JP6471013B2 - Anionic surfactant composition for emulsion polymerization - Google Patents
Anionic surfactant composition for emulsion polymerization Download PDFInfo
- Publication number
- JP6471013B2 JP6471013B2 JP2015062761A JP2015062761A JP6471013B2 JP 6471013 B2 JP6471013 B2 JP 6471013B2 JP 2015062761 A JP2015062761 A JP 2015062761A JP 2015062761 A JP2015062761 A JP 2015062761A JP 6471013 B2 JP6471013 B2 JP 6471013B2
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- mass
- internal olefin
- component
- emulsion
- surfactant composition
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- 239000000203 mixture Substances 0.000 title claims description 124
- 238000007720 emulsion polymerization reaction Methods 0.000 title claims description 39
- 239000003945 anionic surfactant Substances 0.000 title claims description 27
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 149
- 150000001336 alkenes Chemical class 0.000 claims description 111
- 239000000839 emulsion Substances 0.000 claims description 81
- 239000011248 coating agent Substances 0.000 claims description 79
- 238000000576 coating method Methods 0.000 claims description 79
- -1 olefin sulfonate Chemical class 0.000 claims description 73
- 239000002994 raw material Substances 0.000 claims description 72
- 125000004432 carbon atom Chemical group C* 0.000 claims description 60
- 229920000642 polymer Polymers 0.000 claims description 56
- 238000004519 manufacturing process Methods 0.000 claims description 50
- 239000003925 fat Substances 0.000 claims description 24
- 239000003921 oil Substances 0.000 claims description 24
- 239000008199 coating composition Substances 0.000 claims description 20
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 16
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 description 70
- 239000010408 film Substances 0.000 description 60
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 53
- 238000006116 polymerization reaction Methods 0.000 description 42
- 239000000126 substance Substances 0.000 description 37
- 239000002245 particle Substances 0.000 description 35
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- 238000006277 sulfonation reaction Methods 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 17
- 239000000049 pigment Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 14
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- 238000004817 gas chromatography Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 13
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000006386 neutralization reaction Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 235000014113 dietary fatty acids Nutrition 0.000 description 11
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- 229930195729 fatty acid Natural products 0.000 description 11
- 150000004665 fatty acids Chemical class 0.000 description 11
- 238000009826 distribution Methods 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 9
- 239000010409 thin film Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 8
- BTFJIXJJCSYFAL-UHFFFAOYSA-N icosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 8
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000004711 α-olefin Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 6
- 239000003346 palm kernel oil Substances 0.000 description 6
- 235000019865 palm kernel oil Nutrition 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000003240 coconut oil Substances 0.000 description 5
- 235000019864 coconut oil Nutrition 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 229960000541 cetyl alcohol Drugs 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 238000003756 stirring Methods 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 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000005262 decarbonization Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
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- 238000004945 emulsification Methods 0.000 description 2
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- QJPQVXSHYBGQGM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QJPQVXSHYBGQGM-UHFFFAOYSA-N 0.000 description 2
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- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
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- OQKFGIANPCRSSK-UHFFFAOYSA-N azanium;methanol;acetate Chemical compound [NH4+].OC.CC([O-])=O OQKFGIANPCRSSK-UHFFFAOYSA-N 0.000 description 1
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- 239000002270 dispersing agent Substances 0.000 description 1
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- 239000002655 kraft paper Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
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- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
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Description
本発明は、乳化重合用アニオン性界面活性剤組成物、及びこれを用いるポリマーエマルションの製造方法等に関する。 The present invention relates to an anionic surfactant composition for emulsion polymerization, a method for producing a polymer emulsion using the same, and the like.
ポリマーエマルションは、酢酸ビニル、（メタ）アクリル酸エステル、スチレン及びその誘導体等のビニル系モノマーの乳化重合によって得られ、そのまま塗料、粘着剤、接着剤、紙加工、繊維加工等の分野に、あるいは重合体が分離されてプラスチック、ゴムとして広く工業的に使用されている。
乳化重合には乳化剤として、直鎖アルキル硫酸エステル塩、直鎖アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩、ポリオキシエチレンアルキルエーテル硫酸エステル塩、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩等のアニオン性界面活性剤、及びポリオキシエチレン直鎖アルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル等の非イオン性界面活性剤が使用されている。
乳化重合における乳化剤は、重合の開始反応、生長反応に影響を及ぼすのみでなく、重合中のポリマーエマルションの安定性（以下、「重合安定性」ともいう）、さらに生成したポリマーエマルションの機械的安定性、化学的安定性に大きな影響を及ぼす。そのため、乳化重合用界面活性剤に要求される性能は、重合安定性、化学的安定性が良好で、ポリマーエマルションの粒径が小さく、さらには環境負荷が小さいことである。
従来、乳化重合用界面活性剤としては、環境への負荷が小さく、重合安定性、化学的安定性に優れる、ポリオキシエチレンアルキルエーテル硫酸エステル塩が汎用的に使用されている。例えば、ポリ塩化ビニル、ＳＢラテックスの製造においては、依然として、石油化学原料由来の直鎖アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩が多量に使用されている。
The polymer emulsion is obtained by emulsion polymerization of vinyl monomers such as vinyl acetate, (meth) acrylic acid ester, styrene and derivatives thereof, and is used as it is in the fields of paints, adhesives, adhesives, paper processing, fiber processing, or the like. The polymer is separated and widely used industrially as plastic and rubber.
In emulsion polymerization, as an emulsifier, an anionic interface such as linear alkyl sulfate salt, linear alkyl benzene sulfonate, alkyl diphenyl ether disulfonate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, etc. Activators and nonionic surfactants such as polyoxyethylene linear alkyl ethers and polyoxyethylene alkylphenyl ethers are used.
Emulsifiers in emulsion polymerization not only affect the initiation and growth reactions of polymerization, but also the stability of the polymer emulsion during polymerization (hereinafter also referred to as “polymerization stability”), and the mechanical stability of the polymer emulsion produced. It has a great influence on the chemical and chemical stability. Therefore, the performance required for the surfactant for emulsion polymerization is that the polymerization stability and chemical stability are good, the particle size of the polymer emulsion is small, and the environmental load is small.
Conventionally, as a surfactant for emulsion polymerization, a polyoxyethylene alkyl ether sulfate salt that has a low environmental load and is excellent in polymerization stability and chemical stability has been used for a wide variety of purposes. For example, in the production of polyvinyl chloride and SB latex, a large amount of linear alkylbenzene sulfonate and alkyldiphenyl ether disulfonate derived from petrochemical raw materials are still used.
特許文献１には、石油化学原料由来の分岐アルコールを原料としたポリオキシアルキレンアルキルエーテルから誘導されたアニオン性界面活性剤を含有する乳化重合用乳化剤が開示されている。
特許文献２には、疎水基が脂肪族アルコール残基である乳化重合用乳化剤として、オキソ法によって合成された炭素数１３のアルコールに、アルキレンオキサイドを付加してなるエーテル型の非イオン又はアニオン性界面活性剤が開示されている。
Patent Document 1 discloses an emulsifier for emulsion polymerization containing an anionic surfactant derived from a polyoxyalkylene alkyl ether using a branched alcohol derived from a petrochemical raw material as a raw material.
Patent Document 2 discloses an ether-type nonionic or anionic property obtained by adding an alkylene oxide to an alcohol having 13 carbon atoms synthesized by an oxo method as an emulsifier for emulsion polymerization in which a hydrophobic group is an aliphatic alcohol residue. Surfactants are disclosed.
近年、カーボンニュートラルという観点から、乳化重合用界面活性剤の製造においても、植物油脂等の天然油脂由来の原料の使用が求められている。
天然油脂由来の界面活性剤としては、天然アルコール由来の高級アルコール硫酸エステル塩、天然アルコールにエチレンオキサイドを付加した後、硫酸化して得られるポリオキシエチレンアルキル硫酸エステル塩が挙げられる。
しかしながら、高級アルコール硫酸エステル塩はクラフト点が高く、十分な機械的安定性及び化学的安定性が得られず、該アルキル硫酸エステル塩を用いて得られるポリマーエマルションを塗料に使用した場合、塗膜光沢、及び塗膜密着性に対する要求を満たすことができない。
また、ポリオキシエチレンアルキル硫酸エステル塩は石油化学原料のエチレンオキサイドを使用するため天然植物原料化率が低く、また該硫酸エステル塩は酸性条件下で加水分解しやすいという問題がある。そのため、環境への影響を考慮し、生分解性が良好で、ジオキサン及びアルデヒドの生成原因となるアルキレンオキサイドを使用しない乳化重合用界面活性剤が求められている。
In recent years, from the viewpoint of carbon neutral, the use of raw materials derived from natural fats and oils such as vegetable fats and oils is also required in the production of surfactants for emulsion polymerization.
Examples of the surfactant derived from natural fats and oils include higher alcohol sulfates derived from natural alcohols, and polyoxyethylene alkyl sulfates obtained by adding ethylene oxide to natural alcohols and then sulfating.
However, the higher alcohol sulfate ester salt has a high Kraft point, and sufficient mechanical stability and chemical stability cannot be obtained. When a polymer emulsion obtained using the alkyl sulfate ester salt is used as a coating, The demand for gloss and coating film adhesion cannot be satisfied.
In addition, since polyoxyethylene alkyl sulfate salts use ethylene oxide, which is a petrochemical raw material, the rate of conversion to natural plant raw materials is low, and the sulfate salts are prone to hydrolysis under acidic conditions. Therefore, in consideration of the influence on the environment, there is a demand for a surfactant for emulsion polymerization that has good biodegradability and does not use alkylene oxide that causes generation of dioxane and aldehyde.
本発明は、天然油脂由来の原料から得られ、かつ、重合安定性及びポリマーエマルションの粒径が良好で、機械的安定性及び化学的安定性に優れ、塗膜光沢、及び塗膜密着性に優れるポリマーエマルションを製造することができる乳化重合用アニオン性界面活性剤組成物、これを用いるポリマーエマルションの製造方法、ポリマーエマルション、塗料組成物及びポリマー塗膜を提供することを課題とする。 The present invention is obtained from a raw material derived from natural fats and oils, and has good polymerization stability and polymer emulsion particle size, excellent mechanical stability and chemical stability, coating film gloss, and coating film adhesion. It is an object of the present invention to provide an anionic surfactant composition for emulsion polymerization capable of producing an excellent polymer emulsion, a method for producing a polymer emulsion using the composition, a polymer emulsion, a coating composition, and a polymer coating film.
本発明者は、ポリマーエマルションの製造に際して、特定の化合物を特定量含有する乳化重合用アニオン性界面活性剤組成物を用いることにより、前記の課題を解決しうることを見出した。
すなわち、本発明は、次の［１］〜［５］を提供する。
［１］（ａ）成分：炭素数１２以上２２以下のヒドロキシアルカンスルホン酸塩、（ｂ）成分：炭素数１２以上２２以下の内部オレフィンスルホン酸塩、及び（ｃ）成分：炭素数１２以上２２以下の内部オレフィンを含有する乳化重合用アニオン性界面活性剤組成物であって、（ａ）成分と（ｂ）成分の合計１００質量部に対して、（ｃ）成分を０．１質量部以上３質量部以下含有する、乳化重合用アニオン性界面活性剤組成物。
［２］前記［１］に記載の乳化重合用アニオン性界面活性剤組成物の存在下、ラジカル重合可能なモノマーを乳化重合する、ポリマーエマルションの製造方法。
［３］前記［２］の製造方法により得られる、ポリマーエマルション。
［４］前記［３］に記載のポリマーエマルションを含有する、塗料組成物。
［５］前記［４］に記載の塗料組成物を、基板に塗布し、乾燥して形成されるポリマー塗膜。
The present inventor has found that the above-mentioned problems can be solved by using an anionic surfactant composition for emulsion polymerization containing a specific amount of a specific compound in the production of a polymer emulsion.
That is, the present invention provides the following [1] to [5].
[1] (a) Component: Hydroxyalkanesulfonate having 12 to 22 carbon atoms, (b) Component: Internal olefin sulfonate having 12 to 22 carbon atoms, and (c) Component: 12 to 22 carbon atoms An anionic surfactant composition for emulsion polymerization containing the following internal olefin, wherein (c) component is 0.1 parts by mass or more with respect to 100 parts by mass in total of component (a) and component (b) An anionic surfactant composition for emulsion polymerization, containing 3 parts by mass or less.
[2] A method for producing a polymer emulsion, comprising subjecting a radical polymerizable monomer to emulsion polymerization in the presence of the anionic surfactant composition for emulsion polymerization according to [1].
[3] A polymer emulsion obtained by the production method of [2].
[4] A coating composition containing the polymer emulsion according to [3].
[5] A polymer coating film formed by applying the coating composition according to [4] to a substrate and drying.
