタクリル酸エチルに由来するセグメント及びメタクリル酸ブチルに由来するセグメントの両方の組成と相性がよく好ましく用いることができる。 The plasticizer preferably has an alkyl group with 2 or more carbon atoms such as ethyl or butyl, and more preferably has an alkyl group with 4 or more carbon atoms.
By containing an alkyl group having 2 or more carbon atoms, the plasticizer suppresses the absorption of water into the plasticizer and prevents defects such as voids and swelling in the obtained inorganic fine particle dispersion sheet. can do. In particular, the alkyl group of the plasticizer is preferably located at the molecular terminal.
Further, the plasticizer preferably has a functional group having 2 carbon atoms such as an ethyl group, a functional group having 4 carbon atoms such as a butyl group, and a functional group such as a butoxyethyl group. Preferably, the functional group is present at the terminal molecular chain.
A plasticizer with a functional group with 2 carbon atoms such as an ethyl group in the terminal molecular chain has good compatibility with a segment derived from ethyl methacrylate, and a plasticizer with a functional group with 4 carbon atoms such as a butyl group in the terminal molecule. The agent is compatible with segments derived from butyl methacrylate. A plasticizer having a functional group with 2 or 4 carbon atoms has good compatibility with the high-molecular-weight (meth)acrylic resin according to the present invention, and can preferably improve the brittleness of the resin. Furthermore, a butoxyethyl group is compatible with the composition of both the segment derived from ethyl methacrylate and the segment derived from butyl methacrylate, and can be preferably used.
上記可塑剤は、炭素：酸素比が５：１～３：１であることが好ましい。
炭素：酸素比を上記範囲とすることで、可塑剤の燃焼性を向上させて、残留炭素の発生を防止することができる。また、（メタ）アクリル樹脂との相溶性を向上させて、少量の可塑剤でも可塑化効果を発揮させることができる。
また、プロピレングリコール骨格やトリメチレングリコール骨格の高沸点有機溶剤も、炭素数が４以上のアルキル基を含有し、炭素：酸素比が５：１～３：１であれば好ましく用いることができる。 The plasticizer preferably has a carbon:oxygen ratio of 5:1 to 3:1.
By setting the carbon:oxygen ratio within the above range, it is possible to improve the combustibility of the plasticizer and prevent the generation of residual carbon. Moreover, compatibility with (meth)acrylic resin can be improved, and a plasticizing effect can be exhibited even with a small amount of plasticizer.
Also, high-boiling organic solvents having a propylene glycol skeleton or a trimethylene glycol skeleton can be preferably used as long as they contain an alkyl group having 4 or more carbon atoms and have a carbon:oxygen ratio of 5:1 to 3:1.
炭素：酸素比を上記範囲とすることで、可塑剤の燃焼性を向上させて、残留炭素の発生を防止することができる。また、（メタ）アクリル樹脂との相溶性を向上させて、少量の可塑剤でも可塑化効果を発揮させることができる。
また、プロピレングリコール骨格やトリメチレングリコール骨格の高沸点有機溶剤も、炭素数が４以上のアルキル基を含有し、炭素：酸素比が５：１～３：１であれば好ましく用いることができる。 The plasticizer preferably has a carbon:oxygen ratio of 5:1 to 3:1.
By setting the carbon:oxygen ratio within the above range, it is possible to improve the combustibility of the plasticizer and prevent the generation of residual carbon. Moreover, compatibility with (meth)acrylic resin can be improved, and a plasticizing effect can be exhibited even with a small amount of plasticizer.
Also, high-boiling organic solvents having a propylene glycol skeleton or a trimethylene glycol skeleton can be preferably used as long as they contain an alkyl group having 4 or more carbon atoms and have a carbon:oxygen ratio of 5:1 to 3:1.
上記可塑剤の沸点は２４０℃以上３９０℃未満であることが好ましい。上記沸点が２４０℃以上であることで、乾燥工程で蒸発しやすくなり、成形体への残留を防止できる。また、３９０℃未満であることで、残留炭素が生じることを防止できる。なお、上記沸点は、常圧での沸点をいう。
The boiling point of the plasticizer is preferably 240°C or higher and lower than 390°C. When the boiling point is 240° C. or higher, it becomes easy to evaporate in the drying step, and can be prevented from remaining in the molded article. In addition, when the temperature is less than 390°C, residual carbon can be prevented from being generated. In addition, the said boiling point means the boiling point in a normal pressure.
本発明の無機微粒子分散スラリー組成物における上記可塑剤の含有量としては特に限定されないが、好ましい下限は０．１重量％、好ましい上限は３．０重量％である。上記範囲内とすることで、可塑剤の焼成残渣を少なくすることができる。
The content of the plasticizer in the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited, but the preferred lower limit is 0.1% by weight and the preferred upper limit is 3.0% by weight. By setting it within the above range, it is possible to reduce the baking residue of the plasticizer.
本発明の無機微粒子分散スラリー組成物における上記（メタ）アクリル樹脂組成物の含有量は特に限定されないが、好ましい下限は０．５重量％、好ましい上限は１０重量％である。
上記範囲とすることで、低温で焼成しても脱脂可能であり、また、無機微粒子の分散性及び凝集抑制効果に優れる無機微粒子分散スラリー組成物とすることができる。
上記（メタ）アクリル樹脂組成物の含有量は、より好ましい下限が１重量％、より好ましい上限が７重量％である。 The content of the (meth)acrylic resin composition in the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited, but the preferred lower limit is 0.5% by weight and the preferred upper limit is 10% by weight.
When the content is within the above range, the inorganic fine particle-dispersed slurry composition can be degreased even when fired at a low temperature, and has excellent dispersibility of the inorganic fine particles and an effect of suppressing aggregation of the inorganic fine particles.
A more preferable lower limit to the content of the (meth)acrylic resin composition is 1% by weight, and a more preferable upper limit is 7% by weight.
上記範囲とすることで、低温で焼成しても脱脂可能であり、また、無機微粒子の分散性及び凝集抑制効果に優れる無機微粒子分散スラリー組成物とすることができる。
上記（メタ）アクリル樹脂組成物の含有量は、より好ましい下限が１重量％、より好ましい上限が７重量％である。 The content of the (meth)acrylic resin composition in the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited, but the preferred lower limit is 0.5% by weight and the preferred upper limit is 10% by weight.
When the content is within the above range, the inorganic fine particle-dispersed slurry composition can be degreased even when fired at a low temperature, and has excellent dispersibility of the inorganic fine particles and an effect of suppressing aggregation of the inorganic fine particles.
A more preferable lower limit to the content of the (meth)acrylic resin composition is 1% by weight, and a more preferable upper limit is 7% by weight.
本発明の無機微粒子分散スラリー組成物は、更に、界面活性剤等の添加剤を含有してもよい。
上記界面活性剤は特に限定されず、例えば、カチオン系界面活性剤、アニオン系界面活性剤、ノニオン系界面活性剤が挙げられる。
上記ノニオン系界面活性剤としては特に限定されないが、ＨＬＢ値が１０以上２０以下のノニオン系界面活性剤であることが好ましい。ここで、ＨＬＢ値とは、界面活性剤の親水性、親油性を表す指標として用いられるものであって、計算方法がいくつか提案されており、例えば、エステル系の界面活性剤について、鹸化価をＳ、界面活性剤を構成する脂肪酸の酸価をＡとし、ＨＬＢ値を２０（１－Ｓ／Ａ）等の定義がある。具体的には、脂肪鎖にアルキレンエーテルを付加させたポリエチレンオキサイドを有するノニオン系界面活性剤が好適であり、具体的には例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンセチルエーテル等が好適に用いられる。なお、上記ノニオン系界面活性剤は、熱分解性がよいが、大量に添加すると無機微粒子分散スラリー組成物の熱分解性が低下することがあるため、含有量の好ましい上限は５重量％である。 The inorganic fine particle-dispersed slurry composition of the present invention may further contain additives such as surfactants.
The surfactant is not particularly limited, and examples thereof include cationic surfactants, anionic surfactants, and nonionic surfactants.
