JP7122789B1 - Composite resin composition and method for producing the same - Google Patents
Composite resin composition and method for producing the same Download PDFInfo
- Publication number
- JP7122789B1 JP7122789B1 JP2022064616A JP2022064616A JP7122789B1 JP 7122789 B1 JP7122789 B1 JP 7122789B1 JP 2022064616 A JP2022064616 A JP 2022064616A JP 2022064616 A JP2022064616 A JP 2022064616A JP 7122789 B1 JP7122789 B1 JP 7122789B1
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- Prior art keywords
- resin composition
- meth
- composite resin
- paramylon
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 98
- 239000000805 composite resin Substances 0.000 title claims abstract description 89
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 108
- 239000002121 nanofiber Substances 0.000 claims abstract description 54
- 229920002984 Paramylon Polymers 0.000 claims abstract description 49
- 239000002245 particle Substances 0.000 claims abstract description 47
- 229920003176 water-insoluble polymer Polymers 0.000 claims abstract description 38
- 239000002612 dispersion medium Substances 0.000 claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 33
- 239000006185 dispersion Substances 0.000 claims description 19
- 230000000379 polymerizing effect Effects 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 58
- 238000000034 method Methods 0.000 description 54
- 239000002134 carbon nanofiber Substances 0.000 description 38
- -1 acrylic ester Chemical class 0.000 description 29
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 27
- 239000000839 emulsion Substances 0.000 description 26
- 239000011347 resin Substances 0.000 description 21
- 229920005989 resin Polymers 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 241000195620 Euglena Species 0.000 description 16
- 239000001913 cellulose Substances 0.000 description 16
- 229920002678 cellulose Polymers 0.000 description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 14
- 239000000835 fiber Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 12
- 239000003995 emulsifying agent Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 206010061592 cardiac fibrillation Diseases 0.000 description 10
- 230000002600 fibrillogenic effect Effects 0.000 description 10
- 239000003505 polymerization initiator Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- 229920002498 Beta-glucan Polymers 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 238000010979 pH adjustment Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000003834 intracellular effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
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- 150000007524 organic acids Chemical class 0.000 description 2
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- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
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- 229910052725 zinc Inorganic materials 0.000 description 2
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- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-UHFFFAOYSA-N 0.000 description 1
- OZFIGURLAJSLIR-UHFFFAOYSA-N 1-ethenyl-2h-pyridine Chemical compound C=CN1CC=CC=C1 OZFIGURLAJSLIR-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
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- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical compound FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 description 1
- JDVGNKIUXZQTFD-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)COC(=O)C=C JDVGNKIUXZQTFD-UHFFFAOYSA-N 0.000 description 1
- VHJHZYSXJKREEE-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropyl prop-2-enoate Chemical compound FC(F)C(F)(F)COC(=O)C=C VHJHZYSXJKREEE-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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- 239000002028 Biomass Substances 0.000 description 1
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
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Abstract
【課題】本発明は、力学特性を向上させる複合樹脂組成物及びその製造方法を提供することを目的とする。【解決手段】エチレン性不飽和単量体からなる水不溶性重合体粒子と、パラミロンナノファイバーと、水性分散媒と、を含み、前記水不溶性重合体粒子の１００質量部に対して、前記エチレン性不飽和単量体として（メタ）アクリル系単量体、スチレン系単量体、及び（メタ）アクリロニトリル系単量体の少なくともいずれかを５０質量部以上含む。【選択図】なしAn object of the present invention is to provide a composite resin composition having improved mechanical properties and a method for producing the same. The water-insoluble polymer particles comprising an ethylenically unsaturated monomer, paramylon nanofibers, and an aqueous dispersion medium are contained, and the ethylenic 50 parts by mass or more of at least one of a (meth)acrylic monomer, a styrene monomer, and a (meth)acrylonitrile monomer as unsaturated monomers. [Selection figure] None
Description
本発明は、複合樹脂組成物とその製造方法に関する。 TECHNICAL FIELD The present invention relates to a composite resin composition and a method for producing the same.
従来、樹脂組成物の層の剛性及び強度等を向上させるために、樹脂組成物にセルロースナノファイバー（以下、ＣＮＦ）を添加することが行われている（特許文献１）。ＣＮＦは、セルロースの化学解繊処理工程（ＴＥＭＰＯ酸化）及び機械解繊処理工程によるトップダウン方式に基づいて製造される。しかし、ＣＮＦは上記の製造工程で強制的に微小化されるため、ＣＮＦは低アスペクト比の形状となっていた。 Conventionally, cellulose nanofibers (hereinafter, CNF) have been added to a resin composition in order to improve the rigidity, strength, etc. of a layer of the resin composition (Patent Document 1). CNF is manufactured based on a top-down method by a chemical fibrillation treatment process (TEMPO oxidation) of cellulose and a mechanical fibrillation treatment process. However, since the CNFs are forcibly miniaturized in the above manufacturing process, the CNFs have a low aspect ratio shape.
このように、特許文献１に記載の先行技術では、ＣＮＦが低アスペクト比の形状となっているため、複合樹脂組成物からなる層の力学特性を更に向上させることが困難であるといった課題がある。 Thus, in the prior art described in Patent Document 1, since the CNF has a shape with a low aspect ratio, there is a problem that it is difficult to further improve the mechanical properties of the layer made of the composite resin composition. .
本発明は、力学特性を向上させる複合樹脂組成物及びその製造方法を提供することを目的とする。 An object of the present invention is to provide a composite resin composition having improved mechanical properties and a method for producing the same.
本発明の目的を達成するために、複合樹脂組成物は、エチレン性不飽和単量体からなる水不溶性重合体粒子と、パラミロンナノファイバーと、水性分散媒と、を含み、前記水不溶性重合体粒子の１００質量部に対して、前記エチレン性不飽和単量体として（メタ）アクリル系単量体、スチレン系単量体、及び（メタ）アクリロニトリル系単量体の少なくともいずれかを５０質量部以上含む、ことを特徴とする。 In order to achieve the object of the present invention, a composite resin composition includes water-insoluble polymer particles made of an ethylenically unsaturated monomer, paramylon nanofibers, and an aqueous dispersion medium, 50 parts by mass of at least one of a (meth)acrylic monomer, a styrene monomer, and a (meth)acrylonitrile monomer as the ethylenically unsaturated monomer with respect to 100 parts by mass of the coalesced particles It is characterized by including more than one part .
本発明によれば、力学特性を向上させる複合樹脂組成物及びその製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the composite resin composition which improves a mechanical property, and its manufacturing method can be provided.
以下、実施形態を詳しく説明する。なお、以下の実施形態は特許請求の範囲に係る発明を限定するものではなく、また実施形態で説明されている特徴の組み合わせの全てが発明に必須のものとは限らない。実施形態で説明されている複数の特徴のうち二つ以上の特徴は任意に組み合わされてもよい。 Embodiments will be described in detail below. It should be noted that the following embodiments do not limit the invention according to the claims, and not all combinations of features described in the embodiments are essential to the invention. Two or more of the features described in the embodiments may be combined arbitrarily.
＜複合樹脂組成物＞
本発明の複合樹脂組成物は、エチレン性不飽和単量体からなる水不溶性重合体粒子と、パラミロンナノファイバーと、水性分散媒と、を含む。
<Composite resin composition>
The composite resin composition of the present invention contains water-insoluble polymer particles composed of an ethylenically unsaturated monomer, paramylon nanofibers, and an aqueous dispersion medium.
一実施形態に係る複合樹脂組成物は、水不溶性重合体粒子の１００質量部に対して、パラミロンナノファイバーを１０～５００質量部含む。 A composite resin composition according to one embodiment contains 10 to 500 parts by mass of paramylon nanofibers with respect to 100 parts by mass of the water-insoluble polymer particles.
なお、パラミロンナノファイバーは、高アスペクト比を有するため、繊維同士の絡み付きが良好となる。そのため、複合樹脂組成物は、少量のパラミロンナノファイバーを含有することで、複合樹脂組成物からなる層の力学特性を向上させる効果を有する。 In addition, since the paramylon nanofiber has a high aspect ratio, the entanglement between the fibers is improved. Therefore, the composite resin composition contains a small amount of paramylon nanofibers, thereby having the effect of improving the mechanical properties of the layer made of the composite resin composition.
（パラミロンナノファイバー）
一実施形態に係るパラミロンナノファイバーは、複合樹脂組成物に対して０．１～１０質量％含まれる。
(paramylon nanofiber)
Paramylon nanofibers according to one embodiment are contained in an amount of 0.1 to 10% by mass with respect to the composite resin composition.
パラミロンナノファイバー（以下、ＰＮＦ）は、ユーグレナの体内に貯蔵されるパラミロンを原料とした繊維のことである（特開２０１７－１７９１８２号公報）。 Paramylon nanofiber (hereinafter, PNF) is a fiber made from paramylon stored in the body of Euglena (Japanese Patent Application Laid-Open No. 2017-179182).
多糖系ナノファイバーの原料物質は、セルロース及びパラミロンである。セルロース及びパラミロンは、いずれもグルコースが重合した多糖（グルカン）である。セルロースは、β－１，４－グリコシド結合によってグルコースが重合した糖鎖を基本骨格として有する。一方、パラミロンは、β－１，３－グリコシド結合によってグルコースが重合した糖鎖を基本骨格として有する。セルロースとパラミロンの結合様式の違いにより、中性の水中における両者の立体構造は明確に相違する。すなわち、セルロースはシート構造を取り、パラミロンは三重らせん構造を取り得る。 Raw materials for polysaccharide nanofibers are cellulose and paramylon. Both cellulose and paramylon are polysaccharides (glucans) in which glucose is polymerized. Cellulose has, as a basic skeleton, sugar chains in which glucose is polymerized through β-1,4-glycosidic bonds. On the other hand, paramylon has, as its basic skeleton, a sugar chain in which glucose is polymerized through β-1,3-glycosidic bonds. The three-dimensional structures of cellulose and paramylon in neutral water are clearly different due to the difference in binding mode. That is, cellulose can have a sheet structure and paramylon can have a triple helical structure.
β－１，３－グルカンは三重らせん構造を有するため、β－１，３－グルカンを原料物質として用いるパラミロンナノファイバーは、セルロースナノファイバーと比較して、繊維直径、引張強度及び持続長のような繊維特性に優れる。 Since β-1,3-glucan has a triple helical structure, paramylon nanofibers using β-1,3-glucan as a raw material have improved fiber diameter, tensile strength and persistence length compared to cellulose nanofibers. Excellent fiber properties.
（アスペクト比）
一実施形態において、パラミロンナノファイバーは、１：３００～１：１００００のアスペクト比を有する。アスペクト比は、パラミロンナノファイバー粒子の長径と短径の比であり、長径を短径で除した数値である。パラミロンナノファイバーの長径と短径の数値は、電子顕微鏡等でパラミロンナノファイバーを観察することで得られる。
(aspect ratio)
In one embodiment, the paramylon nanofibers have an aspect ratio of 1:300 to 1:10000. The aspect ratio is the ratio of the major axis to the minor axis of the paramylon nanofiber particles, and is a numerical value obtained by dividing the major axis by the minor axis. Numerical values of the major axis and minor axis of the paramylon nanofibers can be obtained by observing the paramylon nanofibers with an electron microscope or the like.