本発明によれば、天然油脂由来の原料から得られ、かつ、重合安定性及びポリマーエマルションの粒径が良好で、機械的安定性、化学的安定性、塗膜光沢、及び塗膜密着性に優れるポリマーエマルションを製造できる乳化重合用アニオン性界面活性剤組成物、これを用いるポリマーエマルションの製造方法、ポリマーエマルション、塗料組成物及びポリマー塗膜を提供することができる。 According to the present invention, it is obtained from a raw material derived from natural fats and oils, the polymerization stability and the particle size of the polymer emulsion are good, and the mechanical stability, chemical stability, coating film gloss, and coating film adhesion are improved. An anionic surfactant composition for emulsion polymerization capable of producing an excellent polymer emulsion, a method for producing a polymer emulsion using the composition, a polymer emulsion, a coating composition, and a polymer coating film can be provided.
＜乳化重合用アニオン性界面活性剤組成物＞
本発明の乳化重合用アニオン性界面活性剤組成物（以下、単に「界面活性剤組成物」ともいう）は、（ａ）成分：炭素数１２以上２２以下のヒドロキシアルカンスルホン酸塩（以下、単に「（ａ）成分ともいう」）、（ｂ）成分：炭素数１２以上２２以下の内部オレフィンスルホン酸塩（以下、単に「（ｂ）成分ともいう」）、及び（ｃ）成分：炭素数１２以上２２以下の内部オレフィン（以下、単に「（ｃ）成分ともいう」）を含有する乳化重合用アニオン性界面活性剤組成物であって、（ａ）成分と（ｂ）成分の合計１００質量部に対して、（ｃ）成分を０．１質量部以上３質量部以下含有する。
内部オレフィンとは、二重結合をオレフィン鎖の内部に有するオレフィンであり、二重結合の位置が炭素鎖の１位に存在する、いわゆるα−オレフィンを微量に含有する場合も含む広義の意味である。
内部オレフィンをスルホン化すると、定量的にβ−サルトンが生成し、β−サルトンの一部は、γ−サルトン、オレフィンスルホン酸へと変化し、更にこれらは中和及び加水分解工程により、ヒドロキシアルカンスルホン酸塩と、内部オレフィンスルホン酸塩へと転換される。ここで、得られるヒドロキシアルカンスルホン酸塩のヒドロキシ基は、アルカン鎖の内部にあり、内部オレフィンスルホン酸塩の二重結合はオレフィン鎖の内部にある。
得られる生成物は、主にこれらの混合物であり、原料の内部オレフィン（以下、単に「原料内部オレフィン」ともいう）が微量に含まれる場合もある。
<Anionic surfactant composition for emulsion polymerization>
The anionic surfactant composition for emulsion polymerization of the present invention (hereinafter also simply referred to as “surfactant composition”) is composed of component (a): a hydroxyalkane sulfonate having 12 to 22 carbon atoms (hereinafter simply referred to as “a surfactant composition”). (Also referred to as “component (a)”), component (b): internal olefin sulfonate having 12 to 22 carbon atoms (hereinafter also simply referred to as “component (b)”), and component (c): carbon number 12 An anionic surfactant composition for emulsion polymerization containing an internal olefin of 22 or less (hereinafter also simply referred to as “component (c)”), and a total of 100 parts by mass of component (a) and component (b) In contrast, the component (c) is contained in an amount of 0.1 to 3 parts by mass.
The internal olefin is an olefin having a double bond inside the olefin chain, and has a broad meaning including a case where a so-called α-olefin is contained in a trace amount in which the position of the double bond is located at the 1st position of the carbon chain. is there.
When the internal olefin is sulfonated, β-sultone is quantitatively produced, and a part of β-sultone is converted into γ-sultone and olefin sulfonic acid, and these are further converted into hydroxyalkane by neutralization and hydrolysis steps. Converted to sulfonate and internal olefin sulfonate. Here, the hydroxy group of the resulting hydroxyalkanesulfonate is inside the alkane chain, and the double bond of the internal olefinsulfonate is inside the olefin chain.
The resulting product is mainly a mixture thereof, and may contain a trace amount of raw internal olefin (hereinafter also simply referred to as “raw internal olefin”).
本明細書において、「重合安定性が良好である」とは、製造されたポリマーエマルション（以下、単に「エマルション」ともいう）中に凝集物が少ないことをいう。重合安定性は、具体的には実施例に記載される方法で、評価することができる。
本明細書において、「エマルション粒径が良好である」とは、製造されたエマルションの平均粒径が大きくならないこと、すなわち小さいことをいう。具体的には、実施例の乳化重合方法において、エマルションの平均粒径が１００ｎｍ以上３００ｎｍ以下であることをいう。エマルションの平均粒径は、動的光散乱法において検出角９０度で測定される散乱強度分布に基づく平均粒径をいい、具体的には実施例に記載される方法で測定することができる。
本明細書において、「化学的安定性が優れる」とは、製造されたエマルションの耐二価金属凝集性のことをいい、具体的には、０．１質量％ＣａＣｌ２水溶液とポリマーエマルションを混合しても、凝集物を生じないことをいう。化学的安定性は、実施例に記載される方法で評価することができる。
In this specification, “good polymerization stability” means that there are few aggregates in the produced polymer emulsion (hereinafter also simply referred to as “emulsion”). Specifically, the polymerization stability can be evaluated by the method described in Examples.
In this specification, “emulsion particle size is good” means that the average particle size of the produced emulsion does not increase, that is, is small. Specifically, in the emulsion polymerization method of the examples, it means that the average particle size of the emulsion is 100 nm or more and 300 nm or less. The average particle diameter of the emulsion refers to the average particle diameter based on the scattering intensity distribution measured at a detection angle of 90 degrees in the dynamic light scattering method, and can be specifically measured by the method described in the examples.
In this specification, “excellent chemical stability” refers to the divalent metal aggregation resistance of the produced emulsion. Specifically, a 0.1 mass% CaCl 2 aqueous solution and a polymer emulsion are mixed. Even if it does not produce an aggregate. Chemical stability can be evaluated by the method described in the examples.
本発明によれば、乳化重合において、（ａ）成分：炭素数１２以上２２以下のヒドロキシアルカンスルホン酸塩、（ｂ）成分：炭素数１２以上２２以下の内部オレフィンスルホン酸塩、及び（ｃ）成分：炭素数１２以上２２以下の内部オレフィンを特定の比率で含有する界面活性剤組成物を用いることにより、重合安定性及びエマルション粒径が良好で、機械的安定性、化学的安定性、塗膜光沢、及び塗膜密着性に優れるポリマーエマルションを製造することができる。その理由は定かではないが、以下のように考えられる。
一般的に、炭素数が１２以上２２以下の内部オレフィンスルホン酸塩を含有すると、得られるエマルションの粒径が小さくなり、重合安定性が低下する。
そこで、本発明は、ヒドロキシアルカンスルホン酸塩及び内部オレフィンスルホン酸塩の合計含有量に対して、内部オレフィンの含有量を特定の比率とすることにより、得られるエマルションの粒径はやや大きくなるものの、重合安定性を改善する効果が発現する。また、ヒドロキシアルカンスルホン酸塩は、含まれる水酸基により、良好な化学的安定性を向上させる効果を発現させる。
これらの効果が相乗的に作用し、重合安定性及びエマルションの粒径が良好で、機械的安定性、化学的安定性、塗膜光沢、及び塗膜密着性に優れる効果が発現すると考えられる。
According to the present invention, in emulsion polymerization, (a) component: hydroxyalkane sulfonate having 12 to 22 carbon atoms, (b) component: internal olefin sulfonate having 12 to 22 carbon atoms, and (c) Component: By using a surfactant composition containing an internal olefin having 12 to 22 carbon atoms in a specific ratio, the polymerization stability and emulsion particle size are good, and the mechanical stability, chemical stability, coating A polymer emulsion excellent in film gloss and coating film adhesion can be produced. The reason is not clear, but it is thought as follows.
Generally, when an internal olefin sulfonate having 12 or more and 22 or less carbon atoms is contained, the particle size of the resulting emulsion becomes small and the polymerization stability is lowered.
Therefore, the present invention has a specific ratio of the content of internal olefin to the total content of hydroxyalkane sulfonate and internal olefin sulfonate, but the resulting emulsion has a slightly larger particle size. The effect of improving the polymerization stability is exhibited. Further, the hydroxyalkanesulfonate exhibits an effect of improving good chemical stability due to the hydroxyl group contained therein.
It is considered that these effects act synergistically, the polymerization stability and emulsion particle size are good, and the effects of excellent mechanical stability, chemical stability, coating film gloss, and coating film adhesion are exhibited.
［（ａ）成分：炭素数１２以上２２以下のヒドロキシアルカンスルホン酸塩］
本発明の乳化重合用アニオン性界面活性剤組成物は、（ａ）成分として、炭素数１２以上２２以下のヒドロキシアルカンスルホン酸塩を含有する。
本発明に用いるヒドロキシアルカンスルホン酸塩の炭素数は、エマルションの平均粒径を小さくし、重合安定性、機械的安定性、化学的安定性、塗膜光沢、及び塗膜密着性の観点から、１２以上であり、好ましくは１４以上、より好ましくは１６以上であり、そして、重合安定性、機械的安定性、化学的安定性、塗膜光沢、及び塗膜密着性の観点から、２２以下であり、好ましくは２０以下、より好ましくは１８以下である。
本発明において（ａ）成分は、炭素数１２以上２２以下に分布を有するヒドロキシアルカンスルホン酸塩であってもよく、単一の炭素数である炭素数１２以上２２以下のヒドロキシアルカンスルホン酸塩であってもよい。また、異なる炭素数を有する２種以上の炭素数の炭素数１２以上２２以下のヒドロキシアルカンスルホン酸塩であってもよい。
なお、炭素数１２以上２２以下に分布を有するヒドロキシアルカンスルホン酸塩とは、（ａ）成分中、炭素数１２以上２２以下のヒドロキシアルカンスルホン酸塩の含有量が８０質量％以上のものをいい、好ましくは９０質量％以上、より好ましくは９５質量％以上である。
[(A) component: hydroxyalkane sulfonate having 12 to 22 carbon atoms]
The anionic surfactant composition for emulsion polymerization of the present invention contains a hydroxyalkanesulfonate having 12 to 22 carbon atoms as the component (a).
The number of carbon atoms of the hydroxyalkane sulfonate used in the present invention reduces the average particle size of the emulsion, from the viewpoint of polymerization stability, mechanical stability, chemical stability, coating gloss, and coating adhesion. 12 or more, preferably 14 or more, more preferably 16 or more, and from the viewpoint of polymerization stability, mechanical stability, chemical stability, coating film gloss, and coating film adhesion, 22 or less. Yes, preferably 20 or less, more preferably 18 or less.
In the present invention, the component (a) may be a hydroxyalkane sulfonate having a distribution of 12 to 22 carbon atoms, or a hydroxyalkane sulfonate having a single carbon number of 12 to 22 carbon atoms. There may be. Further, it may be a hydroxyalkane sulfonate having 12 or more and 22 or less carbon atoms having two or more carbon numbers having different carbon numbers.
The hydroxyalkane sulfonate having a distribution of 12 to 22 carbon atoms means that the content of the hydroxyalkane sulfonate having 12 to 22 carbon atoms in the component (a) is 80% by mass or more. , Preferably it is 90 mass% or more, More preferably, it is 95 mass% or more.
（ａ）成分であるヒドロキシアルカンスルホン酸塩は、炭素数１２以上２２以下のα−オレフィン又は原料内部オレフィンをスルホン化し、中和し、次いで加水分解することにより得ることができる。スルホン化、中和、加水分解の条件は特に制限はなく、例えば、特公昭４９−４１１７９号公報や特開平２−７３０５１号公報等に記載の条件を参照することができる。
（ａ）成分は、カーボンニュートラルの観点からは、天然油脂由来の原料内部オレフィンを用いて得られることが好ましい。該原料内部オレフィンは、天然油脂由来の炭素数１２以上２２以下の脂肪族アルコール（以下、単に「脂肪族アルコール」ともいう）の脱水反応により得られたもの、及び天然油脂由来の炭素数１４以上２２以下の脂肪酸（以下、単に「脂肪酸」ともいう）の脱一酸化炭素反応により得られたものから選ばれる１種以上のものが好ましい。
前記原料内部オレフィンの原料として用いられる脂肪族アルコールとしては、後述する本発明の界面活性剤組成物の製造方法において挙げられる脂肪族アルコールが好ましい。
前記原料内部オレフィンの原料として用いられる脂肪酸としては、天然油脂由来のパルミチン酸、ステアリン酸、アラキン酸、ベヘン酸等の飽和脂肪酸等が挙げられ、これらの中では、パルミチン酸、ステアリン酸及びアラキン酸から選ばれる１種以上が好ましく、ステアリン酸がより好ましい。
The hydroxyalkane sulfonate which is component (a) can be obtained by sulfonating, neutralizing and then hydrolyzing an α-olefin having 12 to 22 carbon atoms or a raw material internal olefin. The conditions for sulfonation, neutralization and hydrolysis are not particularly limited, and for example, the conditions described in JP-B-49-41179, JP-A-2-73051 and the like can be referred to.