Although the nonionic surfactant is not particularly limited, it is preferably a nonionic surfactant having an HLB value of 10 or more and 20 or less. Here, the HLB value is used as an index representing the hydrophilicity and lipophilicity of a surfactant, and several calculation methods have been proposed. is defined as S, the acid value of the fatty acid constituting the surfactant as A, and the HLB value as 20 (1-S/A). Specifically, nonionic surfactants having polyethylene oxide in which an alkylene ether is added to the fatty chain are suitable, and specifically, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, etc. are preferably used. be done. The above nonionic surfactant has good thermal decomposability, but if added in a large amount, the thermal decomposability of the inorganic fine particle-dispersed slurry composition may decrease, so the preferred upper limit of the content is 5% by weight. .
上記界面活性剤は特に限定されず、例えば、カチオン系界面活性剤、アニオン系界面活性剤、ノニオン系界面活性剤が挙げられる。
上記ノニオン系界面活性剤としては特に限定されないが、ＨＬＢ値が１０以上２０以下のノニオン系界面活性剤であることが好ましい。ここで、ＨＬＢ値とは、界面活性剤の親水性、親油性を表す指標として用いられるものであって、計算方法がいくつか提案されており、例えば、エステル系の界面活性剤について、鹸化価をＳ、界面活性剤を構成する脂肪酸の酸価をＡとし、ＨＬＢ値を２０（１－Ｓ／Ａ）等の定義がある。具体的には、脂肪鎖にアルキレンエーテルを付加させたポリエチレンオキサイドを有するノニオン系界面活性剤が好適であり、具体的には例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンセチルエーテル等が好適に用いられる。なお、上記ノニオン系界面活性剤は、熱分解性がよいが、大量に添加すると無機微粒子分散スラリー組成物の熱分解性が低下することがあるため、含有量の好ましい上限は５重量％である。 The inorganic fine particle-dispersed slurry composition of the present invention may further contain additives such as surfactants.
The surfactant is not particularly limited, and examples thereof include cationic surfactants, anionic surfactants, and nonionic surfactants.
Although the nonionic surfactant is not particularly limited, it is preferably a nonionic surfactant having an HLB value of 10 or more and 20 or less. Here, the HLB value is used as an index representing the hydrophilicity and lipophilicity of a surfactant, and several calculation methods have been proposed. is defined as S, the acid value of the fatty acid constituting the surfactant as A, and the HLB value as 20 (1-S/A). Specifically, nonionic surfactants having polyethylene oxide in which an alkylene ether is added to the fatty chain are suitable, and specifically, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, etc. are preferably used. be done. The above nonionic surfactant has good thermal decomposability, but if added in a large amount, the thermal decomposability of the inorganic fine particle-dispersed slurry composition may decrease, so the preferred upper limit of the content is 5% by weight. .
本発明の無機微粒子分散スラリー組成物の粘度は特に限定されないが、２０℃においてＢ型粘度計を用いプローブ回転数を５ｒｐｍに設定して測定した場合の粘度の好ましい下限が０．１Ｐａ・ｓ、好ましい上限が１００Ｐａ・ｓである。
上記粘度を０．１Ｐａ・ｓ以上とすることで、ダイコート印刷法等により塗工した後、得られる無機微粒子分散シートが所定の形状を維持することが可能となる。また、上記粘度を１００Ｐａ・ｓ以下とすることで、ダイの塗出痕が消えない等の不具合を防止して、印刷性に優れるものとできる。 The viscosity of the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited. A preferable upper limit is 100 Pa·s.
By setting the viscosity to 0.1 Pa·s or more, the obtained inorganic fine particle-dispersed sheet can maintain a predetermined shape after being coated by a die coat printing method or the like. Further, by setting the viscosity to 100 Pa·s or less, it is possible to prevent problems such as not erasing the coating marks of the die, and to achieve excellent printability.
上記粘度を０．１Ｐａ・ｓ以上とすることで、ダイコート印刷法等により塗工した後、得られる無機微粒子分散シートが所定の形状を維持することが可能となる。また、上記粘度を１００Ｐａ・ｓ以下とすることで、ダイの塗出痕が消えない等の不具合を防止して、印刷性に優れるものとできる。 The viscosity of the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited. A preferable upper limit is 100 Pa·s.
By setting the viscosity to 0.1 Pa·s or more, the obtained inorganic fine particle-dispersed sheet can maintain a predetermined shape after being coated by a die coat printing method or the like. Further, by setting the viscosity to 100 Pa·s or less, it is possible to prevent problems such as not erasing the coating marks of the die, and to achieve excellent printability.
本発明の無機微粒子分散スラリー組成物を作製する方法は特に限定されず、従来公知の攪拌方法が挙げられ、具体的には、例えば、上記（メタ）アクリル樹脂組成物、上記無機微粒子、上記有機溶剤及び必要に応じて添加される可塑剤等の他の成分を３本ロール等で攪拌する方法等が挙げられる。上記無機微粒子分散スラリー組成物の構成成分の添加順序は適宜設定することができる。
The method for producing the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited, and conventionally known stirring methods can be mentioned. Examples thereof include a method of stirring other components such as a solvent and optionally added plasticizer with a three-roll roller or the like. The addition order of the components of the inorganic fine particle-dispersed slurry composition can be appropriately set.
本発明の無機微粒子分散スラリー組成物を、片面離型処理を施した支持フィルム上に塗工し、有機溶剤を乾燥させ、成形することで、無機微粒子分散成形物を製造することができる。このような無機微粒子分散成形物もまた本発明の１つである。
本発明の無機微粒子分散成形物の形状は特に限定されないが、例えば、シート等の形状とすることができる。 The inorganic fine particle dispersion slurry composition of the present invention is applied onto a support film that has been subjected to mold release treatment on one side, the organic solvent is dried, and an inorganic fine particle dispersion molding can be produced by molding. Such an inorganic fine particle dispersion molding is also one aspect of the present invention.
The shape of the inorganic fine particle-dispersed molding of the present invention is not particularly limited, but may be, for example, a sheet shape.
本発明の無機微粒子分散成形物の形状は特に限定されないが、例えば、シート等の形状とすることができる。 The inorganic fine particle dispersion slurry composition of the present invention is applied onto a support film that has been subjected to mold release treatment on one side, the organic solvent is dried, and an inorganic fine particle dispersion molding can be produced by molding. Such an inorganic fine particle dispersion molding is also one aspect of the present invention.
The shape of the inorganic fine particle-dispersed molding of the present invention is not particularly limited, but may be, for example, a sheet shape.
本発明の無機微粒子分散成形物の製造方法としては、例えば、本発明の無機微粒子分散スラリー組成物をロールコーター、ダイコーター、スクイズコーター、カーテンコーター等の塗工方式によって支持フィルム上に均一に塗膜を形成する方法等が挙げられる。
なお、無機微粒子分散成形物を製造する場合、重合液をそのまま無機微粒子分散スラリー組成物として、高分子量（メタ）アクリル樹脂を乾燥させずに、無機微粒子分散成形物に加工することが好ましい。
高分子量（メタ）アクリル樹脂を乾燥させると、再度溶液化した際にパーティクルと呼ばれる未乾燥粒子が発生し、このようなパーティクルは、カートリッジフィルター等を用いた濾過でも除去することが難しく、無機微粒子分散成形物の強度に悪影響を及ぼすためである。 As a method for producing the inorganic fine particle dispersion molding of the present invention, for example, the inorganic fine particle dispersion slurry composition of the present invention is uniformly coated on a support film by a coating method such as a roll coater, a die coater, a squeeze coater, a curtain coater, or the like. A method of forming a film and the like can be mentioned.
When producing an inorganic fine particle dispersed molded product, it is preferable to use the polymerization liquid as it is as an inorganic fine particle dispersed slurry composition and process it into an inorganic fine particle dispersed molded product without drying the high molecular weight (meth)acrylic resin.
When high-molecular-weight (meth)acrylic resin is dried, undried particles called particles are generated when it is resolubilized, and such particles are difficult to remove even by filtration using a cartridge filter or the like. This is because it adversely affects the strength of the dispersion molding.