ここで、ＰＮＦとＣＮＦのアスペクト比の違いについて説明する。ＣＮＦには、機械解繊によるナチュラルファイバー（本明細書ではＣＮＦ１と呼ぶ）と化学解繊（ＴＥＭＰＯ酸化）による化学修飾ファイバー（本明細書ではＣＮＦ２と呼ぶ）がある。ＣＮＦのなかでも比較的大きなアスペクト比を有するＴＥＭＰＯ酸化ＣＮＦは、１：３０～３００程度のアスペクト比を有するにすぎない。このように、ＰＮＦのアスペクト比は、ＣＮＦのアスペクト比に比して、非常に大きい。通常、複合樹脂組成物に添加する添加剤のアスペクト比が大きければ大きいほど、複合樹脂組成物からなる層の剛性及び強度が高くなることが知られている。 Here, the difference in aspect ratio between PNF and CNF will be described. CNF includes natural fibers (herein called CNF1) by mechanical fibrillation and chemically modified fibers (herein called CNF2) by chemical fibrillation (TEMPO oxidation). TEMPO-oxidized CNF, which has a relatively large aspect ratio among CNFs, only has an aspect ratio of about 1:30 to 300. Thus, the aspect ratio of PNF is much larger than that of CNF. Generally, it is known that the higher the aspect ratio of the additive added to the composite resin composition, the higher the rigidity and strength of the layer made of the composite resin composition.
複合樹脂組成物が上記のアスペクト比のＰＮＦを含有することで、基材にフィルム状に塗布した複合樹脂組成物からなる層の乾燥時のクラックを抑制することができる。一方で、複合樹脂組成物が上記のアスペクト比のＰＮＦを含有しない場合、複合樹脂組成物の流動性の低下等により、複合樹脂組成物からなる層にクラックが発生する。 When the composite resin composition contains PNF having the above aspect ratio, it is possible to suppress cracks during drying of the layer composed of the composite resin composition applied in the form of a film to the substrate. On the other hand, when the composite resin composition does not contain the PNF having the above aspect ratio, cracks occur in the layer made of the composite resin composition due to deterioration in the fluidity of the composite resin composition and the like.
ＰＮＦは、ＣＮＦとは異なり、製造工程で解繊処理されないため、繊維幅及び繊維長が揃った形状を有する。そのため、ＰＮＦを含む複合樹脂組成物からなる層の力学特性は、層全体において均一になるものと推察される。 Unlike CNF, PNF is not fibrillated in the manufacturing process, so it has a uniform fiber width and fiber length. Therefore, it is presumed that the mechanical properties of the layer composed of the composite resin composition containing PNF are uniform throughout the layer.
また、ＰＮＦを複合樹脂組成物に含有させることで、高Ｔｇ化を要することなく、複合樹脂組成物からなる層の強度（従来比５０％以上）、弾性率（屈曲性）（従来比１００％以上）及び耐熱性（耐熱クリープ性）が向上する。 In addition, by including PNF in the composite resin composition, the strength of the layer made of the composite resin composition (50% or more compared to conventional) and elastic modulus (flexibility) (100% compared to conventional) can be achieved without increasing Tg. above) and heat resistance (heat resistance creep resistance) are improved.
さらに、本発明のＰＮＦを含む複合樹脂組成物からなる層は、力学特性（強度、伸度、形態安定性）、熱特性（耐熱性、熱伝導性）、光学特性（透光性、屈折率）、及び電気特性（誘電率、停電防止性）等を向上させることができる。 Furthermore, the layer made of the composite resin composition containing the PNF of the present invention has mechanical properties (strength, elongation, shape stability), thermal properties (heat resistance, thermal conductivity), optical properties (transparency, refractive index ), electrical properties (dielectric constant, power failure prevention), etc. can be improved.
（親水性・疎水性）
一実施形態において、ＰＮＦは、化学修飾されていないナチュラルファイバーである。そのため、ＰＮＦの親水性又は疎水性を考慮することなく、複合樹脂組成物からなる層の耐水性及び耐油性の向上を図ることが可能である。なお、ＰＮＦは、後工程で任意に化学変性することができ、例えば、疎水化（アルキルエステル化）又は親水化する。
(hydrophilic/hydrophobic)
In one embodiment, the PNF is a natural fiber that has not been chemically modified. Therefore, it is possible to improve the water resistance and oil resistance of the layer made of the composite resin composition without considering the hydrophilicity or hydrophobicity of the PNF. In addition, PNF can optionally be chemically modified in a post-process, for example, hydrophobization (alkyl esterification) or hydrophilization.
ＰＮＦはナチュラルファイバーであることから、ＰＮＦ含有複合樹脂組成物の用途に制限はない。一方で、ナチュラルナノファイバーの機械解繊ＣＮＦはアスペクト比が低く、比較的にアスペクト比が高いとされているＴＥＭＰＯ酸化型ＣＮＦは、イオン反発力による解繊処理により、ＣＮＦ自身のイオン性が高くなるため、ＣＮＦ含有複合樹脂組成物は、高親水性、高増粘性、及び低耐水性となってしまう。そのため、ＣＮＦ含有複合樹脂組成物の用途に制限がある。 Since PNF is a natural fiber, there are no restrictions on the applications of the PNF-containing composite resin composition. On the other hand, natural nanofiber mechanical fibrillation CNF has a low aspect ratio, and TEMPO oxidized CNF, which is said to have a relatively high aspect ratio, has high ionicity due to the fibrillation treatment by ion repulsion. Therefore, the CNF-containing composite resin composition has high hydrophilicity, high viscosity, and low water resistance. Therefore, there are restrictions on the applications of the CNF-containing composite resin composition.
水に分散した繊維状ナノファイバーと、水に分散した球状樹脂微粒子は、各々単独では、水に安定に分散した状態である。しかし、互いに形状の異なる物質を共有溶媒（水等）に存在させると、凝集化が進行し易くなる傾向にある。これは、互いの物質が熱力学的により安定な状態になろうとする性質があるためである。特に、ＣＮＦ及びＰＮＦ等の水素結合の強いナノファイバーは水中で凝集しやすい。つまり、ＣＮＦ又はＰＮＦの繊維状ナノファイバーと球状樹脂微粒子を単純に配合して水中で撹拌しても均一に分散することは困難である。 The fibrous nanofibers dispersed in water and the spherical resin fine particles dispersed in water are each in a state of being stably dispersed in water. However, if substances having different shapes are allowed to exist in a common solvent (such as water), aggregation tends to proceed more easily. This is because each other's substances tend to be thermodynamically more stable. In particular, nanofibers with strong hydrogen bonds such as CNF and PNF tend to aggregate in water. In other words, it is difficult to uniformly disperse CNF or PNF fibrous nanofibers and spherical resin fine particles by simply mixing them in water and stirring them.
ＰＮＦはＣＮＦに比して高アスペクト比で絡まり易いため、通常の配合撹拌では樹脂エマルション中でＰＮＦの均一分散が非常に困難である。分散性を改善する方法は、例えば、ホットブレンド法、好ましくはＰＮＦ存在下での重合方法、より好ましくは高ｐＨブレンド法を含む。高ｐＨブレンド法は、ＰＮＦが高ｐＨ（強アルカリ性域としてｐＨ１１以上）下で溶解し、ｐＨの低下に伴いＰＮＦのナノ繊維が析出する特性を利用している。高ｐＨ下のＰＮＦの溶解状態で樹脂エマルションを配合することで、容易にＰＮＦが均一分散する。ＰＮＦが樹脂エマルション中に均一分散した状態から、ｐＨをゆっくり低下させ、分散液を弱アルカリ性域（ｐＨ８以上１１未満）、中性域（ｐＨ６以上８未満）及び弱酸性域（ｐＨ３以上６未満）のいずれかに戻す。これにより、ＰＮＦのナノ繊維を再びゆっくりと析出させることで、従来にはないＰＮＦ繊維が樹脂エマルション中に均一分散した複合樹脂組成物が得られる。 Compared to CNF, PNF has a high aspect ratio and is easily entangled, so it is very difficult to uniformly disperse PNF in a resin emulsion by ordinary mixing and stirring. Methods of improving dispersibility include, for example, hot blending methods, preferably polymerization methods in the presence of PNFs, more preferably high pH blending methods. The high pH blending method utilizes the property that PNF dissolves at high pH (pH 11 or higher as a strongly alkaline range), and PNF nanofibers precipitate as the pH decreases. PNF can be uniformly dispersed easily by blending a resin emulsion in a state where PNF is dissolved at a high pH. From the state in which the PNF is uniformly dispersed in the resin emulsion, the pH is slowly lowered, and the dispersion is changed to a weak alkaline range (pH 8 or more and less than 11), a neutral range (pH 6 or more and less than 8) and a weak acid range (pH 3 or more and less than 6). return to either As a result, the PNF nanofibers are slowly precipitated again to obtain a composite resin composition in which the PNF fibers are uniformly dispersed in the resin emulsion.
また、本発明では、（１）パラミロンナノファイバーを含有する水性分散媒中でエチレン性不飽和単量体を重合する方法を用いて複合樹脂組成物を製造した。なお、複合樹脂組成物の他の製造方法として、（２）パラミロンナノファイバー存在下でエチレン性不飽和単量体を重合した後、パラミロンナノファイバーを更に添加する方法、及び、（３）エチレン性不飽和単量体からなる水不溶性重合体粒子を含有する水性分散媒と、パラミロンナノファイバーを含有する水性分散媒とを混合する方法、のいずれかに基づいて、複合樹脂組成物が製造され得る。 In the present invention, a composite resin composition was produced by (1) polymerizing an ethylenically unsaturated monomer in an aqueous dispersion medium containing paramylon nanofibers. As other methods for producing the composite resin composition, (2) a method of polymerizing ethylenically unsaturated monomers in the presence of paramylon nanofibers and then further adding paramylon nanofibers, and (3) ethylenic A composite resin composition can be produced based on either method of mixing an aqueous dispersion medium containing water-insoluble polymer particles made of unsaturated monomers and an aqueous dispersion medium containing paramylon nanofibers. .
（ユーグレナ）
ＰＮＦの説明に戻って、ユーグレナ（和名:ミドリムシ）は、単細胞の微細藻類のことである。ユーグレナは、ムシではなく、ワカメや昆布、テングサ等と同じ藻類に属するが、鞭毛を動かして活発に運動することから、植物と動物の両方の特徴を持つ。ユーグレナは、環境への適応力に非常に優れ、光合成での成長及び暗中での成長も可能である。
(Euglena)
Returning to the explanation of PNF, Euglena (Japanese name: Euglena) is a single-celled microalgae. Euglena is not a bug but belongs to algae like wakame seaweed, kelp, and agar-agar, but since it actively moves by moving flagella, it has characteristics of both plants and animals. Euglena is extremely adaptable to the environment and is capable of growing through photosynthesis and growing in the dark.
ユーグレナの体内に貯蔵されるパラミロンからナノファイバーを抽出する際に、ＣＮＦの製造とは異なり、大きなエネルギーや多くの時間を必要とすることがない。具体的には、ＰＮＦは、ボトムアップ方式によるマイルドな条件（透明液体化工程を含む）に基づいて製造される。また、ナノファイバーの抽出時に緩い撹拌のみを行うことにより、太さと長さが均一であるＰＮＦが得られる。そこで、本発明の発明者は、ＣＮＦが有していた課題（繊維の不均一性及び高コスト）を解消できる素材としてＰＮＦに着目した。 Unlike the production of CNF, the extraction of nanofibers from paramylon stored in the body of Euglena does not require large amounts of energy or much time. Specifically, PNF is manufactured under mild conditions (including a process of making a transparent liquid) by a bottom-up method. In addition, PNF having a uniform thickness and length can be obtained by performing only gentle agitation when extracting nanofibers. Therefore, the inventors of the present invention focused on PNF as a material that can solve the problems of CNF (non-uniformity of fibers and high cost).