The component (a) is preferably obtained using a raw material internal olefin derived from natural fats and oils from the viewpoint of carbon neutral. The raw material internal olefin is obtained by a dehydration reaction of an aliphatic alcohol having 12 to 22 carbon atoms derived from natural fats and oils (hereinafter also simply referred to as “aliphatic alcohol”), and 14 or more carbon atoms derived from natural fats and oils. One or more selected from those obtained by carbon monoxide reaction of 22 or less fatty acids (hereinafter also simply referred to as “fatty acids”) are preferred.
As the aliphatic alcohol used as a raw material for the raw material internal olefin, aliphatic alcohols mentioned in the method for producing a surfactant composition of the present invention described later are preferable.
Examples of the fatty acid used as a raw material for the raw material internal olefin include saturated fatty acids such as palmitic acid, stearic acid, arachidic acid, and behenic acid derived from natural fats and oils. Among these, palmitic acid, stearic acid, and arachidic acid are included. 1 or more types selected from are preferred, and stearic acid is more preferred.
［（ｂ）成分：炭素数１２以上２２以下の内部オレフィンスルホン酸塩］
本発明の乳化重合用アニオン性界面活性剤組成物は、（ｂ）成分として、炭化水素基内部に二重結合を有する不飽和スルホン酸塩である、炭素数１２以上２２以下の内部オレフィンスルホン酸塩を含有する。
本発明に用いる内部オレフィンスルホン酸塩の炭素数は、エマルションの平均粒径を小さくし、重合安定性、機械的安定性、化学的安定性、塗膜光沢、塗膜密着性の観点から、１２以上であり、好ましくは１４以上、より好ましくは１６以上であり、そして、重合安定性、機械的安定性、化学的安定性、塗膜光沢、塗膜密着性の観点から、２２以下であり、好ましくは２０以下、より好ましくは１８以下である。
本発明において（ｂ）成分は、炭素数１２以上２２以下に分布を有する内部オレフィンスルホン酸塩であってもよく、単一の炭素数である炭素数１２以上２２以下の内部オレフィンスルホン酸塩であってもよい。また、異なる炭素数を有する２種以上の炭素数の炭素数１２以上２２以下の内部オレフィンスルホン酸塩であってもよい。
なお、炭素数１２以上２２以下に分布を有する内部オレフィンスルホン酸塩とは、（ｂ）成分中、炭素数１２以上２２以下の内部オレフィンスルホン酸塩の含有量が８０質量％以上のものをいい、好ましくは９０質量％以上、より好ましくは９５質量％以上である。
[Component (b): Internal olefin sulfonate having 12 to 22 carbon atoms]
The anionic surfactant composition for emulsion polymerization of the present invention is an internal olefin sulfonic acid having 12 to 22 carbon atoms, which is an unsaturated sulfonate having a double bond inside a hydrocarbon group as component (b). Contains salt.
The carbon number of the internal olefin sulfonate used in the present invention is 12 from the viewpoints of reducing the average particle size of the emulsion, polymerization stability, mechanical stability, chemical stability, coating film gloss, and coating film adhesion. Or more, preferably 14 or more, more preferably 16 or more, and from the viewpoint of polymerization stability, mechanical stability, chemical stability, coating film gloss, coating film adhesion, 22 or less, Preferably it is 20 or less, More preferably, it is 18 or less.
In the present invention, the component (b) may be an internal olefin sulfonate having a distribution of 12 to 22 carbon atoms, or an internal olefin sulfonate having 12 to 22 carbon atoms, which is a single carbon number. There may be. Further, it may be an internal olefin sulfonate having 12 or more and 22 or less carbon atoms having two or more carbon atoms having different carbon numbers.
The internal olefin sulfonate having a distribution of 12 to 22 carbon atoms means that the content of the internal olefin sulfonate having 12 to 22 carbon atoms in the component (b) is 80% by mass or more. , Preferably it is 90 mass% or more, More preferably, it is 95 mass% or more.
（ｂ）成分である内部オレフィンスルホン酸塩は、原料内部オレフィンをスルホン化し、中和し、次いで加水分解することにより得ることが好ましい。スルホン化、中和、加水分解の条件は特に制限はなく、（ａ）成分と同様に、特公昭４９−４１１７９号公報や特開平２−７３０５１号公報等に記載の条件を参照することができる。
（ｂ）成分は、カーボンニュートラルの観点から、天然油脂由来の原料内部オレフィンを用いて得られることが好ましい。該原料内部オレフィンは、天然油脂由来の炭素数１２以上２２以下の脂肪族アルコールの脱水反応により得られたもの、及び天然油脂由来の炭素数１４以上２２以下の脂肪酸の脱一酸化炭素反応により得られたものから選ばれる１種以上のものが好ましい。
前記原料内部オレフィンの原料として用いられる脂肪族アルコールは、後述する本発明の界面活性剤組成物の製造方法において挙げられる脂肪族アルコールが好ましい。また、前記原料内部オレフィンの原料として用いられる脂肪酸は、前述と同様の脂肪酸が好ましい。
The internal olefin sulfonate which is component (b) is preferably obtained by sulfonating, neutralizing and then hydrolyzing the raw internal olefin. The conditions for sulfonation, neutralization and hydrolysis are not particularly limited, and the conditions described in JP-B-49-41179 and JP-A-2-73051 can be referred to as in the case of component (a). .
(B) It is preferable that a component is obtained using the raw material internal olefin derived from natural fats and oils from a carbon neutral viewpoint. The raw material internal olefin is obtained by a dehydration reaction of an aliphatic alcohol having 12 to 22 carbon atoms derived from natural fats and oils and a decarbonization reaction of a fatty acid having 14 to 22 carbon atoms derived from natural fats and oils. One or more selected from those obtained are preferred.
The aliphatic alcohol used as a raw material for the raw material internal olefin is preferably an aliphatic alcohol exemplified in the method for producing a surfactant composition of the present invention described later. The fatty acid used as the raw material for the raw material internal olefin is preferably the same fatty acid as described above.
［（ｃ）成分：炭素数１２以上２２以下の内部オレフィン］
本発明の乳化重合用アニオン性界面活性剤組成物は、（ｃ）成分として、炭素数１２以上２２以下の内部オレフィンを含有する。
（ｃ）成分である内部オレフィンの炭素数は、エマルションの平均粒径を小さくし、重合安定性、機械的安定性、化学的安定性、塗膜光沢、及び塗膜密着性の観点から、１２以上であり、好ましくは１４以上、より好ましくは１６以上であり、そして、重合安定性、機械的安定性、化学的安定性、塗膜光沢、及び塗膜密着性の観点から、２２以下であり、好ましくは２０以下、より好ましくは１８以下である。
本発明において（ｃ）成分は、炭素数１２以上２２以下に分布を有する内部オレフィンであってもよく、単一の炭素数である炭素数１２以上２２以下の内部オレフィンであってもよい。また、異なる炭素数を有する２種以上の炭素数の炭素数１２以上２２以下の内部オレフィンであってもよい。
なお、炭素数１２以上２２以下に分布を有する内部オレフィンとは、（ｃ）成分中、炭素数１２以上２２以下の内部オレフィンの含有量が８０質量％以上のものをいい、好ましくは９０質量％以上、より好ましくは９５質量％以上である。
[Component (c): Internal olefin having 12 to 22 carbon atoms]
The anionic surfactant composition for emulsion polymerization of the present invention contains an internal olefin having 12 to 22 carbon atoms as the component (c).
The number of carbon atoms of the internal olefin as the component (c) is 12 from the viewpoints of reducing the average particle size of the emulsion, polymerization stability, mechanical stability, chemical stability, coating gloss, and coating adhesion. Or more, preferably 14 or more, more preferably 16 or more, and 22 or less from the viewpoint of polymerization stability, mechanical stability, chemical stability, coating film gloss, and coating film adhesion. , Preferably 20 or less, more preferably 18 or less.
In the present invention, the component (c) may be an internal olefin having a distribution of 12 to 22 carbon atoms, or an internal olefin having 12 to 22 carbon atoms, which is a single carbon number. Moreover, the C12 or more and 22 or less internal olefin of 2 or more types of carbon number which has different carbon number may be sufficient.
The internal olefin having a distribution of 12 to 22 carbon atoms means that the content of the internal olefin having 12 to 22 carbon atoms in the component (c) is 80% by mass or more, preferably 90% by mass. As mentioned above, More preferably, it is 95 mass% or more.
本発明において、製造容易性の観点から、（ａ）及び（ｂ）成分を製造する際に、原料内部オレフィンをスルホン化し、中和し、次いで加水分解した後の未反応オレフィンを（ｃ）成分として用いて、（ａ）成分と（ｂ）成分の合計１００質量部に対して、（ｃ）成分を０．１質量部以上３質量部以下となることが好ましい。また、（ａ）及び（ｂ）成分を、原料内部オレフィンをスルホン化、中和、加水分解により得た後、（ｃ）成分を後添加してもよい。
（ｃ）成分は、カーボンニュートラルの観点から、天然油脂由来の原料である内部オレフィンが好ましい。該原料内部オレフィンは、天然油脂由来の炭素数１２以上２２以下の脂肪族アルコールの脱水反応により得られたもの、及び天然油脂由来の炭素数１４以上２２以下の脂肪酸の脱一酸化炭素反応により得られたものから選ばれる１種以上のものがより好ましい。
前記原料内部オレフィンの原料として用いられる脂肪族アルコールは、後述する本発明の界面活性剤組成物の製造方法において挙げられる脂肪族アルコールが好ましい。また、前記原料内部オレフィンの原料として用いられる脂肪酸は、前述と同様の脂肪酸が好ましい。
In the present invention, from the viewpoint of ease of production, when the components (a) and (b) are produced, the raw material internal olefin is sulfonated, neutralized, and then hydrolyzed, the unreacted olefin is the component (c). It is preferable that the component (c) is 0.1 parts by mass or more and 3 parts by mass or less with respect to a total of 100 parts by mass of the component (a) and the component (b). Further, after the components (a) and (b) are obtained by sulfonation, neutralization and hydrolysis of the raw material internal olefin, the component (c) may be added afterwards.
The component (c) is preferably an internal olefin which is a raw material derived from natural fats and oils from the viewpoint of carbon neutral. The raw material internal olefin is obtained by a dehydration reaction of an aliphatic alcohol having 12 to 22 carbon atoms derived from natural fats and oils and a decarbonization reaction of a fatty acid having 14 to 22 carbon atoms derived from natural fats and oils. One or more types selected from those obtained are more preferable.
The aliphatic alcohol used as a raw material for the raw material internal olefin is preferably an aliphatic alcohol exemplified in the method for producing a surfactant composition of the present invention described later. The fatty acid used as the raw material for the raw material internal olefin is preferably the same fatty acid as described above.
［各成分の含有量］
本発明の界面活性剤組成物中の（ｃ）成分の含有量は、エマルションの平均粒径を小さくし、重合安定性、機械的安定性、化学的安定性、塗膜光沢、塗膜密着性の観点から、（ａ）成分と（ｂ）成分の合計１００質量部に対し、０．１質量部以上であり、好ましくは０．３質量部以上であり、より好ましくは１．０質量部以上であり、更に好ましくは１．２質量部以上であり、そして、同様の観点から、３質量部以下であり、好ましくは２．５質量部以下であり、より好ましくは２．０質量部以下であり、更に好ましくは１．６質量部以下である。
[Content of each component]
The content of the component (c) in the surfactant composition of the present invention reduces the average particle size of the emulsion, polymerization stability, mechanical stability, chemical stability, coating gloss, and coating adhesion. In view of the above, it is 0.1 parts by mass or more, preferably 0.3 parts by mass or more, more preferably 1.0 parts by mass or more with respect to 100 parts by mass of the total of the component (a) and the component (b). More preferably, it is 1.2 parts by mass or more, and from the same viewpoint, it is 3 parts by mass or less, preferably 2.5 parts by mass or less, more preferably 2.0 parts by mass or less. Yes, more preferably 1.6 parts by mass or less.
本発明の界面活性剤組成物中の（ａ）成分の含有量は、エマルションの平均粒径を小さくし、重合安定性、機械的安定性、化学的安定性、塗膜光沢、塗膜密着性の観点から、（ａ）成分と（ｂ）成分の合計１００質量部中、好ましくは４０質量部以上、より好ましくは５０質量部以上、更に好ましくは６０質量部以上、より更に好ましくは７０質量部以上であり、そして、同様の観点から、好ましくは９５質量部以下、より好ましくは９０質量部以下、更に好ましくは８５質量部以下である。 The content of the component (a) in the surfactant composition of the present invention reduces the average particle size of the emulsion, polymerization stability, mechanical stability, chemical stability, coating gloss, and coating adhesion. From the viewpoint of the above, the total of 100 parts by mass of the component (a) and the component (b) is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more, and still more preferably 70 parts by mass. From the same viewpoint, it is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, and still more preferably 85 parts by mass or less.