なお、無機微粒子分散成形物を製造する場合、重合液をそのまま無機微粒子分散スラリー組成物として、高分子量（メタ）アクリル樹脂を乾燥させずに、無機微粒子分散成形物に加工することが好ましい。
高分子量（メタ）アクリル樹脂を乾燥させると、再度溶液化した際にパーティクルと呼ばれる未乾燥粒子が発生し、このようなパーティクルは、カートリッジフィルター等を用いた濾過でも除去することが難しく、無機微粒子分散成形物の強度に悪影響を及ぼすためである。 As a method for producing the inorganic fine particle dispersion molding of the present invention, for example, the inorganic fine particle dispersion slurry composition of the present invention is uniformly coated on a support film by a coating method such as a roll coater, a die coater, a squeeze coater, a curtain coater, or the like. A method of forming a film and the like can be mentioned.
When producing an inorganic fine particle dispersed molded product, it is preferable to use the polymerization liquid as it is as an inorganic fine particle dispersed slurry composition and process it into an inorganic fine particle dispersed molded product without drying the high molecular weight (meth)acrylic resin.
When high-molecular-weight (meth)acrylic resin is dried, undried particles called particles are generated when it is resolubilized, and such particles are difficult to remove even by filtration using a cartridge filter or the like. This is because it adversely affects the strength of the dispersion molding.
例えば、本発明の無機微粒子分散成形物がシート状である場合、本発明の無機微粒子分散成形物を製造する際に用いる支持フィルムは、耐熱性及び耐溶剤性を有するとともに可撓性を有する樹脂フィルムであることが好ましい。支持フィルムが可撓性を有することにより、ロールコーター、ブレードコーターなどによって支持フィルムの表面に無機微粒子分散スラリー組成物を塗布することができ、得られる無機微粒子分散シート形成フィルムをロール状に巻回した状態で保存し、供給することができる。
For example, when the inorganic fine particle-dispersed molded article of the present invention is in the form of a sheet, the support film used in producing the inorganic fine particle-dispersed molded article of the present invention is a flexible resin having heat resistance and solvent resistance. A film is preferred. Since the support film has flexibility, the inorganic fine particle-dispersed slurry composition can be applied to the surface of the support film by a roll coater, a blade coater, or the like, and the resulting inorganic fine particle-dispersed sheet-forming film is wound into a roll. It can be stored and supplied as is.
上記支持フィルムを形成する樹脂としては、例えばポリエチレンテレフタレート、ポリエステル、ポリエチレン、ポリプロピレン、ポリスチレン、ポリイミド、ポリビニルアルコール、ポリ塩化ビニル、ポリフロロエチレン等の含フッ素樹脂、ナイロン、セルロース等が挙げられる。
上記支持フィルムの厚みは、例えば、２０～１００μｍが好ましい。
また、支持フィルムの表面には離型処理が施されていることが好ましく、これにより、転写工程において、支持フィルムの剥離操作を容易に行うことができる。 Examples of the resin forming the support film include fluorine-containing resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose.
The thickness of the support film is preferably 20 to 100 μm, for example.
Moreover, it is preferable that the surface of the support film is subjected to a release treatment, so that the support film can be easily peeled off in the transfer step.
上記支持フィルムの厚みは、例えば、２０～１００μｍが好ましい。
また、支持フィルムの表面には離型処理が施されていることが好ましく、これにより、転写工程において、支持フィルムの剥離操作を容易に行うことができる。 Examples of the resin forming the support film include fluorine-containing resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose.
The thickness of the support film is preferably 20 to 100 μm, for example.
Moreover, it is preferable that the surface of the support film is subjected to a release treatment, so that the support film can be easily peeled off in the transfer step.
本発明の無機微粒子分散スラリー組成物を塗工乾燥することで無機微粒子分散成形物を製造することができる。
また、本発明の無機微粒子分散スラリー組成物、無機微粒子分散成形物を、誘電体グリーンシート、電極ペーストに用いることで積層セラミクスコンデンサを製造することができる。また、本発明の無機微粒子分散スラリー組成物、無機微粒子分散成形物を使用することで磁性材料を製造することができる。 An inorganic fine particle-dispersed molding can be produced by coating and drying the inorganic fine particle-dispersed slurry composition of the present invention.
Moreover, a laminated ceramic capacitor can be produced by using the inorganic fine particle-dispersed slurry composition and the inorganic fine particle-dispersed molded product of the present invention for dielectric green sheets and electrode pastes. A magnetic material can be produced by using the inorganic fine particle-dispersed slurry composition and the inorganic fine particle-dispersed molding of the present invention.
また、本発明の無機微粒子分散スラリー組成物、無機微粒子分散成形物を、誘電体グリーンシート、電極ペーストに用いることで積層セラミクスコンデンサを製造することができる。また、本発明の無機微粒子分散スラリー組成物、無機微粒子分散成形物を使用することで磁性材料を製造することができる。 An inorganic fine particle-dispersed molding can be produced by coating and drying the inorganic fine particle-dispersed slurry composition of the present invention.
Moreover, a laminated ceramic capacitor can be produced by using the inorganic fine particle-dispersed slurry composition and the inorganic fine particle-dispersed molded product of the present invention for dielectric green sheets and electrode pastes. A magnetic material can be produced by using the inorganic fine particle-dispersed slurry composition and the inorganic fine particle-dispersed molding of the present invention.
上記積層セラミクスコンデンサを製造する方法としては、本発明の無機微粒子分散成形物に導電ペーストを印刷、乾燥して、誘電体シートを作製する工程、及び、前記誘電体シートを積層する工程を有する製造方法が挙げられる。
The method for producing the laminated ceramic capacitor includes the steps of printing a conductive paste on the inorganic fine particle-dispersed molding of the present invention and drying it to produce a dielectric sheet, and laminating the dielectric sheet. method.
上記導電ペーストは、導電粉末を含有するものである。
上記導電粉末の材質は、導電性を有する材質であれば特に限定されず、例えば、ニッケル、パラジウム、白金、金、銀、銅、モリブデン、錫及びこれらの合金等が挙げられる。これらの導電粉末は、単独で用いてもよく、２種以上を併用してもよい。 The conductive paste contains conductive powder.
The material of the conductive powder is not particularly limited as long as it has conductivity, and examples thereof include nickel, palladium, platinum, gold, silver, copper, molybdenum, tin, and alloys thereof. These conductive powders may be used alone or in combination of two or more.
上記導電粉末の材質は、導電性を有する材質であれば特に限定されず、例えば、ニッケル、パラジウム、白金、金、銀、銅、モリブデン、錫及びこれらの合金等が挙げられる。これらの導電粉末は、単独で用いてもよく、２種以上を併用してもよい。 The conductive paste contains conductive powder.
The material of the conductive powder is not particularly limited as long as it has conductivity, and examples thereof include nickel, palladium, platinum, gold, silver, copper, molybdenum, tin, and alloys thereof. These conductive powders may be used alone or in combination of two or more.
上記導電ペーストを印刷する方法は特に限定されず、例えば、スクリーン印刷法、ダイコート印刷法、オフセット印刷法、グラビア印刷法、インクジェット印刷法等が挙げられる。
A method for printing the conductive paste is not particularly limited, and examples thereof include a screen printing method, a die coat printing method, an offset printing method, a gravure printing method, an inkjet printing method, and the like.
上記積層セラミクスコンデンサの製造方法では、上記導電ペーストを印刷した誘電体シートを積層することで、積層セラミクスコンデンサが得られる。
In the manufacturing method of the laminated ceramic capacitor, the laminated ceramic capacitor is obtained by laminating the dielectric sheets printed with the conductive paste.
本発明によれば、低温で優れた分解性を有するとともに、無機微粒子の分散性や凝集抑制効果を向上させることができる（メタ）アクリル樹脂組成物を提供することができる。また、該（メタ）アクリル樹脂組成物を用いる無機微粒子分散スラリー組成物、無機微粒子分散成形物を提供することができる。
According to the present invention, it is possible to provide a (meth)acrylic resin composition that has excellent decomposability at low temperatures and that can improve the dispersibility of inorganic fine particles and the effect of suppressing aggregation. Further, an inorganic fine particle-dispersed slurry composition and an inorganic fine particle-dispersed molded product using the (meth)acrylic resin composition can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。
EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples.