パラミロン（β－１，３－グルカン）は、ユーグレナ属（Ｅｕｇｌｅｎａｇｒａｃｉｌｉｓ）のみが細胞内貯蔵物質として生成する多糖類のことであり、食物繊維の一種である。パラミロンは、全ての種類のユーグレナにおいて存在する。しかし、パラミロンの個数、形状、及び粒子の均一性は、ユーグレナの種類に応じて異なる。 Paramylon (β-1,3-glucan) is a polysaccharide produced as an intracellular storage substance only by the genus Euglena (Euglenagracilis), and is a kind of dietary fiber. Paramylon is present in all types of Euglena. However, the number, shape, and uniformity of particles of paramylon differ depending on the type of Euglena.
特に、ユーグレナの体内に貯蔵されるパラミロンの細胞内含有量は、ユーグレナの培養条件（温度、培地成分、及び光の有無等）によって大きく影響を受ける。例えば、１匹のユーグレナが貯蔵するパラミロンの細胞内含有量が、最大乾燥重量で７０％を超えるユーグレナの種類があることが確認されている。 In particular, the intracellular content of paramylon stored in the body of Euglena is greatly affected by the culture conditions of Euglena (temperature, medium components, presence or absence of light, etc.). For example, it has been confirmed that there are types of Euglena in which the intracellular content of paramylon stored in one Euglena exceeds 70% in maximum dry weight.
（セルロースナノファイバー）
一方で、セルロースナノファイバー（以下、ＣＮＦ）は、主に植物の細胞壁に由来するセルロース繊維をナノサイズまで細かく解きほぐす（解繊する）ことで得られる繊維素材である。ＣＮＦは、軽量、高強度、高弾性率、及び熱による変形が小さい等の多くの利点を有する。また、ＣＮＦは、植物由来の様々なバイオマスから取り出すことができる点で環境負荷が小さいといった持続可能型資源でもある。ＣＮＦは、例えば、ゴム又は樹脂等の他の素材と組み合わせた複合材料として利用されている。
(cellulose nanofiber)
On the other hand, cellulose nanofiber (hereinafter referred to as CNF) is a fiber material obtained by finely disentangling (fibrillating) cellulose fibers mainly derived from plant cell walls to nano-size. CNF has many advantages such as light weight, high strength, high modulus and low thermal deformation. In addition, CNF is also a sustainable resource that has a low environmental load in that it can be extracted from various plant-derived biomass. CNF is used, for example, as a composite material in combination with other materials such as rubber or resin.
ＣＮＦは、他のフィラー類（樹脂の機能を高めるために充填する無機又は有機性の微粒子）と同様に、複合樹脂組成物中に混合され得る。これにより、ＣＮＦを含有した複合樹脂組成物形物からなる層の強度が向上する。このように、複合樹脂組成物の層の力学特性が改善することから、複合樹脂組成物にＣＮＦを添加することが行われている。 CNF can be mixed in the composite resin composition, like other fillers (inorganic or organic fine particles filled to enhance the functionality of the resin). As a result, the strength of the layer made of the CNF-containing composite resin composition is improved. Since the mechanical properties of the layer of the composite resin composition are thus improved, CNF is added to the composite resin composition.
例えば、特許文献１は、ＣＮＦの分散液中で、エチレン性不飽和単量体を共重合させることで、高い強度を発現するＣＮＦと樹脂との複合体の製造方法を開示している。また、特許文献１は、複合体中でＣＮＦがゴム又は樹脂に均一に分散することを開示している。 For example, Patent Document 1 discloses a method for producing a CNF-resin composite that exhibits high strength by copolymerizing an ethylenically unsaturated monomer in a CNF dispersion. Patent document 1 also discloses that CNF is uniformly dispersed in the rubber or resin in the composite.
本明細書の冒頭で説明した通り、ＣＮＦは、化学解繊処理工程（ＴＥＭＰＯ酸化）及び機械解繊処理工程によるトップダウン方式に基づいて、セルロースを強制的微小化することで得られる。化学解繊処理工程（ＴＥＭＰＯ酸化）は、木材チップからセルロースを抽出する工程のことをいう。このように、ＣＮＦの製造は、多くの処理工程を必要とするため、大きなエネルギーと多大な時間がかかっている。つまり、ＣＮＦのコストが高額となるといった問題がある。 As explained at the beginning of this specification, CNFs are obtained by forced micronization of cellulose based on a top-down approach with a chemical fibrillation process (TEMPO oxidation) and a mechanical fibrillation process. The chemical defibration process (TEMPO oxidation) refers to the process of extracting cellulose from wood chips. Thus, the production of CNF requires a large amount of energy and a great deal of time because it requires many processing steps. That is, there is a problem that the cost of CNF becomes high.
（水不溶性重合体粒子）
水不溶性重合体粒子は、エチレン性不飽和単量体、好ましくは（メタ）アクリル酸エステルに由来する構造単位を有する。水不溶性重合体粒子は、１種類のエチレン性不飽和単量体からなる単独重合体、又は、２種類以上のエチレン性不飽和単量体からなる共重合体の粒子である、なお、本明細書中において、「（メタ）アクリル」の文言には、「アクリル」及び「メタクリル」の両方の文言が含まれることを意味する。
(Water-insoluble polymer particles)
The water-insoluble polymer particles have structural units derived from ethylenically unsaturated monomers, preferably (meth)acrylic acid esters. The water-insoluble polymer particles are particles of a homopolymer consisting of one type of ethylenically unsaturated monomer, or particles of a copolymer consisting of two or more types of ethylenically unsaturated monomers. In this document, the term "(meth)acrylic" is meant to include the terms "acrylic" and "methacrylic".
水不溶性重合体粒子は、（メタ）アクリル系単量体からなる群の単量体のみを重合して得られた（メタ）アクリル系単量体に由来する構造単位のみを有するものであって良い。なお、水不溶性重合体粒子は、これに限定されず、（メタ）アクリル系単量体と共重合可能な（メタ）アクリル系単量体以外のビニル基を有するエチレン性不飽和単量体を重合させて得られたものであっても良い。この場合、水不溶性重合体粒子は、（メタ）アクリル系単量体に由来する構造単位と、（メタ）アクリル系単量体と共重合可能なその他の単量体に由来する構造単位を有する。 The water-insoluble polymer particles have only structural units derived from (meth)acrylic monomers obtained by polymerizing only monomers of the group consisting of (meth)acrylic monomers. good. In addition, the water-insoluble polymer particles are not limited to this, and an ethylenically unsaturated monomer having a vinyl group other than a (meth)acrylic monomer copolymerizable with a (meth)acrylic monomer is used. It may be obtained by polymerization. In this case, the water-insoluble polymer particles have a structural unit derived from a (meth)acrylic monomer and a structural unit derived from another monomer copolymerizable with the (meth)acrylic monomer. .
（エチレン性不飽和単量体）
水不溶性重合体粒子は、エチレン性不飽和単量体を構成単位として含む。エチレン性不飽和単量体は、（メタ）アクリル系単量体、スチレン系単量体、（メタ）アクリロニトリル系単量体、及びその他の単量体である。
(Ethylenically unsaturated monomer)
The water-insoluble polymer particles contain an ethylenically unsaturated monomer as a structural unit. Ethylenically unsaturated monomers are (meth)acrylic monomers, styrenic monomers, (meth)acrylonitrile monomers, and other monomers.
一実施形態において、複合樹脂組成物は、水不溶性重合体粒子１００質量部に対して、エチレン性不飽和単量体として（メタ）アクリル系単量体、スチレン系単量体、及び（メタ）アクリロニトリル系単量体の少なくともいずれかを５０質量部以上、好ましくは６０質量部以上、より好ましくは７０質量部以上含む。 In one embodiment, the composite resin composition contains, with respect to 100 parts by mass of the water-insoluble polymer particles, a (meth)acrylic monomer, a styrene monomer, and (meth) as ethylenically unsaturated monomers. 50 parts by mass or more, preferably 60 parts by mass or more, and more preferably 70 parts by mass or more of at least one acrylonitrile-based monomer.
（メタ）アクリル系単量体は、（メタ）アクリル酸エステル（ａ１）、水酸基含有（メタ）アクリル酸エステル（ａ２）、窒素原子含有（メタ）アクリル酸エステル（ａ３）、及びフッ素原子含有（メタ）アクリル酸エステル（ａ４）を含む。 The (meth) acrylic monomer includes (meth) acrylic ester (a1), hydroxyl group-containing (meth) acrylic ester (a2), nitrogen atom-containing (meth) acrylic ester (a3), and fluorine atom-containing ( Contains meth)acrylic acid ester (a4).
スチレン系単量体は、芳香族を有する重合性単量体（ａ５）を含む。 The styrenic monomer includes a polymerizable monomer (a5) having an aromatic group.
（メタ）アクリロニトリル系単量体は、アクリロニトリル及びメタクリロニトリルを含む。 (Meth)acrylonitrile-based monomers include acrylonitrile and methacrylonitrile.
その他の単量体は、カルボキシ基を有する重合性単量体（ａ６）及び重合性二重結合を２つ以上有する単量体（ａ７）を含む。 Other monomers include a polymerizable monomer (a6) having a carboxy group and a monomer (a7) having two or more polymerizable double bonds.
（メタ）アクリル系単量体として（メタ）アクリル酸エステル（ａ１）と、カルボキシ基を有する重合性単量体（ａ５）として（メタ）アクリル酸とを用いることが好ましく、（メタ）アクリル酸エステル（ａ１）を用いることがより好ましい。 It is preferable to use (meth)acrylic acid ester (a1) as the (meth)acrylic monomer and (meth)acrylic acid as the polymerizable monomer (a5) having a carboxy group. More preferably, ester (a1) is used.
水不溶性重合体粒子は、水酸基含有（メタ）アクリル酸エステル（ａ２）、窒素原子含有（メタ）アクリル酸エステル（ａ３）、又はフッ素原子含有（メタ）アクリル酸エステル（ａ４）のいずれかをさらに含んでも良い。 The water-insoluble polymer particles further contain any of a hydroxyl group-containing (meth)acrylic ester (a2), a nitrogen atom-containing (meth)acrylic ester (a3), or a fluorine atom-containing (meth)acrylic ester (a4). may include.
一実施形態において、複合樹脂組成物は、水不溶性重合体粒子１００質量部に対して、（メタ）アクリル酸エステル（ａ１）を５０質量部以上、好ましくは６０質量部以上、より好ましくは７０質量部以上を含む。 In one embodiment, the composite resin composition contains 50 parts by mass or more, preferably 60 parts by mass or more, more preferably 70 parts by mass of the (meth)acrylic acid ester (a1) with respect to 100 parts by mass of the water-insoluble polymer particles. Including part and above.