本発明の界面活性剤組成物中の（ｂ）成分の含有量は、エマルションの平均粒径を小さくし、重合安定性、機械的安定性、化学的安定性、塗膜光沢、塗膜密着性の観点から、（ａ）成分と（ｂ）成分の合計１００質量部中、好ましくは５質量部以上、より好ましくは１０質量部以上であり、そして、同様の観点から、好ましくは６０質量部以下、より好ましくは４０質量部以下、更に好ましくは３０質量部以下、より更に好ましくは２０質量部以下である。 The content of the component (b) in the surfactant composition of the present invention reduces the average particle size of the emulsion, polymerization stability, mechanical stability, chemical stability, coating gloss, and coating adhesion. From the viewpoint, the total of 100 parts by mass of the component (a) and the component (b) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and from the same viewpoint, preferably 60 parts by mass or less. More preferably, it is 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less.
本発明の界面活性剤組成物中の（ａ）成分と（ｂ）成分との質量比〔（ａ）成分／（ｂ）成分〕は、エマルションの平均粒径を小さくし、重合安定性、機械的安定性、化学的安定性、塗膜光沢、塗膜密着性の観点から、好ましくは２０以下、より好ましくは１４以下、更に好ましくは９以下であり、そして、エマルションの平均粒径を小さくし、重合安定性、機械的安定性、塗膜光沢、塗膜密着性の観点から、好ましくは０．２５以上、より好ましくは０．８以上、更に好ましくは２以上である。 The mass ratio of the component (a) to the component (b) [(a) component / (b) component] in the surfactant composition of the present invention reduces the average particle size of the emulsion, and provides polymerization stability, machine Is preferably 20 or less, more preferably 14 or less, and still more preferably 9 or less, from the viewpoint of mechanical stability, chemical stability, coating film gloss, and coating film adhesion, and the average particle size of the emulsion is reduced. From the viewpoints of polymerization stability, mechanical stability, coating film gloss, and coating film adhesion, it is preferably 0.25 or more, more preferably 0.8 or more, and even more preferably 2 or more.
本発明の界面活性剤組成物中の（ａ）成分、（ｂ）成分、及び（ｃ）成分の合計含有量は、エマルションの平均粒径を小さくし、重合安定性、機械的安定性、化学的安定性、塗膜光沢、塗膜密着性の観点から、好ましくは９５質量％以上であり、より好ましくは９７質量％以上であり、更に好ましくは９９質量％以上であり、そして、エマルションの平均粒径を小さくし、重合安定性、機械的安定性、塗膜光沢、塗膜密着性の観点から、好ましくは１００質量％以下である。
また、本発明の界面活性剤組成物は、本発明の効果を損なわない範囲内で、界面活性剤組成物の製造における副生成物であるサルトン類を含有してもよい。
The total content of the component (a), the component (b), and the component (c) in the surfactant composition of the present invention reduces the average particle size of the emulsion, and provides polymerization stability, mechanical stability, chemistry. From the viewpoint of mechanical stability, coating film gloss, and coating film adhesion, it is preferably 95% by mass or more, more preferably 97% by mass or more, still more preferably 99% by mass or more, and the average of the emulsion The particle size is reduced, and from the viewpoint of polymerization stability, mechanical stability, coating film gloss, and coating film adhesion, it is preferably 100% by mass or less.
Further, the surfactant composition of the present invention may contain sultone which is a by-product in the production of the surfactant composition within a range not impairing the effects of the present invention.
（その他の界面活性剤）
本発明の界面活性剤組成物には、本発明の効果を損なわない範囲で、その他の成分をさらに含むことができる。その他の成分としては、例えば、アルコールエトキシレート、アルキルポリグリコシド、アルカノールアミドなどの非イオン性界面活性剤；アルキルサルフェート、アルキルエーテルサルフェート、脂肪酸石鹸、アルキルエーテルカルボキシレートなどのアニオン性界面活性剤；水溶性保護コロイド等が挙げられる。
(Other surfactants)
The surfactant composition of the present invention can further contain other components as long as the effects of the present invention are not impaired. Examples of other components include nonionic surfactants such as alcohol ethoxylates, alkyl polyglycosides, and alkanolamides; anionic surfactants such as alkyl sulfates, alkyl ether sulfates, fatty acid soaps, and alkyl ether carboxylates; Protective colloids and the like.
＜乳化重合用アニオン性界面活性剤組成物の製造方法＞
本発明の界面活性剤組成物は、炭素数１２以上２２以下の原料内部オレフィンをスルホン化した後、中和し、次いで加水分解して得られる（ａ）〜（ｃ）成分を含有する乳化重合用アニオン性界面活性剤組成物であって、該原料内部オレフィンが天然油脂由来の炭素数１２以上２２以下の脂肪族アルコールの脱水反応により得られることが好ましい。
<Method for producing anionic surfactant composition for emulsion polymerization>
The surfactant composition of the present invention is an emulsion polymerization containing components (a) to (c) obtained by sulfonating a raw material internal olefin having 12 to 22 carbon atoms, neutralizing, and then hydrolyzing. It is preferable that the raw material internal olefin is obtained by a dehydration reaction of an aliphatic alcohol having 12 to 22 carbon atoms derived from natural fats and oils.
本発明の界面活性剤組成物の製造方法で用いる炭素数１２以上２２以下の原料内部オレフィンは、天然油脂由来の炭素数１２以上２２以下の脂肪族アルコールの脱水反応により得られる。
前記脂肪族アルコールの脱水反応は、例えば特許第５２２１７７３号に記載されている脂肪族アルコールの液相脱水反応を参照することができ、アルミナ又はリン酸アルミニウムの固体酸触媒の存在下、反応温度１６０℃以上２９０℃以下で、０．０３ＭＰａ以上０．０９ＭＰａ以下の減圧下又は常圧で反応系内に窒素を導入し、生成する水を系外に除去しながら反応を行うことが好ましい。
The raw material internal olefin having 12 to 22 carbon atoms used in the method for producing the surfactant composition of the present invention is obtained by dehydration reaction of an aliphatic alcohol having 12 to 22 carbon atoms derived from natural fats and oils.
For the dehydration reaction of the aliphatic alcohol, for example, the liquid phase dehydration reaction of the aliphatic alcohol described in Japanese Patent No. 5221773 can be referred to. The reaction temperature is 160 in the presence of an alumina or aluminum phosphate solid acid catalyst. It is preferable to carry out the reaction while introducing nitrogen into the reaction system at a reduced pressure of 0.03 MPa or more and 0.09 MPa or less or normal pressure at a temperature of 290 ° C. or higher and 290 ° C. or lower and removing generated water from the system.
前記脂肪族アルコールの炭素数は、得られる界面活性剤組成物を用いて製造されるエマルションの平均粒径を小さくし、重合安定性、機械的安定性、化学的安定性、塗膜光沢、及び塗膜密着性の観点から、１２以上であり、好ましくは１４以上、より好ましくは１６以上であり、そして、重合安定性、機械的安定性、化学的安定性、塗膜光沢、及び塗膜密着性の観点から、２２以下であり、好ましくは２０以下、より好ましくは１８以下である。 The number of carbon atoms of the aliphatic alcohol reduces the average particle size of an emulsion produced using the resulting surfactant composition, polymerization stability, mechanical stability, chemical stability, coating gloss, and From the viewpoint of coating film adhesion, it is 12 or more, preferably 14 or more, more preferably 16 or more, and polymerization stability, mechanical stability, chemical stability, coating gloss, and coating film adhesion From the viewpoint of property, it is 22 or less, preferably 20 or less, more preferably 18 or less.
本発明の界面活性剤組成物の製造方法に用いる原料内部オレフィンの原料である脂肪族アルコールは、天然油脂由来のアルコールであり、好ましくは天然油脂由来の第一級脂肪族アルコールである。
天然油脂由来の第一級脂肪族アルコールとしては、ヤシ油、パーム油、パーム核油、大豆油、なたね油、牛脂、豚脂、トール油、及び魚油等の天然油脂を原料としたものが挙げられ、エマルションの平均粒径を小さくし、重合安定性、機械的安定性、化学的安定性、塗膜光沢、及び塗膜密着性の観点から、パーム核油及びヤシ油から選ばれる１種以上の天然油脂を原料とする第一級脂肪族アルコールが好ましく、パーム核油由来の第一級脂肪族アルコールがより好ましい。
前記天然油脂由来の第一級脂肪族アルコールとしては、例えば、１−ドデカノール、１−テトラデカノール、１−ヘキサデカノール、１−オクタデカノール、１−エイコサノール、１−ドコサノール等が挙げられ、１−テトラデカノール、１−ヘキサデカノール、１−オクタデカノール、及び１−エイコサノールから選ばれる１種以上が好ましく、１−テトラデカノール、１−ヘキサデカノール、１−オクタデカノールから選ばれる１種以上がより好ましく、１−オクタデカノールが更に好ましい。
The aliphatic alcohol which is the raw material of the raw material internal olefin used in the method for producing the surfactant composition of the present invention is an alcohol derived from natural fats and oils, preferably a primary aliphatic alcohol derived from natural fats and oils.
Examples of the primary aliphatic alcohols derived from natural fats and oils include those made from natural fats and oils such as coconut oil, palm oil, palm kernel oil, soybean oil, rapeseed oil, beef tallow, pork fat, tall oil, and fish oil. One or more kinds selected from palm kernel oil and coconut oil from the viewpoints of reducing the average particle size of the emulsion, polymerization stability, mechanical stability, chemical stability, coating film gloss, and coating film adhesion Primary aliphatic alcohols made from natural fats and oils are preferred, and primary aliphatic alcohols derived from palm kernel oil are more preferred.
Examples of the primary aliphatic alcohol derived from natural fats and oils include 1-dodecanol, 1-tetradecanol, 1-hexadecanol, 1-octadecanol, 1-eicosanol, 1-docosanol, and the like. One or more selected from 1-tetradecanol, 1-hexadecanol, 1-octadecanol, and 1-eicosanol is preferable, and selected from 1-tetradecanol, 1-hexadecanol, and 1-octadecanol. 1 or more types are more preferable, and 1-octadecanol is still more preferable.
スルホン化、中和、加水分解の条件は特に制限はなく、前記と同様に、特公昭４９−４１１７９号公報や特開平２−７３０５１号公報等に記載の条件を参照することができる。
本発明の製造方法に用いるスルホン化剤としては、ＳＯ３ガスが挙げられる。ＳＯ３ガスでスルホン化した場合は、アンモニア、アルカリ金属の水酸化物等で中和することが好ましい。
前記スルホン化反応は、例えば、原料内部オレフィン１モルに対しＳＯ３ガスを１．０以上１．２モル以下反応させることにより行うことができる。反応温度は、２０℃以上４０℃以下で行うことが好ましい。
The conditions for sulfonation, neutralization and hydrolysis are not particularly limited, and as described above, the conditions described in JP-B-49-41179, JP-A-2-73051 and the like can be referred to.
Examples of the sulfonating agent used in the production method of the present invention include SO 3 gas. In the case of sulfonation with SO 3 gas, neutralization with ammonia, alkali metal hydroxide or the like is preferable.
The sulfonation reaction can be performed, for example, by reacting 1.0 to 1.2 mol of SO 3 gas with 1 mol of raw material internal olefin. The reaction temperature is preferably 20 ° C or higher and 40 ° C or lower.
中和は、スルホン酸基の理論値に対し１．０モル倍量以上１．５モル倍量以下の水酸化ナトリウム、アンモニア、２−アミノエタノール等のアルカリ水溶液を反応させることにより行われる。
加水分解反応は、水の存在下９０℃以上２００℃以下で、３０分以上３時間以下で行うことが好ましい。これらの反応は、連続して行うことができる。また反応終了後は、抽出、洗浄等により精製することができる。
Neutralization is performed by reacting an alkali aqueous solution such as sodium hydroxide, ammonia, 2-aminoethanol, etc. in an amount of 1.0 mol times to 1.5 mol times the theoretical value of the sulfonic acid group.
The hydrolysis reaction is preferably performed in the presence of water at 90 ° C. or more and 200 ° C. or less and for 30 minutes or more and 3 hours or less. These reactions can be performed continuously. Moreover, after completion | finish of reaction, it can refine | purify by extraction, washing | cleaning, etc.
本発明の界面活性剤組成物の製造方法における（ａ）〜（ｃ）成分の含有量は、スルホン化反応後、中和前の熟成時間を調整することによってもできる。該熟成時間が短いほど（ａ）成分の含有量が増加し、（ｂ）成分の含有量は低下する。また、原料内部オレフィン１モルに対するＳＯ３ガスの使用量を調整することにより（ｃ）成分の含有量を調整することもできる。
また、（ｃ）成分の含有量は、上記調整のほか、（ｃ）成分の含有量が所望の範囲内になるように後添加することにより調整することもできる。
炭素数１２以上２２以下の原料内部オレフィンを用いてスルホン化、中和、加水分解処理して得られる組成物（ｘ）に（ｃ）成分を、前記界面活性剤組成物中の（ａ）成分と（ｂ）成分の合計１００質量部に対して、０．１質量部以上３質量部以下となるように添加してもよい。
The contents of the components (a) to (c) in the method for producing the surfactant composition of the present invention can also be adjusted by adjusting the aging time after the sulfonation reaction and before neutralization. As the aging time is shorter, the content of the component (a) increases and the content of the component (b) decreases. It is also possible to adjust the content of the component (c) by adjusting the amount of SO 3 gas to the raw material internal olefin mole.