（製造例１～２８、高分子量（メタ）アクリル樹脂の作製）
攪拌機、冷却器、温度計、湯浴、及び、窒素ガス導入口を備えた２Ｌセパラブルフラスコを用意し、２Ｌセパラブルフラスコに、表１に示す配合となるようにモノマー合計１００重量部を投入した。更に、有機溶剤として酢酸ブチル５０重量部とを混合し、モノマー混合液を得た。
なお、モノマーとしては、以下のものを用いた。
ＭＭＡ：メチルメタクリレート
ＥＭＡ：エチルメタクリレート
ｎＢＭＡ：ｎ－ブチルメタクリレート
ｉＢＭＡ：イソブチルメタクリレート
２ＥＨＭＡ：２－エチルヘキシルメタクリレート
ＨＥＭＡ：２－ヒドロキシエチルメタクリレート
ＨＰＭＡ：２－ヒドロキシプロピルメタクリレート
ＨＢＭＡ：２－ヒドロキシブチルメタクリレート (Production Examples 1 to 28, Production of High Molecular Weight (Meth) Acrylic Resin)
A 2 L separable flask equipped with a stirrer, cooler, thermometer, hot water bath, and nitrogen gas inlet is prepared, and a total of 100 parts by weight of monomers are added to the 2 L separable flask so that the composition shown in Table 1 is obtained. did. Furthermore, 50 parts by weight of butyl acetate was mixed as an organic solvent to obtain a monomer mixture.
In addition, the following were used as a monomer.
MMA: methyl methacrylate EMA: ethyl methacrylate nBMA: n-butyl methacrylate iBMA: isobutyl methacrylate 2EHMA: 2-ethylhexyl methacrylate HEMA: 2-hydroxyethyl methacrylate HPMA: 2-hydroxypropyl methacrylate HBMA: 2-hydroxybutyl methacrylate
攪拌機、冷却器、温度計、湯浴、及び、窒素ガス導入口を備えた２Ｌセパラブルフラスコを用意し、２Ｌセパラブルフラスコに、表１に示す配合となるようにモノマー合計１００重量部を投入した。更に、有機溶剤として酢酸ブチル５０重量部とを混合し、モノマー混合液を得た。
なお、モノマーとしては、以下のものを用いた。
ＭＭＡ：メチルメタクリレート
ＥＭＡ：エチルメタクリレート
ｎＢＭＡ：ｎ－ブチルメタクリレート
ｉＢＭＡ：イソブチルメタクリレート
２ＥＨＭＡ：２－エチルヘキシルメタクリレート
ＨＥＭＡ：２－ヒドロキシエチルメタクリレート
ＨＰＭＡ：２－ヒドロキシプロピルメタクリレート
ＨＢＭＡ：２－ヒドロキシブチルメタクリレート (Production Examples 1 to 28, Production of High Molecular Weight (Meth) Acrylic Resin)
A 2 L separable flask equipped with a stirrer, cooler, thermometer, hot water bath, and nitrogen gas inlet is prepared, and a total of 100 parts by weight of monomers are added to the 2 L separable flask so that the composition shown in Table 1 is obtained. did. Furthermore, 50 parts by weight of butyl acetate was mixed as an organic solvent to obtain a monomer mixture.
In addition, the following were used as a monomer.
MMA: methyl methacrylate EMA: ethyl methacrylate nBMA: n-butyl methacrylate iBMA: isobutyl methacrylate 2EHMA: 2-ethylhexyl methacrylate HEMA: 2-hydroxyethyl methacrylate HPMA: 2-hydroxypropyl methacrylate HBMA: 2-hydroxybutyl methacrylate
得られたモノマー混合液を、窒素ガスを用いて２０分間バブリングすることにより溶存酸素を除去した後、セパラブルフラスコ系内を窒素ガスで置換し攪拌しながら湯浴が沸騰するまで昇温した。重合開始剤及び連鎖移動剤を表１に示す添加量となるように加えた。
重合開始から７時間後、室温まで冷却し重合を終了させた。その後１３０℃のオーブンで得られた樹脂溶液を乾燥させ有機溶剤を取り除いた。これにより、高分子量（メタ）アクリル樹脂を得た。
なお、重合開始剤及び連鎖移動剤としては、以下のものを用いた。
＜重合開始剤＞
ｔ－ブチルパーオキシピバレート
＜連鎖移動剤＞
ＣＴ－１：３－メルカプト－１，２－プロパンジオール
ＣＴ－２：３－メルカプト－１－プロパノール
ＣＴ－３：３－メルカプト－２－ブタノール
ＣＴ－４：８－メルカプト－１－オクタノール
ＣＴ－５：メルカプトコハク酸 After nitrogen gas was bubbled through the obtained monomer mixture for 20 minutes to remove dissolved oxygen, the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised until the water bath boiled while stirring. A polymerization initiator and a chain transfer agent were added in amounts shown in Table 1.
After 7 hours from the initiation of polymerization, the mixture was cooled to room temperature to complete the polymerization. After that, the obtained resin solution was dried in an oven at 130° C. to remove the organic solvent. Thus, a high molecular weight (meth)acrylic resin was obtained.
In addition, the following were used as a polymerization initiator and a chain transfer agent.
<Polymerization initiator>
t-butyl peroxypivalate <chain transfer agent>
CT-1: 3-mercapto-1,2-propanediol CT-2: 3-mercapto-1-propanol CT-3: 3-mercapto-2-butanol CT-4: 8-mercapto-1-octanol CT-5 : Mercaptosuccinic acid
重合開始から７時間後、室温まで冷却し重合を終了させた。その後１３０℃のオーブンで得られた樹脂溶液を乾燥させ有機溶剤を取り除いた。これにより、高分子量（メタ）アクリル樹脂を得た。
なお、重合開始剤及び連鎖移動剤としては、以下のものを用いた。
＜重合開始剤＞
ｔ－ブチルパーオキシピバレート
＜連鎖移動剤＞
ＣＴ－１：３－メルカプト－１，２－プロパンジオール
ＣＴ－２：３－メルカプト－１－プロパノール
ＣＴ－３：３－メルカプト－２－ブタノール
ＣＴ－４：８－メルカプト－１－オクタノール
ＣＴ－５：メルカプトコハク酸 After nitrogen gas was bubbled through the obtained monomer mixture for 20 minutes to remove dissolved oxygen, the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised until the water bath boiled while stirring. A polymerization initiator and a chain transfer agent were added in amounts shown in Table 1.
After 7 hours from the initiation of polymerization, the mixture was cooled to room temperature to complete the polymerization. After that, the obtained resin solution was dried in an oven at 130° C. to remove the organic solvent. Thus, a high molecular weight (meth)acrylic resin was obtained.
In addition, the following were used as a polymerization initiator and a chain transfer agent.
<Polymerization initiator>
t-butyl peroxypivalate <chain transfer agent>
CT-1: 3-mercapto-1,2-propanediol CT-2: 3-mercapto-1-propanol CT-3: 3-mercapto-2-butanol CT-4: 8-mercapto-1-octanol CT-5 : Mercaptosuccinic acid
（製造例２９～６２、低分子量（メタ）アクリル樹脂及びその他の（メタ）アクリル樹脂の作製）
攪拌機、冷却器、温度計、湯浴、及び、窒素ガス導入口を備えた２Ｌセパラブルフラスコを用意した。２Ｌセパラブルフラスコに、表２に示す配合となるようにモノマー合計１００重量部投入した。更に、有機溶剤として酢酸ブチル５０重量部とを混合し、モノマー混合液を得た。
なお、モノマーとしては、製造例１～２８で挙げたものと同様のものを用いた。 (Production Examples 29 to 62, Preparation of Low Molecular Weight (Meth) Acrylic Resins and Other (Meth) Acrylic Resins)
A 2 L separable flask equipped with a stirrer, cooler, thermometer, hot water bath, and nitrogen gas inlet was prepared. A total of 100 parts by weight of the monomers were charged into a 2-L separable flask so as to obtain the formulation shown in Table 2. Furthermore, 50 parts by weight of butyl acetate was mixed as an organic solvent to obtain a monomer mixture.
As the monomer, the same monomers as mentioned in Production Examples 1 to 28 were used.