（メタ）アクリル酸エステル（ａ１）は、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｎ－アミル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ｎ－ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、テトラデシル（メタ）アクリレート、ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、フェニル（メタ）アクリレート、２－メトキシエチル（メタ）アクリレート、エチルカルビトールアクリレート、β－カルボキシエチル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、アリル（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、２－クロロエチル（メタ）アクリレート、トリフルオロエチル（メタ）アクリレート、及びパーフルオロオクチルエチル（メタ）アクリレート等である。（メタ）アクリル酸エステル（ａ１）は、上記のうち１種を単独で又は２種以上を組み合わせて用いられても良い。 (Meth)acrylate (a1) is, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, ) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate ) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate ) acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, phenyl (meth)acrylate, 2-methoxyethyl (meth)acrylate , ethyl carbitol acrylate, β-carboxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di ( meth)acrylate, allyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, 2-chloroethyl (meth)acrylate, trifluoroethyl (meth)acrylate, perfluorooctylethyl (meth)acrylate and the like. The (meth)acrylic acid ester (a1) may be used alone or in combination of two or more of the above.
一実施形態において、複合樹脂組成物は、水不溶性重合体粒子１００質量部に対して、水酸基含有（メタ）アクリル酸エステル（ａ２）を０．１質量部以上、好ましくは０．５質量部以上、より好ましくは１．０質量部以上含む。 In one embodiment, the composite resin composition contains 0.1 parts by mass or more, preferably 0.5 parts by mass or more of the hydroxyl group-containing (meth)acrylic acid ester (a2) with respect to 100 parts by mass of the water-insoluble polymer particles. , more preferably 1.0 parts by mass or more.
水酸基含有（メタ）アクリル酸エステル（ａ２）は、炭素原子数１～１２のアルキル基を有するアルキル（メタ）アクリレートである。アルキル基は、直鎖状でも分岐状でもよく、アルキル基の炭素原子数は１～８である。水酸基含有（メタ）アクリル酸エステルは、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、カプロラクトン変性ヒドロキシ（メタ）アクリレート（例えば、ダイセル化学工業製の「プラクセルＦ」シリーズ等）等である。水酸基含有（メタ）アクリル酸エステル（ａ２）は、上記のうち１種を単独で又は２種以上を組み合わせて用いられても良い。 The hydroxyl group-containing (meth)acrylic acid ester (a2) is an alkyl (meth)acrylate having an alkyl group having 1 to 12 carbon atoms. The alkyl group may be linear or branched and has 1 to 8 carbon atoms. Hydroxyl group-containing (meth) acrylic acid esters, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy (meth)acrylate (for example, "PLAXEL F" series manufactured by Daicel Chemical Industries, etc.), and the like. The hydroxyl group-containing (meth)acrylic acid ester (a2) may be used alone or in combination of two or more of the above.
また、水酸基含有（メタ）アクリル酸エステル（ａ２）は、ラジカル重合モノマーからなる機能付与型の界面活性剤である反応性の乳化重合用乳化剤を含む。反応性の乳化重合用乳化剤は、例えば、商品名：アデカリアソープ ＥＲ－１０、ＥＲ－２０、ＥＲ－３０、ＥＲ－４０（アデカ社製）等である。 In addition, the hydroxyl group-containing (meth)acrylic acid ester (a2) contains a reactive emulsifier for emulsion polymerization, which is a function-imparting surfactant composed of a radically polymerizable monomer. Examples of reactive emulsifiers for emulsion polymerization include trade names: ADEKA ARISOAP ER-10, ER-20, ER-30, ER-40 (manufactured by ADEKA CORPORATION).
窒素原子含有（メタ）アクリル酸エステル（ａ３）は、例えば、（メタ）アクリルアミド、Ｎ－モノメチル（メタ）アクリルアミド、Ｎ－モノエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ－ｎ－プロピル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ－ブチル（メタ）アクリルアミド、メチレンビス（メタ）アクリルアミド、モルホリンアクリルアミド、Ｎ－メトキシメチル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－メチロールプロパン（メタ）アクリルアミド、Ｎ－ブトキシメチル（メタ）アクリルアミド、ジアセトンアクリルアミド、（メタ）アクリロイルオキシエチルトリメチルアンモニウムクロライド、ジメチルアミノエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリルアミド、モルホリンのエチレンオキサイド付加（メタ）アクリレート、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ｔ－ブチルアミノエチル、Ｎ－ビニルピリジン、Ｎ－ビニルイミダゾール、Ｎ－ビニルピロール、Ｎ－ビニルピロリドン、Ｎ－ビニルオキサゾリドン、Ｎ－ビニルサクシンイミド、Ｎ－ビニルメチルカルバメート、Ｎ，Ｎ－メチルビニルアセトアミド、２－イソプロペニル－２－オキサゾリン、２－ビニル－２－オキサゾリン、（メタ）アクリロニトリル、及びＮ－ビニルカルボン酸アミド等である。窒素原子含有（メタ）アクリル酸エステル（ａ３）は、上記のうち１種を単独で又は２種以上を組み合わせて用いられても良い。 Nitrogen atom-containing (meth)acrylic acid ester (a3) is, for example, (meth)acrylamide, N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N - diethyl (meth)acrylamide, Nn-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, methylenebis (meth)acrylamide, morpholine acrylamide, N-methoxymethyl (meth)acrylamide , N-methylol (meth)acrylamide, N-methylolpropane (meth)acrylamide, N-butoxymethyl (meth)acrylamide, diacetone acrylamide, (meth)acryloyloxyethyltrimethylammonium chloride, dimethylaminoethyl (meth)acrylate, dimethyl Aminoethyl (meth)acrylamide, ethylene oxide addition (meth)acrylate of morpholine, dimethylaminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate, N-vinylpyridine, N-vinylimidazole, N-vinyl pyrrole, N-vinylpyrrolidone, N-vinyloxazolidone, N-vinylsuccinimide, N-vinylmethylcarbamate, N,N-methylvinylacetamide, 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline, ( meth)acrylonitrile, N-vinylcarboxylic acid amide, and the like. The nitrogen atom-containing (meth)acrylic acid ester (a3) may be used alone or in combination of two or more of the above.
フッ素原子含有（メタ）アクリル酸エステル（ａ４）は、例えば、２，２，２－トリフルオロエチルアクリレート、２，２，３，３，３－ペンタフルオロプロピルアクリレート、２－（パーフルオロブチル）エチルアクリレート、２－（パーフルオロヘキシル）エチルアクリレート、１Ｈ，１Ｈ，３Ｈ－テトラフルオロプロピルアクリレート等、及びフッ化ビニル等を含む。フッ素原子含有（メタ）アクリル酸エステル（ａ４）は、上記のうち１種を単独で又は２種以上を組み合わせて用いられても良い。 The fluorine atom-containing (meth)acrylic acid ester (a4) is, for example, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-(perfluorobutyl)ethyl acrylates, 2-(perfluorohexyl)ethyl acrylate, 1H,1H,3H-tetrafluoropropyl acrylate and the like, and vinyl fluoride and the like. The fluorine atom-containing (meth)acrylic acid ester (a4) may be used alone or in combination of two or more of the above.
一実施形態において、複合樹脂組成物は、水不溶性重合体粒子１００質量部に対して、芳香族を有する重合性単量体（ａ５）を２０質量部以上、好ましくは３０質量部以上、より好ましくは４０質量部以上含む。 In one embodiment, the composite resin composition contains 20 parts by mass or more, preferably 30 parts by mass or more, more preferably 30 parts by mass or more of the polymerizable monomer (a5) having an aromatic group relative to 100 parts by mass of the water-insoluble polymer particles. contains 40 parts by mass or more.
芳香族を有する重合性単量体（ａ５）は、例えば、スチレン、α－メチルスチレン、ビニルトルエン、エチルビニルベンゼン、クロロスチレン、クロロメチルスチレン、４－ヒドロキシスチレン、ジビニルベンゼン、バーサチック酸ビニル、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル及び塩化ビニル等である。芳香族を有する重合性単量体（ａ５）は、上記のうち１種を単独で又は２種以上を組み合わせて用いられても良い。 Polymerizable monomers (a5) having aromatics are, for example, styrene, α-methylstyrene, vinyltoluene, ethylvinylbenzene, chlorostyrene, chloromethylstyrene, 4-hydroxystyrene, divinylbenzene, vinyl versatate, and formic acid. Examples include vinyl, vinyl acetate, vinyl propionate and vinyl chloride. The aromatic-containing polymerizable monomer (a5) may be used alone or in combination of two or more of the above.
一実施形態において、複合樹脂組成物は、水不溶性重合体粒子１００質量部に対して、重合性単量体（ａ６）を０．１質量部以上、好ましくは０．１５質量部以上、より好ましくは０．２質量部以上含む。 In one embodiment, the composite resin composition contains 0.1 parts by mass or more, preferably 0.15 parts by mass or more, more preferably 0.15 parts by mass or more of the polymerizable monomer (a6) with respect to 100 parts by mass of the water-insoluble polymer particles. contains 0.2 parts by mass or more.
カルボキシ基を有する重合性単量体（ａ６）は、（メタ）アクリル系単量体と共重合可能な単量体であり、例えば、（メタ）アクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸、シトラコン酸、イタコン酸、イタコン酸ハーフエステル、マレイン酸ハーフエステル、無水マレイン酸及び無水イタコン酸等である。重合性単量体（ａ６）は、上記のうち１種を単独で又は２種以上を組み合わせて用いられても良い。 The polymerizable monomer (a6) having a carboxy group is a monomer copolymerizable with a (meth)acrylic monomer, such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, Examples include fumaric acid, citraconic acid, itaconic acid, itaconic acid half ester, maleic acid half ester, maleic anhydride and itaconic anhydride. The polymerizable monomer (a6) may be used alone or in combination of two or more of the above.
さらに、水不溶性重合体粒子を構成する単量体は、樹脂粒子を架橋させ得る単量体を含む。樹脂粒子を架橋させ得る単量体は、例えば、重合性二重結合を２つ以上有する単量体である。 Furthermore, the monomers constituting the water-insoluble polymer particles include monomers capable of cross-linking the resin particles. A monomer capable of cross-linking resin particles is, for example, a monomer having two or more polymerizable double bonds.
重合性二重結合を２つ以上有する単量体（ａ７）は、例えば、エチレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、アリル（メタ）アクリレート、及び、トリメチロールプロパントリ（メタ）アクリレート等の重合性二重結合を２つ以上有する（メタ）アクリル系単量体のほか、ジビニルベンゼン、及び、ジアリルフタレート等である。重合性二重結合を２つ以上有する単量体（ａ７）は、上記のうち１種を単独で又は２種以上を組み合わせて用いられても良い。 The monomer (a7) having two or more polymerizable double bonds is, for example, ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth) In addition to (meth)acrylic monomers having two or more polymerizable double bonds such as acrylate, diethylene glycol di(meth)acrylate, allyl(meth)acrylate, and trimethylolpropane tri(meth)acrylate, divinylbenzene , and diallyl phthalate. The monomer (a7) having two or more polymerizable double bonds may be used alone or in combination of two or more of the above.
＜その他の添加剤＞
水不溶性重合体粒子は、重合開始剤、乳化剤、及び連鎖移動剤を更に含む。
<Other additives>
The water-insoluble polymer particles further contain polymerization initiators, emulsifiers, and chain transfer agents.
（重合開始剤）
重合開始剤は、例えば、過硫酸塩、有機過酸化物、及び過酸化水素等の過酸化物、並びに、アゾ化合物等を含む。重合開始剤は、上記の１種を単独で又は２種以上を組み合わせて用いられても良い。また、過酸化物と併用するレドックス重合開始剤、又は、重合促進剤として１種又は２種以上の還元剤が用いられても良い。
(Polymerization initiator)
Polymerization initiators include, for example, persulfates, organic peroxides, peroxides such as hydrogen peroxide, and azo compounds. The polymerization initiator may be used alone or in combination of two or more. In addition, one or two or more reducing agents may be used as a redox polymerization initiator or a polymerization accelerator used in combination with the peroxide.