In addition to the above adjustment, the content of component (c) can also be adjusted by post-adding so that the content of component (c) falls within the desired range.
The component (c) is added to the composition (x) obtained by sulfonation, neutralization, and hydrolysis treatment using a raw material internal olefin having 12 to 22 carbon atoms, and the component (a) in the surfactant composition. And (b) component may be added so as to be 0.1 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass in total.
本発明の界面活性剤組成物の製造方法は、炭素数１２以上２２以下に分布を有する原料内部オレフィンを用いてスルホン化、中和、加水分解の処理を行ってもよく、単一の炭素数を有する原料内部オレフィンを用いてスルホン化、中和、加水分解の処理を行ってもよい。また必要に応じて予め製造した異なる炭素数を有する２種以上の前記界面活性剤組成物を混合してもよい。
炭素数１２以上２２以下に分布を有する原料内部オレフィンとは、炭素数１２以上２２以下の内部オレフィンの含有量が８０質量％以上のものをいい、好ましくは９０質量％以上、より好ましくは９５質量％以上である。
In the method for producing the surfactant composition of the present invention, the raw material internal olefin having a distribution of 12 to 22 carbon atoms may be used for sulfonation, neutralization, and hydrolysis treatment, and a single carbon number may be used. Sulfonation, neutralization, and hydrolysis treatment may be performed using the raw material internal olefin. Moreover, you may mix the 2 or more types of said surfactant composition which has a different carbon number manufactured previously as needed.
The raw material internal olefin having a distribution of 12 to 22 carbon atoms refers to those having an internal olefin content of 12 to 22 carbon atoms of 80 mass% or more, preferably 90 mass% or more, more preferably 95 mass%. % Or more.
＜ポリマーエマルションの製造方法＞
本発明のポリマーエマルションの製造方法は、前記乳化重合用アニオン性界面活性剤組成物の存在下、ラジカル重合可能なモノマーを乳化重合する方法である。
本発明に用いるモノマーは、ラジカル重合可能なモノマーであり、具体例には、スチレン、α−メチルスチレン、クロロスチレン等のスチレン系モノマー；アクリル酸、メタクリル酸等の（メタ）アクリル酸；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル等の好ましくは炭素数１以上２２以下、より好ましくは１以上１２以下、更に好ましくは１以上６以下のアルキル基を有する、（メタ）アクリル酸エステル；塩化ビニル、臭化ビニル等のハロゲン化ビニル及び塩化ビニリデン等のハロゲン化ビニリデン；酢酸ビニル、プロピオン酸ビニル等のビニルエステル等が挙げられる。
その他のモノマーとしては、アクリロニトリル、メタクリロニトリル等のニトリル類；ブタジエン、イソプレン等の共役ジエン類等が挙げられる。これらのモノマーは単独で重合させても、２種以上を併用して共重合させてもよい。
なお、（メタ）アクリル酸は、メタクリル酸及びアクリル酸から選ばれる１種又は２種を意味する。（メタ）アクリル酸エステルは、メタクリル酸エステル及びアクリル酸エステルから選ばれる１種又は２種を意味する。以下においても同様である。
<Method for producing polymer emulsion>
The method for producing a polymer emulsion of the present invention is a method in which a radically polymerizable monomer is emulsion-polymerized in the presence of the anionic surfactant composition for emulsion polymerization.
The monomer used in the present invention is a radically polymerizable monomer. Specific examples include styrene monomers such as styrene, α-methylstyrene, and chlorostyrene; (meth) acrylic acid such as acrylic acid and methacrylic acid; ) Methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and the like, preferably having an alkyl group having 1 to 22 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 6 carbon atoms, (Meth) acrylic acid esters; vinyl halides such as vinyl chloride and vinyl bromide and vinylidene halides such as vinylidene chloride; vinyl esters such as vinyl acetate and vinyl propionate.
Other monomers include nitriles such as acrylonitrile and methacrylonitrile; conjugated dienes such as butadiene and isoprene. These monomers may be polymerized alone or in combination of two or more.
In addition, (meth) acrylic acid means 1 type or 2 types chosen from methacrylic acid and acrylic acid. (Meth) acrylic acid ester means one or two selected from methacrylic acid esters and acrylic acid esters. The same applies to the following.
本発明のポリマーエマルションの製造方法における前記界面活性剤組成物の使用量は、エマルションの平均粒径を小さくし、重合安定性、機械的安定性、化学的安定性、塗膜光沢、塗膜密着性の観点から、モノマー１００質量部に対して、好ましくは０．１質量部以上、より好ましくは０．５質量部以上、更に好ましくは１質量部以上、そして、同様の観点から、好ましくは２０質量部以下、より好ましくは５質量部以下、更に好ましくは３質量部以下で用いる。また、異なる炭素数を有する２種以上の前記界面活性剤組成物を混合して用いてもよい。 The amount of the surfactant composition used in the method for producing a polymer emulsion of the present invention is such that the average particle size of the emulsion is reduced, polymerization stability, mechanical stability, chemical stability, coating gloss, and coating adhesion. From the viewpoint of safety, it is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and from the same viewpoint, preferably 20 parts by mass or more with respect to 100 parts by mass of the monomer. It is used in an amount of not more than part by mass, more preferably not more than 5 parts by mass, still more preferably not more than 3 parts by mass. Further, two or more kinds of the surfactant compositions having different carbon numbers may be mixed and used.
本発明のポリマーエマルションの製造方法に用いる前記界面活性剤組成物には、本発明の効果を損なわない範囲で、その他の成分をさらに含むことができる。その他の成分としては、例えば、アルコールエトキシレート、アルキルポリグリコシド、アルカノールアミドなどの非イオン性界面活性剤；アルキルサルフェート、アルキルエーテルサルフェート、脂肪酸石鹸、アルキルエーテルカルボキシレートなどのアニオン性界面活性剤、更に水溶性保護コロイド等が挙げられる。 The surfactant composition used in the method for producing a polymer emulsion of the present invention can further contain other components as long as the effects of the present invention are not impaired. Other components include, for example, nonionic surfactants such as alcohol ethoxylates, alkyl polyglycosides, and alkanolamides; anionic surfactants such as alkyl sulfates, alkyl ether sulfates, fatty acid soaps, and alkyl ether carboxylates; Examples include water-soluble protective colloids.
本発明のポリマーエマルションの製造方法に用いるラジカル重合開始剤は、通常の乳化重合に用いられるものであればいずれも使用できる。ラジカル重合開始剤としては、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩；過酸化水素、ｔ−ブチルハイドロパーオキサイド、ベンゾイルパーオキサイド、クメンハイドロパーオキサイド等の有機過酸化物；アゾビスジイソブチロニトリル、２，２−アゾビス（２−アミジノプロパン）ジハイドロクロライド等のアゾ系開始剤等が挙げられ、重合反応性、作業性及び経済性の観点から、過硫酸塩が好ましい。さらに、重合開始剤としては、過酸化化合物に亜硫酸ナトリウム、ロンガリット、アスコルビン酸等の還元剤を組み合わせたレドックス系の開始剤も使用できる。 Any radical polymerization initiator used in the method for producing a polymer emulsion of the present invention can be used as long as it is used in ordinary emulsion polymerization. As radical polymerization initiators, persulfates such as potassium persulfate and ammonium persulfate; organic peroxides such as hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide; azobisdiisobutyronitrile Azo initiators such as 2,2-azobis (2-amidinopropane) dihydrochloride and the like, and persulfates are preferred from the viewpoints of polymerization reactivity, workability and economy. Furthermore, as the polymerization initiator, a redox initiator in which a peroxide compound is combined with a reducing agent such as sodium sulfite, Rongalite, and ascorbic acid can be used.
本発明のポリマーエマルションの製造方法における乳化重合条件は特に制限がないが、モノマーの使用量は、全系に対して、好ましくは３０質量％以上７０質量％以下、より好ましくは４０質量％以上６０重量％以下である。またモノマーの添加方法として、モノマー滴下法、モノマー一括仕込み法、プレエマルション法等のいずれの乳化重合法にも用いることができるが、重合安定性の観点から、プレエマルション法が好ましい。
プレエマルションの滴下時間は１時間以上８時間以下、熟成時間は１時間以上５時間以下が好ましい。重合温度は、開始剤の分解温度により調整されるが、５０℃以上９０℃以下が好ましく、特に過硫酸塩の場合は７０℃以上８５℃以下が好ましい。
The emulsion polymerization conditions in the method for producing a polymer emulsion of the present invention are not particularly limited, but the amount of the monomer used is preferably 30% by mass or more and 70% by mass or less, more preferably 40% by mass or more and 60% by mass relative to the total system. % By weight or less. Moreover, as a monomer addition method, it can be used for any emulsion polymerization method such as a monomer dropping method, a monomer batch charging method, a pre-emulsion method, etc., but the pre-emulsion method is preferable from the viewpoint of polymerization stability.
The dropping time of the pre-emulsion is preferably 1 hour or more and 8 hours or less, and the aging time is preferably 1 hour or more and 5 hours or less. The polymerization temperature is adjusted by the decomposition temperature of the initiator, but is preferably 50 ° C. or higher and 90 ° C. or lower, and particularly 70 ° C. or higher and 85 ° C. or lower in the case of persulfate.
＜ポリマーエマルション＞
本発明のポリマーエマルションは、前記乳化重合用アニオン性界面活性剤組成物を用い、前記製造方法により得られる。
本発明のポリマーエマルションの平均粒径は、機械的安定性、化学的安定性、塗膜光沢、塗膜密着性の観点から、好ましくは３００ｎｍ以下、より好ましくは２００ｎｍ以下、更に好ましくは１５０ｎｍ以下、より更に好ましくは１３０ｎｍ以下であり、そして、重合安定性の観点から、好ましくは１００ｎｍ以上、より好ましくは１０５ｎｍ以上、更に好ましくは１１０ｎｍ以上である。
<Polymer emulsion>
The polymer emulsion of the present invention is obtained by the production method using the anionic surfactant composition for emulsion polymerization.
The average particle size of the polymer emulsion of the present invention is preferably 300 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, from the viewpoint of mechanical stability, chemical stability, coating film gloss, and coating film adhesion. Still more preferably, it is 130 nm or less, and from the viewpoint of polymerization stability, it is preferably 100 nm or more, more preferably 105 nm or more, still more preferably 110 nm or more.
＜塗料組成物＞
本発明の塗料組成物は、前記ポリマーエマルションを含有する。顔料や、必要に応じて、水、粘性制御剤、消泡剤、酸化防止剤、紫外線吸収剤等を更に含有することができる。
顔料としては、タルク、カオリン、炭酸カルシウム、硫酸バリウム等の体質顔料；ベンガラ、カーボンブラック、群青、黄酸化鉄等の着色顔料；二酸化チタン、酸化亜鉛等の白色顔料、雲母チタン、オキシ塩化ビスマス等のパール系顔料等の無機系顔料；有機合成色素としての染料、有機顔料等が挙げられる。これらの顔料は単独又は２種以上であってもよい。
本発明の塗料組成物は、前記ポリマーエマルションを含有することにより、塗膜光沢及び塗膜密着性を向上することができる。
<Coating composition>
The coating composition of the present invention contains the polymer emulsion. A pigment, and if necessary, can further contain water, a viscosity control agent, an antifoaming agent, an antioxidant, an ultraviolet absorber and the like.
Examples of pigments include extender pigments such as talc, kaolin, calcium carbonate, and barium sulfate; colored pigments such as bengara, carbon black, ultramarine, and yellow iron oxide; white pigments such as titanium dioxide and zinc oxide, titanium mica, and bismuth oxychloride Inorganic pigments such as pearl pigments; dyes as organic synthetic dyes, organic pigments, and the like. These pigments may be used alone or in combination of two or more.
The coating composition of the present invention can improve coating film gloss and coating film adhesion by containing the polymer emulsion.
本発明の塗料組成物中のポリマーエマルションの含有量は、塗膜光沢及び塗膜密着性の観点から、塗料組成物中の全固形分に対し固形分換算で、好ましくは５質量％以上、より好ましくは１０質量％以上、更に好ましくは１５質量％以上であり、そして、好ましくは９０質量％以下、より好ましくは８５質量％以下、更に好ましくは８０質量％以下である。 The content of the polymer emulsion in the coating composition of the present invention is preferably 5% by mass or more in terms of solid content with respect to the total solid content in the coating composition from the viewpoint of coating film gloss and coating film adhesion. Preferably it is 10 mass% or more, More preferably, it is 15 mass% or more, Preferably it is 90 mass% or less, More preferably, it is 85 mass% or less, More preferably, it is 80 mass% or less.