攪拌機、冷却器、温度計、湯浴、及び、窒素ガス導入口を備えた２Ｌセパラブルフラスコを用意した。２Ｌセパラブルフラスコに、表２に示す配合となるようにモノマー合計１００重量部投入した。更に、有機溶剤として酢酸ブチル５０重量部とを混合し、モノマー混合液を得た。
なお、モノマーとしては、製造例１～２８で挙げたものと同様のものを用いた。 (Production Examples 29 to 62, Preparation of Low Molecular Weight (Meth) Acrylic Resins and Other (Meth) Acrylic Resins)
A 2 L separable flask equipped with a stirrer, cooler, thermometer, hot water bath, and nitrogen gas inlet was prepared. A total of 100 parts by weight of the monomers were charged into a 2-L separable flask so as to obtain the formulation shown in Table 2. Furthermore, 50 parts by weight of butyl acetate was mixed as an organic solvent to obtain a monomer mixture.
As the monomer, the same monomers as mentioned in Production Examples 1 to 28 were used.
得られたモノマー混合液を、窒素ガスを用いて２０分間バブリングすることにより溶存酸素を除去した後、セパラブルフラスコ系内を窒素ガスで置換し攪拌しながら湯浴が沸騰するまで昇温した。重合開始剤及び連鎖移動剤を表２に示す種類及び添加量となるように加えた。
重合開始から７時間後、室温まで冷却し重合を終了させた。その後１３０℃のオーブンで得られた樹脂溶液を乾燥させ有機溶剤を取り除いた。これにより、低分子量（メタ）アクリル樹脂を得た。
なお、重合開始剤及び連鎖移動剤としては、製造例１～２８で挙げたものと同様のものを用いた。 After nitrogen gas was bubbled through the obtained monomer mixture for 20 minutes to remove dissolved oxygen, the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised until the water bath boiled while stirring. Polymerization initiators and chain transfer agents were added in the types and amounts shown in Table 2.
After 7 hours from the initiation of polymerization, the mixture was cooled to room temperature to complete the polymerization. After that, the obtained resin solution was dried in an oven at 130° C. to remove the organic solvent. A low-molecular-weight (meth)acrylic resin was thus obtained.
As the polymerization initiator and the chain transfer agent, the same ones as mentioned in Production Examples 1 to 28 were used.
重合開始から７時間後、室温まで冷却し重合を終了させた。その後１３０℃のオーブンで得られた樹脂溶液を乾燥させ有機溶剤を取り除いた。これにより、低分子量（メタ）アクリル樹脂を得た。
なお、重合開始剤及び連鎖移動剤としては、製造例１～２８で挙げたものと同様のものを用いた。 After nitrogen gas was bubbled through the obtained monomer mixture for 20 minutes to remove dissolved oxygen, the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised until the water bath boiled while stirring. Polymerization initiators and chain transfer agents were added in the types and amounts shown in Table 2.
After 7 hours from the initiation of polymerization, the mixture was cooled to room temperature to complete the polymerization. After that, the obtained resin solution was dried in an oven at 130° C. to remove the organic solvent. A low-molecular-weight (meth)acrylic resin was thus obtained.
As the polymerization initiator and the chain transfer agent, the same ones as mentioned in Production Examples 1 to 28 were used.
（実施例１～２９、比較例１～８）
（１）樹脂組成物の作製
表４に示す通りの配合となるように有機溶剤を混合して混合溶剤を得た。表３に示す配合となるように（メタ）アクリル樹脂、混合溶剤を混合して（メタ）アクリル樹脂組成物を得た。
なお、有機溶剤としては、以下のものを用いた。
トルエン
酢酸エチル
メチルエチルケトン
エタノール
イソプロパノール
２－ブチル－２－エチル－１，３－プロパンジオール（ＢＥＰＧ）
ネオペンチルグリコール（ＮＰＧ）
テキサノール (Examples 1 to 29, Comparative Examples 1 to 8)
(1) Preparation of resin composition Organic solvents were mixed so as to have the composition shown in Table 4 to obtain a mixed solvent. A (meth)acrylic resin and a mixed solvent were mixed so as to have the formulation shown in Table 3 to obtain a (meth)acrylic resin composition.
In addition, the following was used as an organic solvent.
toluene ethyl methyl ethyl ketone ethanol isopropanol 2-butyl-2-ethyl-1,3-propanediol (BEPG)
Neopentyl glycol (NPG)
Texanol
（１）樹脂組成物の作製
表４に示す通りの配合となるように有機溶剤を混合して混合溶剤を得た。表３に示す配合となるように（メタ）アクリル樹脂、混合溶剤を混合して（メタ）アクリル樹脂組成物を得た。
なお、有機溶剤としては、以下のものを用いた。
トルエン
酢酸エチル
メチルエチルケトン
エタノール
イソプロパノール
２－ブチル－２－エチル－１，３－プロパンジオール（ＢＥＰＧ）
ネオペンチルグリコール（ＮＰＧ）
テキサノール (Examples 1 to 29, Comparative Examples 1 to 8)
(1) Preparation of resin composition Organic solvents were mixed so as to have the composition shown in Table 4 to obtain a mixed solvent. A (meth)acrylic resin and a mixed solvent were mixed so as to have the formulation shown in Table 3 to obtain a (meth)acrylic resin composition.
In addition, the following was used as an organic solvent.
toluene ethyl methyl ethyl ketone ethanol isopropanol 2-butyl-2-ethyl-1,3-propanediol (BEPG)
Neopentyl glycol (NPG)
Texanol
（２）無機微粒子分散スラリー組成物の作製
得られた（メタ）アクリル樹脂組成物に表３の配合となるようにセラミック粉末、可塑剤を添加して、高速撹拌機で混錬して、無機微粒子分散スラリー組成物を作製した。
なお、セラミック粉末としては、銅粉末（藤野金属社製、平均粒子径０．１μｍ）、ガラスフリット（ＡＧＣ社製、平均粒子径０．８μｍ）、可塑剤としては、アジピン酸ジ（ブトキシエチル）を用いた。 (2) Preparation of Inorganic Fine Particle Dispersed Slurry Composition Ceramic powder and a plasticizer were added to the obtained (meth)acrylic resin composition so as to have the composition shown in Table 3, and the mixture was kneaded with a high-speed stirrer to obtain an inorganic powder. A microparticle-dispersed slurry composition was prepared.
As the ceramic powder, copper powder (manufactured by Fujino Metal Co., Ltd., average particle size 0.1 μm), glass frit (manufactured by AGC, average particle size 0.8 μm), and as the plasticizer, di(butoxyethyl) adipate. was used.
得られた（メタ）アクリル樹脂組成物に表３の配合となるようにセラミック粉末、可塑剤を添加して、高速撹拌機で混錬して、無機微粒子分散スラリー組成物を作製した。
なお、セラミック粉末としては、銅粉末（藤野金属社製、平均粒子径０．１μｍ）、ガラスフリット（ＡＧＣ社製、平均粒子径０．８μｍ）、可塑剤としては、アジピン酸ジ（ブトキシエチル）を用いた。 (2) Preparation of Inorganic Fine Particle Dispersed Slurry Composition Ceramic powder and a plasticizer were added to the obtained (meth)acrylic resin composition so as to have the composition shown in Table 3, and the mixture was kneaded with a high-speed stirrer to obtain an inorganic powder. A microparticle-dispersed slurry composition was prepared.
As the ceramic powder, copper powder (manufactured by Fujino Metal Co., Ltd., average particle size 0.1 μm), glass frit (manufactured by AGC, average particle size 0.8 μm), and as the plasticizer, di(butoxyethyl) adipate. was used.
＜評価＞
実施例及び比較例で得られた高分子量（メタ）アクリル樹脂、低分子量（メタ）アクリル樹脂、無機微粒子分散スラリー組成物について以下の評価を行った。結果を表１～３に示した。 <Evaluation>
The high-molecular-weight (meth)acrylic resins, low-molecular-weight (meth)acrylic resins, and inorganic fine particle-dispersed slurry compositions obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Tables 1-3.
実施例及び比較例で得られた高分子量（メタ）アクリル樹脂、低分子量（メタ）アクリル樹脂、無機微粒子分散スラリー組成物について以下の評価を行った。結果を表１～３に示した。 <Evaluation>
The high-molecular-weight (meth)acrylic resins, low-molecular-weight (meth)acrylic resins, and inorganic fine particle-dispersed slurry compositions obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Tables 1-3.