過硫酸塩は、例えば、過硫酸カリウム、過硫酸ナトリウム、及び過硫酸アンモニウム等である。有機過酸化物は、例えば、過酸化ベンゾイル及びジラウロイルパーオキサイド等のジアシルパーオキサイド類、ｔ－ブチルクミルパーオキサイド及びジクミルパーオキサイド等のジアルキルパーオキサイド類、ｔ－ブチルパーオキシラウレート及びｔ－ブチルパーオキシベンゾエート等のパーオキシエステル類、クメンハイドロパーオキサイド及びｔ－ブチルハイドロパーオキサイド等のハイドロパーオキサイド類等である。 Persulfates are, for example, potassium persulfate, sodium persulfate, ammonium persulfate, and the like. Organic peroxides are, for example, diacyl peroxides such as benzoyl peroxide and dilauroyl peroxide, dialkyl peroxides such as t-butyl cumyl peroxide and dicumyl peroxide, t-butyl peroxylaurate and t peroxyesters such as -butyl peroxybenzoate, and hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide.
アゾ化合物は、例えば、２，２'－アゾビス（２－アミジノプロパン）二塩酸塩及び４，４'－アゾビス（４－シアノペンタン酸）等である。 Azo compounds include, for example, 2,2′-azobis(2-amidinopropane) dihydrochloride and 4,4′-azobis(4-cyanopentanoic acid).
重合促進剤としての還元剤は、特に限定されるものではないが、例えば、アスコルビン酸及びその塩、エリソルビン酸及びその塩、酒石酸及びその塩、亜硫酸及びその塩、重亜硫酸及びその塩、チオ硫酸及びその塩、並びに鉄（II）塩等を挙げることができる。 The reducing agent as a polymerization accelerator is not particularly limited, but examples include ascorbic acid and its salts, erythorbic acid and its salts, tartaric acid and its salts, sulfurous acid and its salts, bisulfite and its salts, thiosulfuric acid. and salts thereof, iron (II) salts, and the like.
（乳化剤）
乳化剤は、水不溶性重合体粒子を構成するエチレン性不飽和単量体を重合する際に用いられる界面活性剤であり、例えば、アニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤、及び両性界面活性剤等である。乳化剤は、上記のうち１種を単独で又は２種以上を組み合わせて用いられても良い。乳化剤として好ましくはアニオン性界面活性剤及びノニオン性界面活性剤であり、より好ましくはアニオン性界面活性剤である。
(emulsifier)
Emulsifiers are surfactants used in polymerizing the ethylenically unsaturated monomers that make up the water-insoluble polymer particles. Examples include anionic surfactants, nonionic surfactants, and cationic surfactants. , and amphoteric surfactants. Among the above emulsifiers, one may be used alone or two or more may be used in combination. Anionic surfactants and nonionic surfactants are preferred as emulsifiers, and anionic surfactants are more preferred.
（連鎖移動剤）
連鎖移動剤は、必要に応じて、水不溶性重合体粒子を構成するエチレン性不飽和単量体を重合する際に用いられ、例えば、ヘキシルメルカプタン、ラウリルメルカプタン、オクチルメルカプタン、ｎ－ドデシルメルカプタン、及び、ｔ－ドデシルメルカプタン等のアルキルメルカプタン類等である。連鎖移動剤は、上記のうち１種を単独で又は２種以上を組み合わせて用いられても良い。
(chain transfer agent)
A chain transfer agent is optionally used when polymerizing the ethylenically unsaturated monomers constituting the water-insoluble polymer particles. , t-dodecyl mercaptan and other alkyl mercaptans. The chain transfer agent may be used alone or in combination of two or more of the above.
（ガラス転移温度（Ｔｇ））
水不溶性重合体粒子のガラス転移温度（Ｔｇ）は、－６０～１００℃、好ましくは－５０～８０℃、より好ましくは－４０～４０℃である。ガラス転移温度（Ｔｇ）とは、物質がゴム状態からガラス状態になる境界温度のことをいう。
(Glass transition temperature (Tg))
The glass transition temperature (Tg) of the water-insoluble polymer particles is -60 to 100°C, preferably -50 to 80°C, more preferably -40 to 40°C. The glass transition temperature (Tg) is the boundary temperature at which a substance changes from a rubbery state to a glassy state.
水不溶性重合体粒子のＴｇは、単独の単量体からなる単独重合体（ホモポリマー）である場合、ＤＳＣ測定による値である。また、水不溶性重合体粒子のＴｇは、２種類以上の単量体からなる共重合体（コポリマー）である場合、上記の単独重合体の場合のＴｇを用いて、以下の式１（ＦＯＸ式）から求められる理論値となる。
１／Ｔｇ＝Ｗ１／Ｔｇ１＋Ｗ２／Ｔｇ２＋・・・Ｗｎ／Ｔｇｎ （式１）
The Tg of the water-insoluble polymer particles is a value obtained by DSC measurement in the case of a homopolymer (homopolymer) consisting of a single monomer. Further, the Tg of the water-insoluble polymer particles, in the case of a copolymer consisting of two or more types of monomers, is expressed by the following formula 1 (FOX formula ) is the theoretical value obtained from
1/Tg=W1/Tg1+W2/Tg2+...Wn/Tgn (Formula 1)
式１で、Ｔｇは、ｎ種類の単量体（単量体１～ｎ）からなる各共重合体を含むガラス転移温度（単位：Ｋ）を表す。Ｗ１、Ｗ２、・・・Ｗｎは、ｎ種類の単量体の総質量に対する各単量体（１、２、・・・ｎ）の質量分率を表す。Ｔｇ１、Ｔｇ２、・・・Ｔｇｎは、各単量体（１、２、・・・ｎ）からなる単独重合体のガラス転移温度（単位：Ｋ）を表す。 In Formula 1, Tg represents the glass transition temperature (unit: K) of each copolymer composed of n kinds of monomers (monomers 1 to n). W1, W2, . . . Wn represent the mass fraction of each monomer (1, 2, . . . n) with respect to the total mass of n kinds of monomers. Tg1, Tg2, . . . Tgn represent glass transition temperatures (unit: K) of homopolymers composed of respective monomers (1, 2, . . . n).
（水不溶性重合体粒子の重合方法）
水不溶性重合体粒子は、溶液重合、塊状重合、乳化重合及び懸濁重合等により合成される。水不溶性重合体粒子の粒子径の調整の容易性及び生産性の観点から、水性媒体中で乳化重合を行う方法が用いられるとよい。乳化重合の方法は、水性媒体、単量体成分、及び重合開始剤等を一括で混合して乳化重合する方法を含む。また、乳化重合の方法は、水性媒体及び単量体成分等を含有するプレエマルションを用いて乳化重合する方法を含む。
(Method for polymerizing water-insoluble polymer particles)
Water-insoluble polymer particles are synthesized by solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and the like. From the viewpoints of easiness in adjusting the particle size of the water-insoluble polymer particles and productivity, it is preferable to use a method of carrying out emulsion polymerization in an aqueous medium. The method of emulsion polymerization includes a method of mixing an aqueous medium, a monomer component, a polymerization initiator, etc. at once and performing emulsion polymerization. Moreover, the method of emulsion polymerization includes a method of emulsion polymerization using a pre-emulsion containing an aqueous medium, a monomer component, and the like.
（分散媒）
複合樹脂組成物は水性分散媒を更に含むエマルションである。分散媒は、水性媒体であり、例えば、水及びイオン交換水である。
(dispersion medium)
The composite resin composition is an emulsion that further contains an aqueous dispersion medium. The dispersion medium is an aqueous medium such as water and ion-exchanged water.
＜塗装品及びその製造方法＞
塗装品は、基材と、基材上の複合樹脂組成物からなる層と、を備える。以下、基材と、複合樹脂組成物からなる層（以下、樹脂層）について説明する。
<Painted product and its manufacturing method>
A coated article includes a substrate and a layer of a composite resin composition on the substrate. The substrate and the layer made of the composite resin composition (hereinafter referred to as the resin layer) will be described below.
（基材）
基材は、本発明に係る複合樹脂組成物が塗布される基材である。基材は、有機材料及び無機材料のいずれでもよい。有機材料は、プラスチック、樹脂、繊維、ゴム、木材、壁紙等を含む。無機材料は、ガラス、セラミックス、シリカ、金属等を含む。
(Base material)
A substrate is a substrate to which the composite resin composition according to the present invention is applied. The base material may be either an organic material or an inorganic material. Organic materials include plastics, resins, fibers, rubber, wood, wallpaper, and the like. Inorganic materials include glasses, ceramics, silica, metals, and the like.
プラスチックは、例えば、ポリエチレンテレフタレート（ＰＥＴフィルム）、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコール（ＰＶＡ）、エチレン?酢酸ビニル共重合体、ポリスチレン、ポリカーボネート、ポリメチルペンテン、ポリスルホン、ポリエーテルエーテルケトン、ポリエーテルスルフォン、ポリフェニレンスルフィド、ポリエーテルイミド、及びポリイミド等を含む。 Plastics include polyesters such as polyethylene terephthalate (PET film), polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol (PVA), ethylene-vinyl acetate copolymer, polystyrene , polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyphenylene sulfide, polyetherimide, and polyimide.
樹脂は、フッ素樹脂、ポリアミド、アクリル樹脂、ノルボルネン系樹脂、シクロオレフィン樹脂、及びトリアセチルセルロース（ＴＡＣ）等を含む。 Resins include fluororesins, polyamides, acrylic resins, norbornene-based resins, cycloolefin resins, triacetyl cellulose (TAC), and the like.
金属は、例えば、鉄、ステンレス等の鉄系金属、及び、アルミニウム、マグネシウム、亜鉛、それらの合金等の非鉄系金属を含む。鉄系金属は、冷延鋼板、熱延鋼板、及びステンレス鋼板等を含む。非鉄系金属は、アルミニウム鋼板、亜鉛鋼板、マグネシウム合金、アルミニウム－亜鉛合金、亜鉛－ニッケルメッキ鋼板、亜鉛－クロムメッキ鋼板、及び亜鉛－マグネシウムメッキ鋼板等を含む。 Metals include, for example, ferrous metals such as iron and stainless steel, and non-ferrous metals such as aluminum, magnesium, zinc, and alloys thereof. Ferrous metals include cold-rolled steel sheets, hot-rolled steel sheets, stainless steel sheets, and the like. Nonferrous metals include aluminum steel sheets, zinc steel sheets, magnesium alloys, aluminum-zinc alloys, zinc-nickel plated steel sheets, zinc-chrome plated steel sheets, zinc-magnesium plated steel sheets, and the like.
（樹脂層）
樹脂層は、本発明に係る複合樹脂組成物を硬化乾燥させた塗膜のことである。複合樹脂組成物の態様は、硬化乾燥前に液体状であり、硬化乾燥後に固体状である。基材の少なくとも一方の表面に塗布する複合樹脂組成物の塗工量は、乾燥後の樹脂層の厚さに応じた量であってよい。樹脂層の厚さは、５～１０００μｍ、好ましくは２０～８００μｍ、より好ましくは４０～６００μｍである。
(resin layer)
The resin layer is a coating film obtained by curing and drying the composite resin composition according to the present invention. The aspect of the composite resin composition is liquid before curing and drying, and solid after curing and drying. The amount of the composite resin composition applied to at least one surface of the substrate may be an amount corresponding to the thickness of the resin layer after drying. The thickness of the resin layer is 5-1000 μm, preferably 20-800 μm, more preferably 40-600 μm.