本発明の塗料組成物に顔料が含まれる場合、塗料組成物中の顔料の含有量は、塗膜光沢、及び塗膜密着性の観点から、塗料組成物中の全固形分に対し固形物換算（ＰＷＣ）で、好ましくは５質量％以上、より好ましくは２０質量％以上、更に好ましくは３０質量％以上であり、そして、好ましくは９５質量％以下、より好ましくは８０質量％以下、更に好ましくは７０質量％以下である。ＰＷＣは下記式により算出される。
ＰＷＣ＝塗料組成物中の顔料固形分 ÷（塗料組成物中の全固形分）×１００
When a pigment is contained in the coating composition of the present invention, the content of the pigment in the coating composition is in terms of solids relative to the total solid content in the coating composition from the viewpoint of coating film gloss and coating film adhesion. (PWC), preferably 5% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and preferably 95% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less. PWC is calculated by the following formula.
PWC = pigment solid content in coating composition / (total solid content in coating composition) × 100
＜ポリマー塗膜＞
本発明のポリマー塗膜（以下、単に「塗膜」ともいう）は、前記塗料組成物を基板に塗布し、乾燥して形成される。
用いられる基板に特に制限はなく、ガラス、金属（アルミニウム、ステンレス等）、セラミックス（碍子、タイル等）、耐熱性高分子材料等からなる基板が挙げられる。
前記塗料組成物を、基板に塗布後、乾燥するが、乾燥工程で加熱することにより、乾燥時間を短縮し、形成される塗膜の硬度を向上させることができる。加熱温度は、好ましくは４０℃以上３００℃以下、より好ましくは１００℃以上１５０℃以下であり、加熱時間は、好ましくは３０秒以上２時間以下、より好ましくは５分以上６０分以下である。
本発明の塗膜の厚さは、用途等により異なるが、生産性、塗膜光沢、及び塗膜密着性の観点から、好ましくは４０μｍ以下、より好ましくは３０μｍ以下であり、そして、硬度を高める観点から、好ましくは１μｍ以上、より好ましくは２μｍ以上である。
<Polymer coating film>
The polymer coating film of the present invention (hereinafter also simply referred to as “coating film”) is formed by applying the coating composition onto a substrate and drying it.
There is no restriction | limiting in particular in the board | substrate used, The board | substrate which consists of glass, a metal (aluminum, stainless steel, etc.), ceramics (an insulator, a tile, etc.), a heat resistant polymer material, etc. is mentioned.
The coating composition is applied to the substrate and then dried. By heating in the drying step, the drying time can be shortened and the hardness of the formed coating film can be improved. The heating temperature is preferably 40 ° C. or higher and 300 ° C. or lower, more preferably 100 ° C. or higher and 150 ° C. or lower, and the heating time is preferably 30 seconds or longer and 2 hours or shorter, more preferably 5 minutes or longer and 60 minutes or shorter.
Although the thickness of the coating film of the present invention varies depending on applications, etc., it is preferably 40 μm or less, more preferably 30 μm or less from the viewpoint of productivity, coating film gloss, and coating film adhesion, and increases hardness. From the viewpoint, it is preferably 1 μm or more, more preferably 2 μm or more.
実施例１〜１２及び比較例１〜６
（１）界面活性剤組成物の製造
〔ａ〕界面活性剤組成物Ａの製造
撹拌装置付きフラスコに、１−オクタデカノール（商品名：カルコール８０９８、パーム核油由来、花王株式会社製）７０００ｇ（２５．９モル）、固体酸触媒としてγ−アルミナ（ＳＴＲＥＭ Ｃｈｅｍｉｃａｌｓ社製）７００ｇ（原料アルコールに対して１０質量％）を仕込み、撹拌下、２８０℃にて窒素を系内に流通させながら（窒素流通量：７０００ｍＬ／ｍｉｎ）、１０時間、反応を行い、Ｃ１８原料内部オレフィンを製造した。
このＣ１８原料内部オレフィンを薄膜流下式スルホン化装置にて、ＳＯ３ガスによりスルホン化し、１分経過後にＮａＯＨで中和、加水分解してスルホン酸塩粗組成物を得た。さらに、石油エーテルを用いて洗浄、精製したところ、得られたスルホン酸塩組成物（ｘ１）中のＣ１８ヒドロキシアルカンスルホン酸塩含有量は８４質量部、Ｃ１８内部オレフィンスルホン酸塩含有量は１６質量部であり、Ｃ１８内部オレフィン含有量は後述するガスクロマトグラフィーでは検出できなかった。次いで、Ｃ１８原料内部オレフィンを添加し、Ｃ１８ヒドロキシアルカンスルホン酸塩とＣ１８内部オレフィンスルホン酸塩の合計１００質量部に対し、Ｃ１８内部オレフィンを０．３質量部含有した界面活性剤組成物Ａを得た。
Examples 1-12 and Comparative Examples 1-6
(1) Manufacture of surfactant composition [a] Manufacture of surfactant composition A In a flask with a stirrer, 1-octadecanol (trade name: Calcoal 8098, derived from palm kernel oil, manufactured by Kao Corporation) 7000 g (25.9 mol), 700 g of γ-alumina (manufactured by STREM Chemicals) as a solid acid catalyst (10% by mass with respect to the raw material alcohol) was charged, and nitrogen was passed through the system at 280 ° C. with stirring ( (Nitrogen flow rate: 7000 mL / min) Reaction was performed for 10 hours to produce a C18 raw material internal olefin.
This C18 raw material internal olefin was sulfonated with SO 3 gas in a thin film flow down type sulfonation apparatus, neutralized with NaOH after 1 minute, and hydrolyzed to obtain a sulfonate crude composition. Furthermore, when it wash | cleans and refine | purifies using petroleum ether, C18 hydroxyalkane sulfonate content in the obtained sulfonate composition (x1) is 84 mass parts, C18 internal olefin sulfonate content is 16 masses. The C18 internal olefin content could not be detected by gas chromatography described later. Subsequently, C18 raw material internal olefin is added, and surfactant composition A containing 0.3 part by mass of C18 internal olefin is obtained with respect to 100 parts by mass in total of C18 hydroxyalkane sulfonate and C18 internal olefin sulfonate. It was.
〔ｂ〕界面活性剤組成物Ｂの製造
前記〔ａ〕の精製後のスルホン酸塩組成物（ｘ１）に、Ｃ１８原料内部オレフィンを添加し、Ｃ１８ヒドロキシアルカンスルホン酸塩とＣ１８内部オレフィンスルホン酸塩の合計１００質量部に対し、Ｃ１８内部オレフィンを１．１質量部含有した界面活性剤組成物Ｂを得た。
[B] Production of surfactant composition B C18 raw material internal olefin is added to the sulfonate composition (x1) after the purification of [a], and C18 hydroxyalkane sulfonate and C18 internal olefin sulfonate are added. A surfactant composition B containing 1.1 parts by mass of C18 internal olefin was obtained with respect to 100 parts by mass in total.
〔ｃ〕界面活性剤組成物Ｃの製造
前記〔ａ〕の精製後のスルホン酸塩組成物（ｘ１）に、Ｃ１８原料内部オレフィンを添加し、Ｃ１８ヒドロキシアルカンスルホン酸塩とＣ１８内部オレフィンスルホン酸塩の合計１００質量部に対し、Ｃ１８内部オレフィンを１．５質量部含有した界面活性剤組成物Ｃを得た。
[C] Production of Surfactant Composition C C18 raw material internal olefin is added to the sulfonate composition (x1) after the purification of [a], and C18 hydroxyalkane sulfonate and C18 internal olefin sulfonate are added. A surfactant composition C containing 1.5 parts by mass of C18 internal olefin was obtained with respect to 100 parts by mass in total.
〔ｄ〕界面活性剤組成物Ｄの製造
前記〔ａ〕の精製後のスルホン酸塩組成物（ｘ１）に、Ｃ１８原料内部オレフィンを添加し、Ｃ１８ヒドロキシアルカンスルホン酸塩とＣ１８内部オレフィンスルホン酸塩の合計１００質量部に対し、Ｃ１８内部オレフィンを２．８質量部含有した界面活性剤組成物Ｄを得た。
[D] Production of Surfactant Composition D To the sulfonate composition (x1) after the purification of [a], a C18 raw material internal olefin is added to obtain a C18 hydroxyalkane sulfonate and a C18 internal olefin sulfonate. A surfactant composition D containing 2.8 parts by mass of C18 internal olefin was obtained with respect to 100 parts by mass in total.
〔ｅ〕界面活性剤組成物Ｅの製造
前記〔ａ〕のＣ１８原料内部オレフィンを薄膜流下式スルホン化装置にて、ＳＯ３ガスによりスルホン化し、３０秒以内にＮａＯＨで中和、加水分解してスルホン酸塩粗組成物を得た。さらに、石油エーテルを用いて精製したところ、スルホン酸塩組成物（ｘ２）中のＣ１８ヒドロキシアルカンスルホン酸塩含有量は９３質量部、Ｃ１８内部オレフィンスルホン酸塩含有量は７質量部であり、Ｃ１８内部オレフィン含有量は後述するガスクロマトグラフィーでは検出できなかった。Ｃ１８原料内部オレフィンを添加し、Ｃ１８ヒドロキシアルカンスルホン酸塩とＣ１８内部オレフィンスルホン酸塩の合計１００質量部に対し、Ｃ１８内部オレフィンを１．５質量部含有した界面活性剤組成物Ｅを得た。
[E] Production of Surfactant Composition E The C18 raw material internal olefin of [a] was sulfonated with SO 3 gas in a thin film flow type sulfonation apparatus, neutralized with NaOH within 30 seconds, and hydrolyzed. A crude sulfonate salt composition was obtained. Furthermore, when refine | purifying using petroleum ether, C18 hydroxyalkanesulfonate content in a sulfonate composition (x2) is 93 mass parts, C18 internal olefin sulfonate content is 7 mass parts, C18 The internal olefin content could not be detected by gas chromatography described later. C18 raw material internal olefin was added, and surfactant composition E containing 1.5 parts by mass of C18 internal olefin was obtained relative to 100 parts by mass in total of C18 hydroxyalkane sulfonate and C18 internal olefin sulfonate.
〔ｆ〕界面活性剤組成物Ｆの製造
前記〔ａ〕のＣ１８原料内部オレフィンを薄膜流下式スルホン化装置にて、ＳＯ３ガスによりスルホン化し、１０分間熟成後、ＮａＯＨで中和、加水分解してスルホン酸塩粗組成物を得た。さらに、石油エーテルを用いて精製したところ、得られたスルホン酸塩組成物（ｘ３）中のＣ１８ヒドロキシアルカンスルホン酸塩含有量は４６質量部、Ｃ１８内部オレフィンスルホン酸塩含有量は５４質量部であり、Ｃ１８内部オレフィン含有量は後述するガスクロマトグラフィーでは検出できなかった。Ｃ１８原料内部オレフィンを添加し、Ｃ１８ヒドロキシアルカンスルホン酸塩とＣ１８内部オレフィンスルホン酸塩の合計１００質量部に対し、Ｃ１８内部オレフィンを１．５質量部含有した界面活性剤組成物Ｆを得た。
[F] Production of Surfactant Composition F The C18 raw material internal olefin of [a] is sulfonated with SO 3 gas in a thin film flow type sulfonation apparatus, aged for 10 minutes, then neutralized with NaOH and hydrolyzed. Thus, a crude sulfonate composition was obtained. Furthermore, when refine | purifying using petroleum ether, C18 hydroxyalkane sulfonate content in the obtained sulfonate composition (x3) is 46 mass parts, C18 internal olefin sulfonate content is 54 mass parts. Yes, the C18 internal olefin content could not be detected by gas chromatography to be described later. C18 raw material internal olefin was added, and surfactant composition F containing 1.5 parts by mass of C18 internal olefin was obtained with respect to 100 parts by mass in total of C18 hydroxyalkane sulfonate and C18 internal olefin sulfonate.
〔ｇ〕界面活性剤組成物Ｇの製造
１−ヘキサデカノール（商品名：「カルコール６０９８」、パーム核油由来、花王株式会社製）を原料にして、前記〔ａ〕と同様に、Ｃ１６原料内部オレフィンを製造した。
このＣ１６原料内部オレフィンを薄膜流下式スルホン化装置にて、ＳＯ３ガスによりスルホン化し、１分経過後にＮａＯＨで中和、加水分解してスルホン酸塩粗組成物を得た。さらに、石油エーテルを用いて精製したところ、得られたスルホン酸塩組成物（ｘ４）中のＣ１６ヒドロキシアルカンスルホン酸塩含有量は８５質量部、Ｃ１６内部オレフィンスルホン酸塩含有量は１５質量部であり、Ｃ１６内部オレフィン含有量は後述するガスクロマトグラフィーでは検出できなかった。Ｃ１６原料内部オレフィンを添加し、Ｃ１６ヒドロキシアルカンスルホン酸塩とＣ１６内部オレフィンスルホン酸塩の合計１００質量部に対し、Ｃ１６内部オレフィンを１．５質量部含有した界面活性剤組成物Ｇを得た。
[G] Production of Surfactant Composition G 1-Hexadecanol (trade name: “CALCOL 6098”, derived from palm kernel oil, manufactured by Kao Corporation) was used as a raw material, and as in [a] above, a C16 raw material An internal olefin was produced.