（１）重量平均分子量測定
得られた高分子量（メタ）アクリル樹脂及び低分子量（メタ）アクリル樹脂について、カラムとしてＬＦ－８０４（ＳＨＯＫＯ社製）を用い、ゲルパーミエーションクロマトグラフィーにより、ポリスチレン換算による重量平均分子量（Ｍｗ）を測定した。 (1) Weight-average molecular weight measurement For the obtained high-molecular-weight (meth)acrylic resin and low-molecular-weight (meth)acrylic resin, using LF-804 (manufactured by SHOKO) as a column, gel permeation chromatography was performed. Weight average molecular weight (Mw) was measured.
得られた高分子量（メタ）アクリル樹脂及び低分子量（メタ）アクリル樹脂について、カラムとしてＬＦ－８０４（ＳＨＯＫＯ社製）を用い、ゲルパーミエーションクロマトグラフィーにより、ポリスチレン換算による重量平均分子量（Ｍｗ）を測定した。 (1) Weight-average molecular weight measurement For the obtained high-molecular-weight (meth)acrylic resin and low-molecular-weight (meth)acrylic resin, using LF-804 (manufactured by SHOKO) as a column, gel permeation chromatography was performed. Weight average molecular weight (Mw) was measured.
（２）ＯＨ基の重量濃度の算出
以下の方法により、高分子量（メタ）アクリル樹脂中に含まれるＯＨ基の重量濃度、低分子量（メタ）アクリル樹脂中に含まれるＯＨ基の重量濃度、有機溶剤中に含まれるＯＨ基の重量濃度を算出した。
高分子量（メタ）アクリル樹脂中に含まれるＯＨ基の重量濃度：［全モノマー中に含まれるＯＨ基の重量／（全モノマーの重量＋重合開始剤の重量）］×１００
低分子量（メタ）アクリル樹脂中に含まれるＯＨ基の重量濃度：［（全モノマー中に含まれるＯＨ基の重量＋連鎖移動剤に含まれるＯＨ基の重量）／（全モノマーの重量＋連鎖移動剤の重量＋重合開始剤の重量）］×１００
有機溶剤中に含まれるＯＨ基の重量濃度：（全有機溶剤中に含まれるＯＨ基の重量／全有機溶剤の重量）×１００ (2) Calculation of the weight concentration of OH groups By the following method, the weight concentration of OH groups contained in the high molecular weight (meth) acrylic resin, the weight concentration of OH groups contained in the low molecular weight (meth) acrylic resin, the organic The weight concentration of OH groups contained in the solvent was calculated.
Weight concentration of OH groups contained in high molecular weight (meth)acrylic resin: [weight of OH groups contained in all monomers/(weight of all monomers + weight of polymerization initiator)] × 100
Weight concentration of OH groups contained in the low molecular weight (meth) acrylic resin: [(weight of OH groups contained in all monomers + weight of OH groups contained in chain transfer agent) / (weight of all monomers + chain transfer Weight of agent + weight of polymerization initiator)] × 100
Weight concentration of OH groups contained in organic solvent: (weight of OH groups contained in all organic solvents/weight of all organic solvents) x 100
以下の方法により、高分子量（メタ）アクリル樹脂中に含まれるＯＨ基の重量濃度、低分子量（メタ）アクリル樹脂中に含まれるＯＨ基の重量濃度、有機溶剤中に含まれるＯＨ基の重量濃度を算出した。
高分子量（メタ）アクリル樹脂中に含まれるＯＨ基の重量濃度：［全モノマー中に含まれるＯＨ基の重量／（全モノマーの重量＋重合開始剤の重量）］×１００
低分子量（メタ）アクリル樹脂中に含まれるＯＨ基の重量濃度：［（全モノマー中に含まれるＯＨ基の重量＋連鎖移動剤に含まれるＯＨ基の重量）／（全モノマーの重量＋連鎖移動剤の重量＋重合開始剤の重量）］×１００
有機溶剤中に含まれるＯＨ基の重量濃度：（全有機溶剤中に含まれるＯＨ基の重量／全有機溶剤の重量）×１００ (2) Calculation of the weight concentration of OH groups By the following method, the weight concentration of OH groups contained in the high molecular weight (meth) acrylic resin, the weight concentration of OH groups contained in the low molecular weight (meth) acrylic resin, the organic The weight concentration of OH groups contained in the solvent was calculated.
Weight concentration of OH groups contained in high molecular weight (meth)acrylic resin: [weight of OH groups contained in all monomers/(weight of all monomers + weight of polymerization initiator)] × 100
Weight concentration of OH groups contained in the low molecular weight (meth) acrylic resin: [(weight of OH groups contained in all monomers + weight of OH groups contained in chain transfer agent) / (weight of all monomers + chain transfer Weight of agent + weight of polymerization initiator)] × 100
Weight concentration of OH groups contained in organic solvent: (weight of OH groups contained in all organic solvents/weight of all organic solvents) x 100
（３）Ｓ原子の重量濃度の算出
以下の方法により、（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度を算出した。
（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度＝［連鎖移動剤に含まれるＳ原子の重量／（全モノマーの重量＋重合開始剤の重量＋連鎖移動剤の重量）］×１００
なお、上記（メタ）アクリル樹脂組成物が複数の（メタ）アクリル樹脂を含有する場合、上記Ｓ原子の重量濃度は、各（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度及び各（メタ）アクリル樹脂の配合割合に基づいて算出した。 (3) Calculation of weight concentration of S atom The weight concentration of S atom contained in the (meth)acrylic resin was calculated by the following method.
Weight concentration of S atoms contained in (meth)acrylic resin = [weight of S atoms contained in chain transfer agent/(weight of all monomers + weight of polymerization initiator + weight of chain transfer agent)] × 100
When the (meth)acrylic resin composition contains a plurality of (meth)acrylic resins, the weight concentration of the S atoms is the weight concentration of the S atoms contained in each (meth)acrylic resin and each (meth)acrylic resin. ) calculated based on the mixing ratio of the acrylic resin.
以下の方法により、（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度を算出した。
（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度＝［連鎖移動剤に含まれるＳ原子の重量／（全モノマーの重量＋重合開始剤の重量＋連鎖移動剤の重量）］×１００
なお、上記（メタ）アクリル樹脂組成物が複数の（メタ）アクリル樹脂を含有する場合、上記Ｓ原子の重量濃度は、各（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度及び各（メタ）アクリル樹脂の配合割合に基づいて算出した。 (3) Calculation of weight concentration of S atom The weight concentration of S atom contained in the (meth)acrylic resin was calculated by the following method.
Weight concentration of S atoms contained in (meth)acrylic resin = [weight of S atoms contained in chain transfer agent/(weight of all monomers + weight of polymerization initiator + weight of chain transfer agent)] × 100
When the (meth)acrylic resin composition contains a plurality of (meth)acrylic resins, the weight concentration of the S atoms is the weight concentration of the S atoms contained in each (meth)acrylic resin and each (meth)acrylic resin. ) calculated based on the mixing ratio of the acrylic resin.
（４）エタノールへの溶解度の測定
２５℃の環境下でエタノール１００重量部に対して、得られた高分子量（メタ）アクリル樹脂を少しずつ溶解させ、析出物が生じるまでに要した高分子量（メタ）アクリル樹脂の添加量をエタノールへの溶解度とした。 (4) Measurement of solubility in ethanol The obtained high molecular weight (meth)acrylic resin was gradually dissolved in 100 parts by weight of ethanol in an environment of 25 ° C., and the high molecular weight ( The amount of meth)acrylic resin added was defined as the solubility in ethanol.
２５℃の環境下でエタノール１００重量部に対して、得られた高分子量（メタ）アクリル樹脂を少しずつ溶解させ、析出物が生じるまでに要した高分子量（メタ）アクリル樹脂の添加量をエタノールへの溶解度とした。 (4) Measurement of solubility in ethanol The obtained high molecular weight (meth)acrylic resin was gradually dissolved in 100 parts by weight of ethanol in an environment of 25 ° C., and the high molecular weight ( The amount of meth)acrylic resin added was defined as the solubility in ethanol.