基材の少なくとも一方の表面に複合樹脂組成物を塗布する方法は、例えば、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法等を含む。上記の方法のいずれかにより複合樹脂組成物を基材に塗布して、塗膜を形成した後、４０～１５０℃、好ましくは６０～１２０℃、より好ましくは７０～１００℃で硬化乾燥する。乾燥時間は、１０～２０時間、好ましくは１２～２０時間、より好ましくは１６～２０時間である。 Methods for applying the composite resin composition to at least one surface of the substrate include, for example, bar coating, knife coating, roll coating, blade coating, die coating, gravure coating and the like. After the composite resin composition is applied to the substrate by any of the above methods to form a coating film, it is cured and dried at 40 to 150°C, preferably 60 to 120°C, more preferably 70 to 100°C. The drying time is 10-20 hours, preferably 12-20 hours, more preferably 16-20 hours.
＜複合樹脂組成物の製造＞
実施例１～４は、パラミロンナノファイバーを含有する水性分散媒中でエチレン性不飽和単量体を重合する方法を用いて複合樹脂組成物を製造した。また参考例１～６は、水性分散媒中でエチレン性不飽和単量体を重合する方法を用いて水不溶性重合体粒子を製造した。表１及び表２の単量体、ＰＮＦ、ＣＮＦ１、及びＣＮＦ２の数値は、部（質量部）を表す。
<Production of composite resin composition>
Examples 1-4 produced composite resin compositions using a method of polymerizing an ethylenically unsaturated monomer in an aqueous dispersion medium containing paramylon nanofibers. In Reference Examples 1 to 6, water-insoluble polymer particles were produced using a method of polymerizing an ethylenically unsaturated monomer in an aqueous dispersion medium. The numerical values of the monomers, PNF, CNF1, and CNF2 in Tables 1 and 2 represent parts (mass parts).
（実施例１）
表１に示した通り、エチレン性不飽和単量体としてメチルメタクリレート（ＭＭＡ）３３部、ブチルアクリレート（ＢＡ）６６部、及びメタクリル酸（ＭＡＡＣ）１．０部、パラミロンナノファイバー（２％）（以下、ＰＮＦ）５０部、イオン交換水１５部、乳化剤／ポリオキシエチレンアルキルエーテル硫酸ナトリウム（２６％）（以下、乳化剤Ａ）２部とを撹拌混合して、単量体混合乳化物を調製した。
(Example 1)
As shown in Table 1, as ethylenically unsaturated monomers, 33 parts of methyl methacrylate (MMA), 66 parts of butyl acrylate (BA), and 1.0 part of methacrylic acid (MAAC), paramylon nanofiber (2%) ( 50 parts of PNF), 15 parts of ion-exchanged water, and 2 parts of emulsifier/sodium polyoxyethylene alkyl ether sulfate (26%) (hereinafter referred to as emulsifier A) were stirred and mixed to prepare a monomer mixed emulsion. .
撹拌機、温度計、還流コンデンサー付の１Ｌの四つ口丸底フラスコに、イオン交換水７０部を仕込み、撹拌下に窒素置換しながら８０℃迄昇温した。そして、内温を８０℃に保ちながら、重合開始剤として過硫酸ナトリウム０．４部を添加し、溶解後、予め調製した単量体混合乳化物を約２時間かけて滴下、反応させた。単量体混合乳化物の滴下終了後、更に８０℃で約３時間の熟成を行い冷却した。その後、５％水酸化ナトリウム水溶液で弱アルカリ性域（ｐＨ８以上１１未満）に調整後、凝集物を除去する目的で濾過をして、蒸発残分約４０％の複合樹脂組成物を得た。 A 1 L four-necked round-bottomed flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 70 parts of ion-exchanged water, and the temperature was raised to 80° C. while stirring and replacing with nitrogen. Then, while maintaining the internal temperature at 80° C., 0.4 part of sodium persulfate was added as a polymerization initiator, and after dissolution, the monomer mixed emulsion prepared in advance was added dropwise over about 2 hours to react. After the completion of dropping of the monomer mixed emulsion, the mixture was further aged at 80° C. for about 3 hours and then cooled. Then, after adjusting to a weakly alkaline range (pH 8 or more and less than 11) with a 5% sodium hydroxide aqueous solution, filtration was carried out for the purpose of removing aggregates to obtain a composite resin composition with an evaporation residue of about 40%.
（実施例２～４、参考例１～６）
実施例１に準じて、表１と表２に示した通り、所定の原料を用いて複合樹脂組成物及び樹脂組成物をそれぞれ調製した。
(Examples 2-4, Reference Examples 1-6)
According to Example 1, as shown in Tables 1 and 2, a composite resin composition and a resin composition were prepared using predetermined raw materials.
実施例５～９、１１及び比較例１、２は、エチレン性不飽和単量体からなる水不溶性重合体粒子を含有する水性分散媒と、ファイバー類（ＰＮＦ又はＣＮＦ）を含有する水性分散媒とを混合する方法を用いて、複合樹脂組成物を製造した。ただし、実施例５～９、１１はＰＮＦを用いて、比較例１、２はＣＮＦを用いて複合樹脂組成物を製造した。 Examples 5 to 9 and 11 and Comparative Examples 1 and 2 are an aqueous dispersion medium containing water-insoluble polymer particles composed of an ethylenically unsaturated monomer and an aqueous dispersion medium containing fibers (PNF or CNF). A composite resin composition was produced using a method of mixing with. However, PNF was used in Examples 5 to 9 and 11, and CNF was used in Comparative Examples 1 and 2 to manufacture composite resin compositions.
（実施例５）
表１に示した通り、単量体としてメチルメタクリレート（ＭＭＡ）２８．５部、ブチルアクリレート（ＢＡ）７０部、及びメタクリル酸（ＭＡＡＣ）１．５部をイオン交換水４０部と乳化剤Ａ１２部と、を撹拌混合して、単量体混合乳化物を調製した。
(Example 5)
As shown in Table 1, 28.5 parts of methyl methacrylate (MMA), 70 parts of butyl acrylate (BA), and 1.5 parts of methacrylic acid (MAAC) as monomers were combined with 40 parts of ion-exchanged water and 12 parts of emulsifier A. , were stirred and mixed to prepare a monomer mixed emulsion.
撹拌機、温度計、還流コンデンサー付の１Ｌの四つ口丸底フラスコに、イオン交換水３０部、撹拌下に窒素置換しながら８０℃迄昇温した。そして、内温を８０℃に保ちながら、重合開始剤として過硫酸ナトリウム０．４部を添加し、溶解後、予め調製した単量体混合乳化物を約２時間かけて滴下、反応させた。更に８０℃で約２時間の熟成後、ＰＮＦ１５０部を８０℃で保持して１時間かけて滴下した後、冷却した。５％水酸化ナトリウム水溶液で弱アルカリ性域（ｐＨ８以上１１未満）に調整後、凝集物を除去する目的で濾過をして、蒸発残分約３０％の複合樹脂組成物を得た。 Into a 1 L four-necked round-bottomed flask equipped with a stirrer, a thermometer and a reflux condenser, 30 parts of ion-exchanged water was stirred and the temperature was raised to 80° C. while substituting nitrogen. Then, while maintaining the internal temperature at 80° C., 0.4 part of sodium persulfate was added as a polymerization initiator, and after dissolution, the monomer mixed emulsion prepared in advance was added dropwise over about 2 hours to react. After aging at 80° C. for about 2 hours, 150 parts of PNF was added dropwise over 1 hour while maintaining the temperature at 80° C., followed by cooling. After adjusting to a weakly alkaline range (pH 8 or more and less than 11) with a 5% sodium hydroxide aqueous solution, filtration was carried out for the purpose of removing aggregates to obtain a composite resin composition with an evaporation residue of about 30%.
（実施例１０）
実施例１０は、パラミロンナノファイバーを含有する水性分散媒中でエチレン性不飽和単量体を重合する方法を用いて複合樹脂組成物を製造した。表１に示した通り、単量体としてメチルメタクリレート（ＭＭＡ）４１部、ブチルアクリレート（ＢＡ）５６部、及びメタクリル酸（ＭＡＡＣ）３部をパラミロンナノファイバー（２％）（ＰＮＦ）５０部、イオン交換水１０部、乳化剤Ａ１２部と、を撹拌混合して、単量体混合乳化物を調製した。
(Example 10)
Example 10 produced a composite resin composition using a method of polymerizing an ethylenically unsaturated monomer in an aqueous dispersion medium containing paramylon nanofibers. As shown in Table 1, 41 parts of methyl methacrylate (MMA), 56 parts of butyl acrylate (BA), and 3 parts of methacrylic acid (MAAC) as monomers, 50 parts of paramylon nanofiber (2%) (PNF), ion 10 parts of exchanged water and 12 parts of emulsifier A were stirred and mixed to prepare a monomer mixed emulsion.
撹拌機、温度計、還流コンデンサー付の１Ｌの四つ口丸底フラスコに、イオン交換水８５部を仕込み、撹拌下に窒素置換しながら８０℃迄昇温した。そして、内温を８０℃に保ちながら、重合開始剤として過硫酸ナトリウム０．４部を添加し、溶解後、予め調製した単量体混合乳化物を約２時間かけて滴下、反応させた。単量体混合乳化物の滴下終了後、更に８０℃で約３時間の熟成後、ＰＮＦ３５０部を８０℃で保持して１時間かけて滴下した後に冷却した。５％水酸化ナトリウム水溶液で弱アルカリ性域（ｐＨ８以上１１未満）に調整後、凝集物を除去する目的で濾過をして、蒸発残分約１８％の複合樹脂組成物を得た。 A 1 L four-necked round-bottomed flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 85 parts of ion-exchanged water, and the temperature was raised to 80° C. while stirring and replacing with nitrogen. Then, while maintaining the internal temperature at 80° C., 0.4 part of sodium persulfate was added as a polymerization initiator, and after dissolution, the monomer mixed emulsion prepared in advance was added dropwise over about 2 hours to react. After dropping of the monomer mixed emulsion was completed, the mixture was further aged at 80°C for about 3 hours, then 350 parts of PNF was dropped at 80°C over 1 hour, and then cooled. After adjusting to a weakly alkaline range (pH 8 or more and less than 11) with a 5% sodium hydroxide aqueous solution, filtration was carried out for the purpose of removing aggregates to obtain a composite resin composition with an evaporation residue of about 18%.