This C16 raw material internal olefin was sulfonated with SO 3 gas in a thin film flow down type sulfonation apparatus, neutralized with NaOH after 1 minute, and hydrolyzed to obtain a sulfonate crude composition. Furthermore, when refine | purifying using petroleum ether, C16 hydroxyalkanesulfonate content in the obtained sulfonate composition (x4) is 85 mass parts, C16 internal olefin sulfonate content is 15 mass parts. Yes, the C16 internal olefin content could not be detected by gas chromatography to be described later. C16 raw material internal olefin was added, and surfactant composition G containing 1.5 parts by mass of C16 internal olefin was obtained with respect to a total of 100 parts by mass of C16 hydroxyalkane sulfonate and C16 internal olefin sulfonate.
〔ｈ〕界面活性剤組成物Ｈの製造
１−テトラデカノール（商品名：「カルコール４０９８」、ヤシ油由来、花王株式会社製）を原料にして、前記〔ａ〕と同様に、Ｃ１４原料内部オレフィンを製造した。
このＣ１４内部オレフィンを薄膜流下式スルホン化装置にて、ＳＯ３ガスによりスルホン化し、３分経過後にＮａＯＨで中和、加水分解してスルホン酸塩粗組成物を得た。さらに、石油エーテルを用いて精製したところ、得られたスルホン酸塩組成物（ｘ５）中のＣ１４ヒドロキシアルカンスルホン酸塩含有量は７５質量部、Ｃ１４内部オレフィンスルホン酸塩含有量は２５質量部であり、Ｃ１４内部オレフィン含有量は後述するガスクロマトグラフィーでは検出できなかった。原料Ｃ１４内部オレフィンを添加し、Ｃ１４ヒドロキシスルホン酸塩とＣ１４内部オレフィンスルホン酸塩の合計量１００質量部に対し、Ｃ１４内部オレフィンを１．５質量部含有した界面活性剤組成物Ｈを得た。
[H] Production of Surfactant Composition H Using 1-tetradecanol (trade name: “Calcoal 4098”, derived from coconut oil, manufactured by Kao Corporation) as a raw material, similarly to the above [a], inside the C14 raw material Olefin was produced.
This C14 internal olefin was sulfonated with SO 3 gas in a thin film flow type sulfonation apparatus, neutralized with NaOH after 3 minutes, and hydrolyzed to obtain a sulfonate crude composition. Furthermore, when refine | purifying using petroleum ether, C14 hydroxyalkane sulfonate content in the obtained sulfonate composition (x5) is 75 mass parts, C14 internal olefin sulfonate content is 25 mass parts. Yes, the C14 internal olefin content could not be detected by gas chromatography to be described later. The raw material C14 internal olefin was added, and surfactant composition H containing 1.5 parts by mass of C14 internal olefin was obtained with respect to 100 parts by mass of the total amount of C14 hydroxysulfonate and C14 internal olefin sulfonate.
〔ｉ〕界面活性剤組成物Ｉの製造
１−ドデカノール（商品名：「カルコール２０９８」、ヤシ油由来、花王株式会社製）を原料にして、前記〔ａ〕と同様に、Ｃ１２内部オレフィンを製造した。このＣ１２内部オレフィンを薄膜流下式スルホン化装置にて、ＳＯ３ガスによりスルホン化し、１分経過後にＮａＯＨで中和、加水分解してスルホン酸塩粗組成物を得た。石油エーテルを用いて精製したところ、得られたスルホン酸塩組成物（ｘ６）中のＣ１２ヒドロキシアルカンスルホン酸塩含有量は８４質量部、Ｃ１２内部オレフィンスルホン酸塩含有量は１６質量部であり、Ｃ１２内部オレフィン含有量は後述するガスクロマトグラフィーでは検出できなかった。Ｃ１２原料内部オレフィンを添加し、Ｃ１２ヒドロキシアルカンスルホン酸塩とＣ１２内部オレフィンスルホン酸塩の合計量１００質量部に対し、Ｃ１２内部オレフィンを１．５質量部含有した界面活性剤組成物Ｉを得た。
[I] Production of Surfactant Composition I 1-Dodecanol (trade name: “Calcoal 2098”, derived from coconut oil, manufactured by Kao Corporation) is used as a raw material to produce C12 internal olefin in the same manner as in [a] above. did. This C12 internal olefin was sulfonated with SO 3 gas in a thin film flow type sulfonation apparatus, neutralized with NaOH after 1 minute, and hydrolyzed to obtain a sulfonate crude composition. When purified using petroleum ether, the C12 hydroxyalkanesulfonate content in the resulting sulfonate composition (x6) is 84 parts by mass, and the C12 internal olefin sulfonate content is 16 parts by mass. The C12 internal olefin content could not be detected by gas chromatography described below. C12 raw material internal olefin was added, and surfactant composition I containing 1.5 parts by mass of C12 internal olefin was obtained with respect to 100 parts by mass of the total amount of C12 hydroxyalkane sulfonate and C12 internal olefin sulfonate. .
〔ｊ〕界面活性剤組成物Ｊの製造
１−エイコサノール（商品名：「１−Ｅｉｃｏｓａｎｏｌ」、東京化成工業株式会社製）を原料にして、前記〔ａ〕と同様に、Ｃ２０内部オレフィンを製造した。このＣ２０内部オレフィンを薄膜流下式スルホン化装置にて、ＳＯ３ガスによりスルホン化し、１分経過後にＮａＯＨで中和、加水分解してスルホン酸塩粗組成物を得た。石油エーテルを用いて精製したところ、得られたスルホン酸塩組成物（ｘ７）中のＣ２０ヒドロキシアルカンスルホン酸塩含有量は８４質量部、Ｃ２０内部オレフィンスルホン酸塩含有量は１６質量部であり、Ｃ２０内部オレフィン含有量は後述するガスクロマトグラフィーでは検出できなかった。Ｃ２０原料内部オレフィンを添加し、Ｃ２０ヒドロキシアルカンスルホン酸塩とＣ２０内部オレフィンスルホン酸塩の合計量１００質量部に対し、Ｃ２０内部オレフィンを１．５質量部含有した界面活性剤組成物Ｊを得た。
[J] Production of Surfactant Composition J Using 1-eicosanol (trade name: “1-Eicosanol”, manufactured by Tokyo Chemical Industry Co., Ltd.) as a raw material, a C20 internal olefin was produced in the same manner as in the above [a]. . This C20 internal olefin was sulfonated with SO 3 gas in a thin film flow type sulfonation apparatus, neutralized with NaOH after 1 minute, and hydrolyzed to obtain a sulfonate crude composition. When purified using petroleum ether, the C20 hydroxyalkanesulfonate content in the obtained sulfonate composition (x7) is 84 parts by mass, and the C20 internal olefin sulfonate content is 16 parts by mass. The C20 internal olefin content could not be detected by gas chromatography described below. C20 raw material internal olefin was added, and surfactant composition J containing 1.5 parts by mass of C20 internal olefin was obtained with respect to 100 parts by mass of the total amount of C20 hydroxyalkane sulfonate and C20 internal olefin sulfonate. .
〔ｋ〕界面活性剤組成物Ｋの製造
ステアリン酸（商品名：「ルナックＳ−９０Ｖ」、パーム核油由来、花王株式会社製）を原料にして、ビス（トリフェニルホスフィン）パラジウム（II）及びトリフェニルホスフィンを用いて、脱一酸化炭素方法によりα―オレフィンと内部オレフィン混合物を得た。さらに固体酸性シリカ−アルミナ触媒（製品名：「Ｘ−６００」、Ｃｒｉｔｅｒｉｏｎ Ｃａｔａｌｙｓｔ社製）を、固定床再循環バッチ反応器に充填した。α―オレフィンと内部オレフィン混合物を、反応器の供給溜めに入れた。触媒を、１００℃の窒素流で１４時間活性化した。反応器（触媒床および供給溜め）を１２０℃に加熱し、オレフィンを、５００ｇ／分の速度で、再循環方式において触媒床上で流動させ、α―オレフィンを異性化し、Ｃ１７原料内部オレフィンを製造した。このＣ１７原料内部オレフィンを薄膜流下式スルホン化装置にて、ＳＯ３ガスによりスルホン化し、３分経過後にＮａＯＨで中和、加水分解してスルホン酸塩粗組成物を得た。石油エーテルを用いて精製したところ、得られたスルホン酸組成物（ｘ８）中のＣ１７ヒドロキシアルカンスルホン酸塩含有量は７２質量部、Ｃ１７内部オレフィンスルホン酸塩含有量は２８質量部であり、Ｃ１７内部オレフィン含有量は後述するガスクロマトグラフィーでは検出できなかった。Ｃ１７原料内部オレフィンを添加し、Ｃ１７ヒドロキシアルカンスルホン酸塩とＣ１７内部オレフィンスルホン酸塩の合計量１００質量部に対し、Ｃ１７内部オレフィンを１．９質量部含有した界面活性剤組成物Ｋを得た。
[K] Production of Surfactant Composition K Using stearic acid (trade name: “Lunac S-90V”, derived from palm kernel oil, manufactured by Kao Corporation) as a raw material, bis (triphenylphosphine) palladium (II) and Using triphenylphosphine, a mixture of α-olefin and internal olefin was obtained by the carbon monoxide method. Further, a solid acidic silica-alumina catalyst (product name: “X-600”, manufactured by Criterion Catalyst) was charged into a fixed bed recirculation batch reactor. The α-olefin and internal olefin mixture was placed in the reactor supply reservoir. The catalyst was activated with a nitrogen flow of 100 ° C. for 14 hours. The reactor (catalyst bed and feed reservoir) was heated to 120 ° C. and the olefin was flowed over the catalyst bed in a recycle mode at a rate of 500 g / min to isomerize the α-olefin to produce a C17 feed internal olefin. . This C17 raw material internal olefin was sulfonated with SO 3 gas in a thin film flow-down sulfonation apparatus, neutralized with NaOH after 3 minutes, and hydrolyzed to obtain a sulfonate crude composition. When refine | purifying using petroleum ether, C17 hydroxyalkanesulfonate content in the obtained sulfonic acid composition (x8) is 72 mass parts, C17 internal olefin sulfonate content is 28 mass parts, C17 The internal olefin content could not be detected by gas chromatography described later. C17 raw material internal olefin was added, and surfactant composition K containing 1.9 parts by mass of C17 internal olefin was obtained with respect to 100 parts by mass of the total amount of C17 hydroxyalkane sulfonate and C17 internal olefin sulfonate. .
〔ｎ〕界面活性剤組成物Ｎの製造
「リニアレン１６８」〔α―オレフィン（Ｃ１６の含有量：５７±３％、Ｃ１８の含有量：４３±３％）、出光興産株式会社製〕を薄膜流下式スルホン化装置にて、ＳＯ３ガスによりスルホン化し、１分以内にＮａＯＨで中和、加水分解してスルホン酸塩粗組成物を得た。石油エーテルを用いて精製し、後述するＨＰＬＣ−ＭＳより定量したところ、得られたスルホン酸塩組成物（ｘ９）中のヒドロキシアルカンスルホン酸塩含有量は５５質量部、内部オレフィンスルホン酸塩含有量は３６質量部、α−オレフィンスルホン酸塩含有量は９質量部であり、内部オレフィン含有量は後述するガスクロマトグラフィーでは検出できなかった。このスルホン酸塩組成物（ｘ９）を界面活性剤組成物Ｎとしてそのまま用いた。
[N] Production of Surfactant Composition N “Linearene 168” [α-olefin (C16 content: 57 ± 3%, C18 content: 43 ± 3%), manufactured by Idemitsu Kosan Co., Ltd.] Sulfonated with SO 3 gas in a type sulfonation apparatus, neutralized with NaOH and hydrolyzed within 1 minute to obtain a sulfonate crude composition. When refine | purifying using petroleum ether and quantifying by HPLC-MS mentioned later, hydroxyalkanesulfonate content in the obtained sulfonate composition (x9) is 55 mass parts, content of internal olefin sulfonate Was 36 parts by mass, the α-olefin sulfonate content was 9 parts by mass, and the internal olefin content could not be detected by gas chromatography described later. This sulfonate composition (x9) was used as the surfactant composition N as it was.