（５）低温分解性（ＴＧＤＴＡ特性）
得られた無機微粒子分散スラリー組成物をＴＧ－ＤＴＡのプラチナパンに詰め、３０℃から５℃／ｍｉｎにて昇温し、溶媒を蒸発、樹脂、可塑剤を熱分解させた。その後、重量が５２．１重量％を示した（９０重量％脱脂が終了した）時間を測定した。 (5) Low temperature decomposability (TGDTA characteristics)
The obtained inorganic fine particle-dispersed slurry composition was packed in a TG-DTA platinum pan, and the temperature was raised from 30° C. to 5° C./min to evaporate the solvent and thermally decompose the resin and plasticizer. After that, the time when the weight showed 52.1% by weight (90% by weight degreasing was completed) was measured.
得られた無機微粒子分散スラリー組成物をＴＧ－ＤＴＡのプラチナパンに詰め、３０℃から５℃／ｍｉｎにて昇温し、溶媒を蒸発、樹脂、可塑剤を熱分解させた。その後、重量が５２．１重量％を示した（９０重量％脱脂が終了した）時間を測定した。 (5) Low temperature decomposability (TGDTA characteristics)
The obtained inorganic fine particle-dispersed slurry composition was packed in a TG-DTA platinum pan, and the temperature was raised from 30° C. to 5° C./min to evaporate the solvent and thermally decompose the resin and plasticizer. After that, the time when the weight showed 52.1% by weight (90% by weight degreasing was completed) was measured.
（６）濾過性
得られた無機微粒子分散スラリー組成物を２．５ｍｌのシリンジに２ｍｌ取り、シリンジの先端に外径０．８１ｍｍ内径０．５１ｍｍ長さ３８ｍｍの注射針を付け、５ｋｇｆの力をかけたときに、スラリー組成物が注射針の先からすべて出るまでの時間を測定した。
スラリー組成物が注射針の先からすべて出るまでの時間が短いと濾過性に優れているといえ、濾過性に優れる場合、無機微粒子の凝集抑制効果が高いといえる。 (6) Filterability 2 ml of the obtained inorganic fine particle dispersion slurry composition was put into a 2.5 ml syringe, and an injection needle with an outer diameter of 0.81 mm, an inner diameter of 0.51 mm and a length of 38 mm was attached to the tip of the syringe, and a force of 5 kgf was applied. The time until all the slurry composition came out of the tip of the injection needle was measured.
It can be said that when the time until the slurry composition is completely discharged from the tip of the injection needle is short, the filterability is excellent.
得られた無機微粒子分散スラリー組成物を２．５ｍｌのシリンジに２ｍｌ取り、シリンジの先端に外径０．８１ｍｍ内径０．５１ｍｍ長さ３８ｍｍの注射針を付け、５ｋｇｆの力をかけたときに、スラリー組成物が注射針の先からすべて出るまでの時間を測定した。
スラリー組成物が注射針の先からすべて出るまでの時間が短いと濾過性に優れているといえ、濾過性に優れる場合、無機微粒子の凝集抑制効果が高いといえる。 (6) Filterability 2 ml of the obtained inorganic fine particle dispersion slurry composition was put into a 2.5 ml syringe, and an injection needle with an outer diameter of 0.81 mm, an inner diameter of 0.51 mm and a length of 38 mm was attached to the tip of the syringe, and a force of 5 kgf was applied. The time until all the slurry composition came out of the tip of the injection needle was measured.
It can be said that when the time until the slurry composition is completely discharged from the tip of the injection needle is short, the filterability is excellent.
（７）表面粗さ
スクリーン印刷機とスクリーン版、印刷ガラス基板を用いて、温度２３℃、湿度５０％の環境下にて無機微粒子分散スラリー組成物の印刷を行い、１００℃３０分の条件下で送風オーブンにて溶剤乾燥を行った。得られた印刷パターンを用いて、表面粗さ計（サーフコム、東京精密社製）にて１０か所測定した。
なお、スクリーン印刷機、スクリーン版、印刷ガラス基板として以下のものを用いた。
スクリーン印刷機（ＭＴ－３２０ＴＶ、マイクロテック社製）
スクリーン版（東京プロセスサービス社製、ＳＴ５００、乳剤２μｍ、２０１２パターン、スクリーン枠３２０ｍｍ×３２０ｍｍ）
印刷ガラス基板（ソーダーガラス、１５０ｍｍ×１５０ｍｍ、厚み１．５ｍｍ）
表面粗さが小さいと、無機微粒子の分散性に優れているといえる。 (7) Surface roughness Using a screen printer, a screen plate, and a printing glass substrate, the inorganic fine particle dispersion slurry composition is printed in an environment of a temperature of 23 ° C. and a humidity of 50%, and the condition is 100 ° C. for 30 minutes. Solvent drying was performed in a blower oven. Using the obtained printed pattern, measurements were made at 10 points with a surface roughness meter (Surfcom, manufactured by Tokyo Seimitsu Co., Ltd.).
In addition, the following were used as a screen printer, a screen plate, and a printing glass substrate.
Screen printer (MT-320TV, manufactured by Microtec)
Screen plate (manufactured by Tokyo Process Service Co., Ltd., ST500, emulsion 2 μm, 2012 pattern, screen frame 320 mm × 320 mm)
Printed glass substrate (soda glass, 150 mm x 150 mm, thickness 1.5 mm)
When the surface roughness is small, it can be said that the dispersibility of the inorganic fine particles is excellent.
スクリーン印刷機とスクリーン版、印刷ガラス基板を用いて、温度２３℃、湿度５０％の環境下にて無機微粒子分散スラリー組成物の印刷を行い、１００℃３０分の条件下で送風オーブンにて溶剤乾燥を行った。得られた印刷パターンを用いて、表面粗さ計（サーフコム、東京精密社製）にて１０か所測定した。
なお、スクリーン印刷機、スクリーン版、印刷ガラス基板として以下のものを用いた。
スクリーン印刷機（ＭＴ－３２０ＴＶ、マイクロテック社製）
スクリーン版（東京プロセスサービス社製、ＳＴ５００、乳剤２μｍ、２０１２パターン、スクリーン枠３２０ｍｍ×３２０ｍｍ）
印刷ガラス基板（ソーダーガラス、１５０ｍｍ×１５０ｍｍ、厚み１．５ｍｍ）
表面粗さが小さいと、無機微粒子の分散性に優れているといえる。 (7) Surface roughness Using a screen printer, a screen plate, and a printing glass substrate, the inorganic fine particle dispersion slurry composition is printed in an environment of a temperature of 23 ° C. and a humidity of 50%, and the condition is 100 ° C. for 30 minutes. Solvent drying was performed in a blower oven. Using the obtained printed pattern, measurements were made at 10 points with a surface roughness meter (Surfcom, manufactured by Tokyo Seimitsu Co., Ltd.).
In addition, the following were used as a screen printer, a screen plate, and a printing glass substrate.
Screen printer (MT-320TV, manufactured by Microtec)
Screen plate (manufactured by Tokyo Process Service Co., Ltd., ST500, emulsion 2 μm, 2012 pattern, screen frame 320 mm × 320 mm)
Printed glass substrate (soda glass, 150 mm x 150 mm, thickness 1.5 mm)
When the surface roughness is small, it can be said that the dispersibility of the inorganic fine particles is excellent.
（８）エタノール洗浄性
無機微粒子分散スラリー組成物１０重量部に対してエタノール１００重量部を添加し、超音波を照射した。樹脂がエタノールに完全に溶解するまでの時間を測定した。 (8) 100 parts by weight of ethanol was added to 10 parts by weight of the inorganic fine particle-dispersed slurry composition for washing with ethanol, and ultrasonic waves were applied. The time required for the resin to completely dissolve in ethanol was measured.
無機微粒子分散スラリー組成物１０重量部に対してエタノール１００重量部を添加し、超音波を照射した。樹脂がエタノールに完全に溶解するまでの時間を測定した。 (8) 100 parts by weight of ethanol was added to 10 parts by weight of the inorganic fine particle-dispersed slurry composition for washing with ethanol, and ultrasonic waves were applied. The time required for the resin to completely dissolve in ethanol was measured.