（実施例１２）
実施例１２と後述の実施例１３は、エチレン性不飽和単量体からなる水不溶性重合体粒子を含有する水性分散媒と、パラミロンナノファイバーを含有する水性分散媒と、を含む分散液を強アルカリ性域に調整した後、分散液を弱アルカリ性域に調整する方法を用いて、複合樹脂組成物を製造した。なお、実施例１２は、分散液のｐＨを強アルカリ性域（ｐＨ１１以上）から弱アルカリ性域（ｐＨ８以上１１未満）に調整するが、分散液のｐＨを強アルカリ性域から中性域（ｐＨ６以上８未満）又は弱酸性域（ｐＨ３以上６未満）に調整しても良い。表１に示した通り、単量体としてメチルメタクリレート（ＭＭＡ）４１部、ブチルアクリレート（ＢＡ）５６部、及びメタクリル酸（ＭＡＡＣ）３部をイオン交換水４０部と乳化剤Ａ１０部と、を撹拌混合して、単量体混合乳化物を調製した。
(Example 12)
In Example 12 and Example 13 described later, a dispersion containing an aqueous dispersion medium containing water-insoluble polymer particles made of an ethylenically unsaturated monomer and an aqueous dispersion medium containing paramylon nanofibers was strongly produced. After adjusting to the alkaline range, a composite resin composition was produced using a method of adjusting the dispersion to the weakly alkaline range. In Example 12, the pH of the dispersion is adjusted from a strongly alkaline range (pH 11 or more) to a weakly alkaline range (pH 8 or more and less than 11). less than) or a weakly acidic range (pH 3 or more and less than 6). As shown in Table 1, 41 parts of methyl methacrylate (MMA), 56 parts of butyl acrylate (BA), and 3 parts of methacrylic acid (MAAC) as monomers are stirred and mixed with 40 parts of ion-exchanged water and 10 parts of emulsifier A. to prepare a monomer mixed emulsion.
撹拌機、温度計、還流コンデンサー付の１Ｌの四つ口丸底フラスコに、イオン交換水７０部、撹拌下に窒素置換しながら８０℃迄昇温した。そして、内温を８０℃に保ちながら、重合開始剤として過硫酸ナトリウム０．４部を添加し、溶解後、予め調製した単量体混合乳化物を約２時間かけて滴下、反応させた。更に８０℃で約２時間の熟成後、ＰＮＦ５０部を８０℃で保持して１時間かけて滴下した後に冷却した。５％水酸化ナトリウム水溶液で強アルカリ性域（ｐＨ１１以上）に調整し、撹拌後に１０％クエン酸水溶液で弱アルカリ性域（ｐＨ８以上１１未満）にし、凝集物を除去する目的で濾過をして、蒸発残分約３５％の複合樹脂組成物を得た。なお、本実施例は、ｐＨ調整で有機酸としてクエン酸を用いたが、これに限定されず、例えば、酢酸、リンゴ酸、乳酸、及びコハク酸を用いても良い。 Into a 1 L four-necked round-bottomed flask equipped with a stirrer, a thermometer and a reflux condenser, 70 parts of ion-exchanged water was stirred and the temperature was raised to 80° C. while substituting nitrogen. Then, while maintaining the internal temperature at 80° C., 0.4 part of sodium persulfate was added as a polymerization initiator, and after dissolution, the monomer mixed emulsion prepared in advance was added dropwise over about 2 hours to react. After aging at 80° C. for about 2 hours, 50 parts of PNF was added dropwise over 1 hour while maintaining the temperature at 80° C., and then cooled. Adjust to a strong alkaline range (pH 11 or higher) with a 5% aqueous sodium hydroxide solution, and after stirring, adjust to a weak alkaline range (pH 8 or higher and lower than 11) with a 10% aqueous citric acid solution, filter for the purpose of removing aggregates, and evaporate. A composite resin composition with a residue of about 35% was obtained. In this example, citric acid was used as an organic acid for pH adjustment, but the organic acid is not limited to this, and acetic acid, malic acid, lactic acid, and succinic acid, for example, may be used.
（ｐＨ調整）
上記のｐＨ調整（例えば、強アルカリ性域から弱アルカリ性域への調整）は、「高ｐＨ先ブレンド法」に相当し、単量体混合乳化物とＰＮＦ分散液とを均一に混合するために行われる。高ｐＨ先ブレンド法とは、単量体混合乳化物とＰＮＦ分散液とを混合した後に、分散液（複合樹脂組成物）に対しｐＨ調整することをいう。なお、高ｐＨ先ブレンド法ではなく後述の「高ｐＨ後ブレンド法」を用いて、複合樹脂組成物を製造しても良い。以下、高ｐＨ後ブレンド法と高ｐＨ先ブレンド法の詳細について説明する。
(pH adjustment)
The above pH adjustment (for example, adjustment from a strong alkaline range to a weakly alkaline range) corresponds to the "high pH pre-blending method" and is performed to uniformly mix the monomer mixed emulsion and the PNF dispersion. will be The high pH pre-blending method refers to adjusting the pH of the dispersion (composite resin composition) after mixing the monomer mixed emulsion and the PNF dispersion. The composite resin composition may be produced not by the high pH pre-blending method but by using the "high pH post-blending method" described below. Details of the high pH post-blending method and the high pH pre-blending method will be described below.
（ホットブレンド法）
従来、単量体混合乳化物とＰＮＦ分散液とを均一に混合させる方法として、「ホットブレンド法」が用いられていた。ホットブレンド法とは、ＰＮＦ分散液中で単量体混合乳化物の重合により生じる熱を利用し、分散液中の温度を上昇させることで、均一な複合樹脂組成物を得る方法のことをいう。
(Hot blend method)
Conventionally, a "hot blending method" has been used as a method for uniformly mixing a monomer mixed emulsion and a PNF dispersion. The hot blending method is a method of obtaining a uniform composite resin composition by utilizing the heat generated by the polymerization of the monomer mixture emulsion in the PNF dispersion to raise the temperature in the dispersion. .
（高ｐＨ後ブレンド法）
本発明では、より高均一な複合樹脂組成物を得るために、ＰＮＦ分散液のｐＨを強アルカリ性域（ｐＨ１１以上）に調製し、それを単量体混合乳化物と撹拌混合した後、ｐＨを中性域（ｐＨ６以上８未満）又は弱酸性域（ｐＨ３以上６未満）まで戻した。すると、溶解状態にあったＰＮＦが表出し、均一に分散した分散液（複合樹脂組成物）が得られることが判明した。このような工程で複合樹脂組成物を得る方法を「高ｐＨ後ブレンド法」と呼ぶ。高ｐＨ後ブレンド法で得られた複合樹脂組成物の分散性は、従来のホットブレンド法で得られる複合樹脂組成物よりも優れていた。なお、高ｐＨ後ブレンド法では、単量体混合乳化物のｐＨを、強アルカリ性域のＰＮＦ分散液のｐＨに合わせる必要があるため、製造工程数が増えるといった課題があった。
(Blending method after high pH)
In the present invention, in order to obtain a more uniform composite resin composition, the pH of the PNF dispersion is adjusted to a strongly alkaline range (pH 11 or higher), and after stirring and mixing it with the monomer mixed emulsion, the pH is adjusted. It was returned to a neutral range (pH 6 or more and less than 8) or a weak acid range (pH 3 or more and less than 6). As a result, it was found that the dissolved PNF was exposed and a uniformly dispersed dispersion (composite resin composition) was obtained. A method of obtaining a composite resin composition through such steps is called a “high pH post-blending method”. The dispersibility of the composite resin composition obtained by the high pH post-blending method was superior to that of the composite resin composition obtained by the conventional hot blending method. In addition, in the post-high-pH blending method, the pH of the monomer mixed emulsion must be adjusted to the pH of the PNF dispersion liquid in the strongly alkaline region, so there is a problem of an increase in the number of manufacturing steps.
（高ｐＨ先ブレンド法）
そこで、高ｐＨ後ブレンド法よりも製造工程数が少ない高ｐＨ先ブレンド法を用いて複合樹脂組成物を製造した。まず、単量体混合乳化物とＰＮＦ分散液とを混合した後に、複合樹脂組成物を強アルカリ性域になるまでｐＨを上げて、再び中性域（ｐＨ６以上８未満）又は弱酸性域（ｐＨ３以上６未満）までｐＨを下げた。すると、高ｐＨ後ブレンド法と同様に、高ｐＨ先ブレンド法を用いても高均一な複合樹脂組成物が得られることが判明した。
(High pH pre-blend method)
Therefore, a composite resin composition was produced using the high pH pre-blending method, which has fewer production steps than the high pH post-blending method. First, after mixing the monomer mixed emulsion and the PNF dispersion, the pH of the composite resin composition is increased to a strong alkaline range, and again the neutral range (pH 6 or more and less than 8) or weakly acidic range (pH 3 The pH was lowered to less than 6). As a result, it was found that a highly uniform composite resin composition can be obtained by using the high pH pre-blending method as well as the high pH post-blending method.
（実施例１３）
実施例１２に準じて、表１に示した通り、所定の原料と高ｐＨ先ブレンド法を用いて複合樹脂組成物を調製した。
(Example 13)
According to Example 12, as shown in Table 1, a composite resin composition was prepared using predetermined raw materials and a high pH pre-blending method.
・メチルメタクリレート（ＭＭＡ）、スチレン（ＳＴ）、２－エチルヘキシルアクリレート（２ＥＨＡ）、ブチルアクリレート（ＢＡ）、メタクリル酸２ヒドロキシエチル（２ＨＥＭＡ）、メタクリル酸（ＭＡＡＣ）、アクリル酸（ＡＡＣ）
・ＰＮＦ：ミドリムシ由来パラミロンナノファイバー（ユーグリード社製、商品名：パラミロンナノファイバー（２％））
・ＣＮＦ１：機械解繊タイプセルロースナノファイバー（スギノマシン社製、商品名：ビンフィス（２％））
・ＣＮＦ２：化学解繊（ＴＥＭＰＯ酸化）タイプのセルロースナノファイバー（日本製紙社製、商品名：セレンピア（１％））
・ PNF: Euglena-derived paramylon nanofiber (manufactured by Uglied, trade name: paramylon nanofiber (2%))
・CNF1: Mechanical defibration type cellulose nanofiber (manufactured by Sugino Machine, trade name: Binfis (2%))
・ CNF2: Chemical fibrillation (TEMPO oxidation) type cellulose nanofiber (manufactured by Nippon Paper Industries, trade name: Celenpia (1%))
・メチルメタクリレート（ＭＭＡ）、スチレン（ＳＴ）、２－エチルヘキシルアクリレート（２ＥＨＡ）、ブチルアクリレート（ＢＡ）、メタクリル酸２ヒドロキシエチル（２ＨＥＭＡ）、メタクリル酸（ＭＡＡＣ）、アクリル酸（ＡＡＣ）
・ＰＮＦ：ミドリムシ由来パラミロンナノファイバー（ユーグリード社製、商品名：パラミロンナノファイバー（２％））
・ＣＮＦ１：機械解繊タイプセルロースナノファイバー（スギノマシン社製、商品名：ビンフィス（２％））
・ＣＮＦ２：化学解繊（ＴＥＭＰＯ酸化）タイプのセルロースナノファイバー（日本製紙社製、商品名：セレンピア（１％））
・ PNF: Euglena-derived paramylon nanofiber (manufactured by Uglied, trade name: paramylon nanofiber (2%))
・CNF1: Mechanical defibration type cellulose nanofiber (manufactured by Sugino Machine, trade name: Binfis (2%))
・ CNF2: Chemical fibrillation (TEMPO oxidation) type cellulose nanofiber (manufactured by Nippon Paper Industries, trade name: Celenpia (1%))
＜複合樹脂組成物の性能評価＞
以下の試験例１と試験例２を行い、実施例１～１３の複合樹脂組成物、比較例１～２の複合樹脂組成物、及び参考例１～６の樹脂組成物（単量体混合乳化物に相当）の性能評価を行った。
<Performance evaluation of composite resin composition>
The following Test Examples 1 and 2 were performed, and the composite resin compositions of Examples 1 to 13, the composite resin compositions of Comparative Examples 1 and 2, and the resin compositions of Reference Examples 1 to 6 (monomer mixed emulsification (equivalent to a product) was evaluated.