本発明によれば、低温で優れた分解性を有するとともに、無機微粒子の分散性や凝集抑制効果を向上させることができる（メタ）アクリル樹脂組成物を提供することができる。また、該（メタ）アクリル樹脂組成物を用いる無機微粒子分散スラリー組成物、無機微粒子分散成形物を提供することができる。
According to the present invention, it is possible to provide a (meth)acrylic resin composition that has excellent decomposability at low temperatures and that can improve the dispersibility of inorganic fine particles and the effect of suppressing aggregation. Further, an inorganic fine particle-dispersed slurry composition and an inorganic fine particle-dispersed molded product using the (meth)acrylic resin composition can be provided.
According to the present invention, it is possible to provide a (meth)acrylic resin composition that has excellent decomposability at low temperatures and that can improve the dispersibility of inorganic fine particles and the effect of suppressing aggregation. Further, an inorganic fine particle-dispersed slurry composition and an inorganic fine particle-dispersed molded product using the (meth)acrylic resin composition can be provided.
Claims (8)
- （メタ）アクリル樹脂、及び、有機溶剤を含有する（メタ）アクリル樹脂組成物であって、
下記（１）～（３）のいずれか１つを満たし、
前記有機溶剤中に含まれるＯＨ基の重量濃度が９．０重量％以上２８．０重量％以下である、（メタ）アクリル樹脂組成物。
（１）前記（メタ）アクリル樹脂は、重量平均分子量が１２万以上３０万以下の高分子量（メタ）アクリル樹脂（Ａ）を含有し、
前記高分子量（メタ）アクリル樹脂（Ａ）中に含まれるＯＨ基の重量濃度が０．４重量％以上２．０重量％以下である。
（２）前記（メタ）アクリル樹脂は、重量平均分子量が３０万を超え５０万以下である高分子量（メタ）アクリル樹脂（Ｂ）を含有し、
前記高分子量（メタ）アクリル樹脂（Ｂ）中に含まれるＯＨ基の重量濃度が１．３重量％以上３．５重量％以下である。
（３）前記（メタ）アクリル樹脂は、重量平均分子量が０．５万以上１０万以下である低分子量（メタ）アクリル樹脂（Ｃ）を含有し、
前記低分子量（メタ）アクリル樹脂（Ｃ）中に含まれるＯＨ基の重量濃度が１．３重量％以上３．５重量％以下であり、
前記（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度が２５０ｐｐｍ以上２００００ｐｐｍ以下である。 (Meth)acrylic resin and a (meth)acrylic resin composition containing an organic solvent,
satisfy any one of the following (1) to (3),
A (meth)acrylic resin composition, wherein the weight concentration of OH groups contained in the organic solvent is 9.0% by weight or more and 28.0% by weight or less.
(1) The (meth)acrylic resin contains a high molecular weight (meth)acrylic resin (A) having a weight average molecular weight of 120,000 or more and 300,000 or less,
The weight concentration of OH groups contained in the high molecular weight (meth)acrylic resin (A) is 0.4% by weight or more and 2.0% by weight or less.
(2) the (meth)acrylic resin contains a high molecular weight (meth)acrylic resin (B) having a weight average molecular weight of more than 300,000 and not more than 500,000,
The weight concentration of OH groups contained in the high molecular weight (meth)acrylic resin (B) is 1.3% by weight or more and 3.5% by weight or less.
(3) The (meth)acrylic resin contains a low molecular weight (meth)acrylic resin (C) having a weight average molecular weight of 5,000 to 100,000,
The weight concentration of OH groups contained in the low molecular weight (meth)acrylic resin (C) is 1.3% by weight or more and 3.5% by weight or less,
The weight concentration of S atoms contained in the (meth)acrylic resin is 250 ppm or more and 20000 ppm or less. - （１）を満たし、かつ、重量平均分子量が０．５万以上１０万以下である低分子量（メタ）アクリル樹脂を含有し、前記低分子量（メタ）アクリル樹脂中に含まれるＯＨ基の重量濃度が１．３重量％以上３．５重量％以下であり、高分子量（メタ）アクリル樹脂（Ａ）１００重量部に対する前記低分子量（メタ）アクリル樹脂の含有量が０．１重量部以上１０重量部以下である、請求項１に記載の（メタ）アクリル樹脂組成物。 It contains a low-molecular-weight (meth)acrylic resin that satisfies (1) and has a weight-average molecular weight of 5,000 to 100,000, and the weight concentration of OH groups contained in the low-molecular-weight (meth)acrylic resin. is 1.3% by weight or more and 3.5% by weight or less, and the content of the low molecular weight (meth)acrylic resin with respect to 100 parts by weight of the high molecular weight (meth)acrylic resin (A) is 0.1 parts by weight or more and 10 parts by weight 3. The (meth)acrylic resin composition according to claim 1, which is 1 part or less.
- （１）又は（２）を満たし、かつ、高分子量（メタ）アクリル樹脂（Ａ）又は（Ｂ）のエタノールへの溶解度が１０重量部／エタノール１００重量部以上である、請求項１に記載の（メタ）アクリル樹脂組成物。 2. The method according to claim 1, wherein (1) or (2) is satisfied, and the solubility of the high-molecular-weight (meth)acrylic resin (A) or (B) in ethanol is 10 parts by weight/100 parts by weight or more in ethanol. (Meth)acrylic resin composition.
- （１）又は（２）を満たし、かつ、高分子量（メタ）アクリル樹脂（Ａ）又は（Ｂ）は、全構成単位に対して、下記式（ａ）で表される構成単位を７９重量％以上９６重量％以下、下記式（ｂ）で表される構成単位を３．１重量％以上１７重量％以下含有する、請求項１又は３に記載の（メタ）アクリル樹脂組成物。
- （１）又は（２）を満たし、かつ、高分子量（メタ）アクリル樹脂（Ａ）又は（Ｂ）中に含まれるＯＨ基の重量濃度に対する有機溶剤中に含まれるＯＨ基の重量濃度の比（有機溶剤中に含まれるＯＨ基の重量濃度／高分子量（メタ）アクリル樹脂（Ａ）又は（Ｂ）中に含まれるＯＨ基の重量濃度）が４．５以上４６．２以下である、請求項１、３又は４に記載の（メタ）アクリル樹脂組成物。 (1) or (2) is satisfied, and the ratio of the weight concentration of OH groups contained in the organic solvent to the weight concentration of OH groups contained in the high molecular weight (meth)acrylic resin (A) or (B) ( The weight concentration of OH groups contained in the organic solvent/the weight concentration of OH groups contained in the high molecular weight (meth)acrylic resin (A) or (B)) is 4.5 or more and 46.2 or less. The (meth)acrylic resin composition according to 1, 3 or 4.
- （２）を満たし、かつ、（メタ）アクリル樹脂は、高分子量（メタ）アクリル樹脂（Ｂ）のみからなるものであり、
前記（メタ）アクリル樹脂中に含まれるＳ原子の重量濃度が２５０ｐｐｍ以上２００００ｐｐｍ以下である、請求項１、３、４又は５に記載の（メタ）アクリル樹脂組成物。 (2) is satisfied, and the (meth)acrylic resin consists only of a high-molecular-weight (meth)acrylic resin (B),
The (meth)acrylic resin composition according to claim 1, 3, 4 or 5, wherein the (meth)acrylic resin has a weight concentration of S atoms of 250 ppm or more and 20000 ppm or less. - 請求項１～６の何れかに記載の（メタ）アクリル樹脂組成物、無機微粒子、及び、可塑剤を含有する、無機微粒子分散スラリー組成物。 An inorganic fine particle-dispersed slurry composition comprising the (meth)acrylic resin composition according to any one of claims 1 to 6, inorganic fine particles, and a plasticizer.
- 請求項７に記載の無機微粒子分散スラリー組成物を用いてなる、無機微粒子分散成形物。 An inorganic fine particle-dispersed molding obtained by using the inorganic fine particle-dispersed slurry composition according to claim 7.
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- 2022-06-20 CN CN202280012445.4A patent/CN116829643A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20240022439A (en) | 2024-02-20 |
| TW202311318A (en) | 2023-03-16 |
| CN116829643A (en) | 2023-09-29 |
| JPWO2022270460A1 (en) | 2022-12-29 |
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