（試験例１ 複合安定性試験）
１２０メッシュのフィルターで単量体混合乳化物エマルション又は複合樹脂組成物エマルションを濾過したときに残存する凝集物の有無を、以下の評価基準に基づいて目視で評価した。
（評価基準）
○・・・残存凝集物なし
△・・・多少の残存凝集物あり
×・・・凝集物が多い
(Test Example 1 Combined stability test)
The existence or non-existence of aggregates remaining when the monomer mixture emulsion or the composite resin composition emulsion was filtered through a 120-mesh filter was visually evaluated based on the following evaluation criteria.
(Evaluation criteria)
○: no residual aggregates △: some residual aggregates ×: many aggregates
（試験例２ 皮膜強伸度試験）
複合安定性試験で調整した弱アルカリ性の複合樹脂組成物エマルションを任意の基材に塗布して、７０℃で１６時間加熱乾燥した。その後、幅×長さ×厚さ＝１０ｍｍ×１０ｍｍ×０．３０ｍｍのサイズに加工して試料皮膜を得た。所定の条件（チャック間距離：２０ｍｍ、引張速度：２００ｍｍ／ｍｉｎ、測定雰囲気：２３℃・５０％ＲＨ）でテンシロン万能引張試験機を用いて試料皮膜の力学特性(皮膜強度及び皮膜伸度)を測定した。
(Test Example 2 Film strength and elongation test)
The weakly alkaline composite resin composition emulsion prepared in the composite stability test was applied to an arbitrary substrate and dried by heating at 70° C. for 16 hours. After that, it was processed into a size of width×length×thickness=10 mm×10 mm×0.30 mm to obtain a sample film. The mechanical properties (film strength and film elongation) of the sample film were measured using a Tensilon universal tensile tester under predetermined conditions (distance between chucks: 20 mm, tensile speed: 200 mm/min, measurement atmosphere: 23°C, 50% RH). It was measured.
実施例１～１３の評価結果を表３に示す。参考例１～６及び比較例１、２の評価結果を表４に示す。また、ＰＮＦ配合の有無による複合樹脂組成物の機械特性に及ぼす効果を確認するために、実施例５～８、１１～１３、及び、参考例１～３、６を、単量体配合量毎に対応するように対比した結果を表５に示す。 Table 3 shows the evaluation results of Examples 1 to 13. Table 4 shows the evaluation results of Reference Examples 1 to 6 and Comparative Examples 1 and 2. In addition, in order to confirm the effect of the presence or absence of PNF blending on the mechanical properties of the composite resin composition, Examples 5 to 8, 11 to 13, and Reference Examples 1 to 3, 6 were tested for each monomer blend amount. Table 5 shows the results of the corresponding comparison.
表３と表４の比較から以下の結果が判明した。実施例１の複合安定性（凝集物の有無）は、比較例１（ＣＮＦ１配合）と比較例２（ＣＮＦ２配合）よりも向上した。 A comparison of Tables 3 and 4 revealed the following results. The composite stability (presence or absence of aggregates) of Example 1 was improved compared to Comparative Example 1 (CNF1 formulation) and Comparative Example 2 (CNF2 formulation).
表５から以下の結果が判明した。 Table 5 revealed the following results.
実施例５の最大皮膜強度（ＭＰａ）は、参考例１（ＣＮＦ及びＰＮＦ非含有）よりも向上した。また、実施例５の初期皮膜強度（（ＭＰａ）、５０％～２００％伸度）は、参考例１よりも顕著に向上した。 The maximum film strength (MPa) of Example 5 was improved over that of Reference Example 1 (CNF and PNF not included). In addition, the initial film strength ((MPa), 50% to 200% elongation) of Example 5 was significantly improved over that of Reference Example 1.
実施例６の最大皮膜強度（ＭＰａ）は、参考例２（ＣＮＦ及びＰＮＦ非含有）よりも向上した。また、実施例６の初期皮膜強度（（ＭＰａ）、５０％～２００％伸度）は、参考例２よりも向上した。 The maximum film strength (MPa) of Example 6 was improved over that of Reference Example 2 (CNF and PNF not included). In addition, the initial film strength ((MPa), 50% to 200% elongation) of Example 6 was improved over that of Reference Example 2.
実施例７、８、１２、１３の最大皮膜強度（ＭＰａ）は、参考例３（ＣＮＦ及びＰＮＦ非含有）よりも向上した。また、実施例７、８、１２、１３の初期皮膜強度（（ＭＰａ）、５０％～２００％伸度）は、参考例３よりも向上した。特に、実施例１３の最大皮膜強度（ＭＰａ）及び初期皮膜強度（（ＭＰａ）、５０％～２００％伸度）は、参考例３よりも顕著に向上した。 The maximum film strength (MPa) of Examples 7, 8, 12, and 13 was improved over that of Reference Example 3 (containing no CNF and PNF). In addition, the initial film strength ((MPa), 50% to 200% elongation) of Examples 7, 8, 12, and 13 was higher than that of Reference Example 3. In particular, the maximum film strength (MPa) and initial film strength ((MPa), 50% to 200% elongation) of Example 13 were significantly improved compared to Reference Example 3.
実施例１１の最大皮膜強度（ＭＰａ）は、参考例６（ＣＮＦ及びＰＮＦ非含有）よりも向上した。また、実施例１１の初期皮膜強度（（ＭＰａ）、５０％～２００％伸度）は、参考例６よりも顕著に向上した。 The maximum film strength (MPa) of Example 11 was improved over that of Reference Example 6 (containing no CNF and PNF). In addition, the initial film strength ((MPa), 50% to 200% elongation) of Example 11 was significantly improved over that of Reference Example 6.
以上の通り、本発明の複合樹脂組成物は、樹脂粒子層の力学特性を向上させる顕著な効果を有する。 As described above, the composite resin composition of the present invention has a remarkable effect of improving the mechanical properties of the resin particle layer.
発明は上記の実施形態に制限されるものではなく、発明の要旨の範囲内で、種々の変形・変更が可能である。 The invention is not limited to the above embodiments, and various modifications and changes are possible within the scope of the invention.
Claims (9)
前記水不溶性重合体粒子の１００質量部に対して、前記エチレン性不飽和単量体として（メタ）アクリル系単量体、スチレン系単量体、及び（メタ）アクリロニトリル系単量体の少なくともいずれかを５０質量部以上含む、
ことを特徴とする複合樹脂組成物。 Water-insoluble polymer particles made of ethylenically unsaturated monomers, paramylon nanofibers, and an aqueous dispersion medium ,
At least one of a (meth)acrylic monomer, a styrene monomer, and a (meth)acrylonitrile monomer as the ethylenically unsaturated monomer per 100 parts by mass of the water-insoluble polymer particles. containing 50 parts by mass or more of
A composite resin composition characterized by:
ことを特徴とする請求項１に記載の複合樹脂組成物。 10 to 500 parts by mass of the paramylon nanofibers per 100 parts by mass of the water-insoluble polymer particles,
The composite resin composition according to claim 1, characterized by:
ことを特徴とする請求項１に記載の複合樹脂組成物。 The paramylon nanofiber is contained in an amount of 0.1 to 10% by mass with respect to the composite resin composition,
The composite resin composition according to claim 1, characterized by:
ことを特徴とする請求項１に記載の複合樹脂組成物。 The paramylon nanofibers have an aspect ratio of 1:300 to 1:10000,
The composite resin composition according to claim 1, characterized by:
ことを特徴とする請求項１に記載の複合樹脂組成物の製造方法。 polymerizing the ethylenically unsaturated monomer in an aqueous dispersion medium containing the paramylon nanofibers;
The method for producing a composite resin composition according to claim 1, characterized in that:
ことを特徴とする請求項５に記載の製造方法。 Further adding the paramylon nanofibers after polymerizing the ethylenically unsaturated monomers;
6. The manufacturing method according to claim 5 , characterized in that:
ことを特徴とする請求項１に記載の複合樹脂組成物の製造方法。 mixing an aqueous dispersion medium containing water-insoluble polymer particles made of an ethylenically unsaturated monomer and an aqueous dispersion medium containing the paramylon nanofibers;
The method for producing a composite resin composition according to claim 1, characterized in that:
ことを特徴とする請求項７に記載の製造方法。 After adjusting a dispersion liquid containing an aqueous dispersion medium containing water-insoluble polymer particles composed of the ethylenically unsaturated monomer and an aqueous dispersion medium containing the paramylon nanofibers to a strongly alkaline range, the dispersion Adjusting the pH of the liquid to either a weakly alkaline range, a neutral range, or a weakly acidic range,
The manufacturing method according to claim 7 , characterized in that:
ことを特徴とする請求項１に記載の複合樹脂組成物の製造方法。 After adjusting the aqueous dispersion medium containing the paramylon nanofibers to a strongly alkaline range, adjusting the aqueous dispersion medium containing the water-insoluble polymer particles composed of the ethylenically unsaturated monomer to the strongly alkaline range, A dispersion containing an aqueous dispersion medium containing the paramylon nanofibers in the strongly alkaline range and an aqueous dispersion medium containing the water-insoluble polymer particles composed of the ethylenically unsaturated monomer in the strongly alkaline range is mixed. and adjusting the pH of the dispersion to any of a weakly alkaline range, a neutral range, and a weakly acidic range;
The method for producing a composite resin composition according to claim 1, characterized in that:
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| JPH02277545A (en) * | 1989-01-19 | 1990-11-14 | Takeda Chem Ind Ltd | Activated carbon composition for molding and molded material of activated carbon |
| JP2013091716A (en) * | 2011-10-26 | 2013-05-16 | Kri Inc | Paramylon granule-containing composite body |
| WO2018116936A1 (en) * | 2016-12-19 | 2018-06-28 | 株式会社神鋼環境ソリューション | Fibrilized paramylon, additive, and method for producing additive |
| JP2018141904A (en) * | 2017-02-28 | 2018-09-13 | 国立研究開発法人産業技術総合研究所 | Optical film and method for manufacturing the same |
| JP2021031785A (en) * | 2019-08-20 | 2021-03-01 | 株式会社ユーグレナ | Paramylum-containing rayon fiber and method of producing paramylum-containing rayon fiber |
| WO2021225172A1 (en) * | 2020-05-08 | 2021-11-11 | 日本電気株式会社 | Paramylon-based resin, molding material, molded body, and production method for paramylon-based resin |
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2022
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02277545A (en) * | 1989-01-19 | 1990-11-14 | Takeda Chem Ind Ltd | Activated carbon composition for molding and molded material of activated carbon |
| JP2013091716A (en) * | 2011-10-26 | 2013-05-16 | Kri Inc | Paramylon granule-containing composite body |
| WO2018116936A1 (en) * | 2016-12-19 | 2018-06-28 | 株式会社神鋼環境ソリューション | Fibrilized paramylon, additive, and method for producing additive |
| JP2018141904A (en) * | 2017-02-28 | 2018-09-13 | 国立研究開発法人産業技術総合研究所 | Optical film and method for manufacturing the same |
| JP2021031785A (en) * | 2019-08-20 | 2021-03-01 | 株式会社ユーグレナ | Paramylum-containing rayon fiber and method of producing paramylum-containing rayon fiber |
| WO2021225172A1 (en) * | 2020-05-08 | 2021-11-11 | 日本電気株式会社 | Paramylon-based resin, molding material, molded body, and production method for paramylon-based resin |
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