〔ｏ〕界面活性剤組成物Ｏの製造
１−デカノール（商品名：「カルコール１０９８」、ヤシ油由来、花王株式会社製）を原料にして、前記〔ａ〕と同様にして、Ｃ１０原料内部オレフィンを製造した。このＣ１０原料内部オレフィンを薄膜流下式スルホン化装置にて、ＳＯ３ガスによりスルホン化し、１分経過後にＮａＯＨで中和、加水分解してスルホン酸塩粗組成物を得た。石油エーテルを用いて精製したところ、スルホン酸塩組成物（ｘ１０）中のＣ１０ヒドロキシスルホン酸塩含有量は８４質量部、Ｃ１０内部オレフィンスルホン酸塩含有量は１６質量部であり、Ｃ１０内部オレフィン含有量は後述するガスクロマトグラフィーでは検出できなかった。Ｃ１０原料内部オレフィンを添加し、Ｃ１０ヒドロキシアルカンスルホン酸塩とＣ１０内部オレフィンスルホン酸塩の合計量１００質量部に対し、Ｃ１０内部オレフィンを１．５質量部含有した界面活性剤組成物Ｏを得た。
[O] Production of Surfactant Composition O Using 1-decanol (trade name: “Calcoal 1098”, derived from coconut oil, manufactured by Kao Corporation) as a raw material, in the same manner as in the above [a], a C10 raw material internal olefin Manufactured. This C10 raw material internal olefin was sulfonated with SO 3 gas in a thin film flow-down sulfonation apparatus, neutralized with NaOH after 1 minute, and hydrolyzed to obtain a sulfonate crude composition. When refined using petroleum ether, the C10 hydroxysulfonate content in the sulfonate composition (x10) is 84 parts by mass, the C10 internal olefin sulfonate content is 16 parts by mass, and the C10 internal olefin is contained. The amount could not be detected by gas chromatography described below. C10 raw material internal olefin was added, and surfactant composition O containing 1.5 parts by mass of C10 internal olefin was obtained with respect to 100 parts by mass of the total amount of C10 hydroxyalkane sulfonate and C10 internal olefin sulfonate. .
〔ｐ〕界面活性剤組成物Ｐの製造
前記（ａ）で得られたスルホン酸塩粗組成物を石油エーテル精製後、原料であるＣ１８内部オレフィンを添加しないものを界面活性剤組成物Ｐとした。Ｃ１８ヒドロキシアルカンスルホン酸塩含有量は８４質量部、Ｃ１８内部オレフィンスルホン酸塩含有量は１６質量部であり、Ｃ１８内部オレフィン含有量は後述するガスクロマトグラフィーでは検出できなかった。
[P] Manufacture of Surfactant Composition P Surfactant Composition P was obtained by refining the crude sulfonate composition obtained in (a) above with petroleum ether and adding no C18 internal olefin as a raw material. . The C18 hydroxyalkanesulfonate content was 84 parts by mass, the C18 internal olefin sulfonate content was 16 parts by mass, and the C18 internal olefin content could not be detected by gas chromatography described below.
〔ｑ〕界面活性剤組成物Ｑの製造
前記（ａ）で得られた界面活性剤組成物Ａに、原料であるＣ１８内部オレフィンを添加して、Ｃ１８ヒドロキシアルカンスルホン酸塩とＣ１８内部オレフィンスルホン酸塩の合計量１００質量部に対し、Ｃ１８内部オレフィンを３．５質量部含有した界面活性剤組成物Ｑを得た。
[Q] Production of Surfactant Composition Q To the surfactant composition A obtained in (a) above, a C18 internal olefin as a raw material is added to obtain a C18 hydroxyalkane sulfonate and a C18 internal olefin sulfonic acid. Surfactant composition Q containing 3.5 parts by mass of C18 internal olefin was obtained with respect to 100 parts by mass of the total amount of salt.
＜組成分析方法＞
各成分の組成は、以下の方法により分析した。分液ロートにサンプルを採取し、５０体積％エタノール水溶液及び石油エーテルを添加し、よく振とうし、静置後、石油エーテル相とエタノール水相に分相した。石油エーテル相を下記条件にてガスクロマトグラフィーを用いてピーク面積から内部オレフィンを定量した。エタノール水相を下記条件にてＨＰＬＣ−ＭＳを用いてヒドロキシアルカンスルホン酸塩と内部オレフィンスルホン酸塩を分離定量した。
<Composition analysis method>
The composition of each component was analyzed by the following method. A sample was collected in a separatory funnel, 50% by volume ethanol aqueous solution and petroleum ether were added, shaken well, allowed to stand, and then separated into a petroleum ether phase and an ethanol aqueous phase. The internal olefin was determined from the peak area of the petroleum ether phase using gas chromatography under the following conditions. The hydroxyalkane sulfonate and the internal olefin sulfonate were separated and quantified from the ethanol aqueous phase using HPLC-MS under the following conditions.
・ガスクロマトグラフィー条件
装置：Ａｇｉｌｅｎｔ ６８５０ＧＣ（アジレントテクノロジー社製）
カラム：Ｕｌｔｒａ Ａｌｌｏｙ ＵＡ＋−１（ＨＴ）キャピラリーカラム １５ｍ×２５０μｍ×０．１５μｍ（フロンティア・ラボ株式会社製）
検出器：水素炎イオン検出器（ＦＩＤ）
インジェクション温度：３００℃
ディテクター温度：３５０℃
Ｈｅ流量：３．８ｍＬ／ｍｉｎ
・ Gas chromatography conditions Apparatus: Agilent 6850GC (manufactured by Agilent Technologies)
Column: Ultra Alloy UA + -1 (HT) capillary column 15 m × 250 μm × 0.15 μm (manufactured by Frontier Laboratories)
Detector: Hydrogen flame ion detector (FID)
Injection temperature: 300 ° C
Detector temperature: 350 ° C
He flow rate: 3.8 mL / min
・ＨＰＬＣ−ＭＳ条件
質量比〔（ａ）成分／（ｂ）成分〕は、ＨＰＬＣ−ＭＳにより測定した。具体的には、ＨＰＬＣによりヒドロキシアルカンスルホン酸塩と内部オレフィンスルホン酸塩を分離し、それぞれをＭＳにかけることで同定した。そのＨＰＬＣ−ＭＳピーク面積から各々の割合を求めた。なお、測定に使用した装置及び条件は次の通りである。
ＨＰＬＣ−ＭＳ装置：Ａｇｉｌｅｎｔ １１００ ＬＣ／ＭＳＤ Ｍｏｄｅｌ Ｇ１９４６Ｄ Ｍａｓｓ Ｓｐｅｃｔｒｏｍｅｔｅｒ（アジレントテクノロジー社製）
カラム：Ｌ−ｃｏｌｕｍｎ ＯＤＳ（一般財団法人化学物質評価研究機構製、粒子径 ５μｍ、４．６×１５０ｍｍ）
サンプル調製：メタノールで１０００倍希釈
溶離液Ａ：１０ｍＭ酢酸アンモニウム水溶液
溶離液Ｂ：１０ｍＭ酢酸アンモニウムメタノール溶液
グラジェント条件：開始時（溶離液Ａ／溶離液Ｂ＝３０／７０（体積比））→１０分（３０／７０）→５５分（０／１００）→６５分（０／１００）→６６分（３０／７０）→７５分（３０／７０）
ＭＳ検出：陰イオン検出 ｍ／ｚ６０〜１６００、ＵＶ２４０ｎｍ
-HPLC-MS conditions Mass ratio [(a) component / (b) component] was measured by HPLC-MS. Specifically, the hydroxyalkane sulfonate and the internal olefin sulfonate were separated by HPLC and each was subjected to MS for identification. Each ratio was calculated | required from the HPLC-MS peak area. In addition, the apparatus and conditions used for the measurement are as follows.
HPLC-MS apparatus: Agilent 1100 LC / MSD Model G1946D Mass Spectrometer (manufactured by Agilent Technologies)
Column: L-column ODS (manufactured by Chemicals Evaluation and Research Institute, particle size 5 μm, 4.6 × 150 mm)
Sample preparation: 1000-fold dilution with methanol Eluent A: 10 mM ammonium acetate aqueous solution Eluent B: 10 mM ammonium acetate methanol solution Gradient condition: At start (eluent A / eluent B = 30/70 (volume ratio)) → 10 Minute (30/70) → 55 minutes (0/100) → 65 minutes (0/100) → 66 minutes (30/70) → 75 minutes (30/70)
MS detection: negative ion detection m / z 60 to 1600, UV 240 nm
（２）ポリマーエマルションの製造
攪拌機（ＰＴＦＥ撹拌羽根付き硼珪酸ガラス棒を取り付けたもの）及び滴下ロートを備えた１Ｌの四つ口フラスコに、イオン交換水１１２．５ｇ、重合開始剤として過硫酸カリウム０．３６ｇ、表１に示す各界面活性剤組成物３．６ｇを混合し、５００ｒ／ｍｉｎで攪拌しながら、室温でアクリル酸ブチル１１０．８ｇ、メタクリル酸メチル１１０．８ｇ及びアクリル酸３．４ｇのモノマー混合物を約５分間かけて滴下ロートから滴下し、滴下後３０分間攪拌して乳化物滴下液を得た。
次に、攪拌機（硼珪酸ガラス製錨型撹拌棒を取り付けたもの）、還流冷却器及び滴下ロートを備えた１Ｌの四つ口セパラブルフラスコ内に、イオン交換水１６２．５ｇ、重合開始剤として過硫酸カリウム０．０９ｇ、表１に示す各界面活性剤組成物０．９０ｇ、前記乳化物滴下液の５質量％（１７．１ｇ）を仕込み、８０℃に昇温し、３０分間１段目重合を行なった。その後、残りの乳化物滴下液を８０℃に維持しながら３時間かけて滴下ロートから滴下し、滴下終了後、さらに１時間熟成し、エマルション（固形分濃度 ４５．５質量％）を得た。
得られたエマルションを３０℃以下に冷却し、２００メッシュステンレス金網でろ過し、エマルション中の凝集物を回収した。さらに、フラスコ内、及び攪拌羽根に付着した凝集物も回収した。
なお、界面活性剤組成物Ｌとしてリニアアルキルベンゼンスルホン酸ナトリウム（商品名：「ネオペレックスＧ−２５」、花王株式会社製）を、界面活性剤組成物Ｍとしてアルカンスルホン酸ナトリウム（商品名：「ラテムルＰＳ」、花王株式会社製）を用いた。
また、実施例１２は、界面活性剤組成物ＣとＧの質量比〔（Ｃ）／（Ｇ）〕が８／２となるように混合したものを用いた。
(2) Production of polymer emulsion In a 1 L four-necked flask equipped with a stirrer (with a borosilicate glass rod with PTFE stirring blades) and a dropping funnel, 112.5 g of ion-exchanged water and potassium persulfate as a polymerization initiator 0.36 g and 3.6 g of each surfactant composition shown in Table 1 were mixed and stirred at 500 r / min at room temperature with 110.8 g of butyl acrylate, 110.8 g of methyl methacrylate and 3.4 g of acrylic acid. The monomer mixture was dropped from the dropping funnel over about 5 minutes, and stirred for 30 minutes after dropping to obtain an emulsion dropping solution.
Next, 162.5 g of ion-exchanged water and a polymerization initiator were placed in a 1 L four-necked separable flask equipped with a stirrer (with a borosilicate glass vertical stirring rod), a reflux condenser and a dropping funnel. First, 0.09 g of potassium persulfate, 0.90 g of each surfactant composition shown in Table 1, and 5% by mass (17.1 g) of the emulsion dropping solution were charged, heated to 80 ° C., and the first stage for 30 minutes. Polymerization was performed. Thereafter, the remaining emulsion dropping liquid was dropped from the dropping funnel over 3 hours while maintaining at 80 ° C., and after completion of the dropping, the mixture was further aged for 1 hour to obtain an emulsion (solid content concentration 45.5% by mass).
The obtained emulsion was cooled to 30 ° C. or lower and filtered through a 200 mesh stainless steel wire mesh to collect aggregates in the emulsion. Furthermore, the aggregate which adhered to the inside of a flask and the stirring blade was also collect | recovered.
The surfactant composition L is sodium linear alkylbenzene sulfonate (trade name: “Neopelex G-25”, manufactured by Kao Corporation), and the surfactant composition M is sodium alkane sulfonate (trade name: “Latemul”). PS "manufactured by Kao Corporation) was used.
In Example 12, a mixture prepared so that the mass ratio [(C) / (G)] of the surfactant compositions C and G was 8/2 was used.
＜ポリマーエマルションの評価方法＞
（重合安定性）
前記（２）で回収した凝集物を水洗後、２６．６ｋＰａ、１０５℃で２時間乾燥し、質量を測定して、凝集物量を求めた。使用したモノマーの総量に対する凝集物の質量％で重合安定性を表した。なお、この値が小さいほど、重合安定性に優れていることを示す。結果を表１に示す。
<Method for evaluating polymer emulsion>
(Polymerization stability)
The aggregate collected in (2) was washed with water, dried at 26.6 kPa and 105 ° C. for 2 hours, and the mass was measured to determine the amount of aggregate. Polymerization stability was expressed in terms of mass% of aggregates based on the total amount of monomers used. In addition, it shows that it is excellent in polymerization stability, so that this value is small. The results are shown in Table 1.
（平均粒径）
前記（２）ポリマーエマルションの製造で得られたエマルションを２５質量％アンモニア水で中和し、ｐＨ８〜９とした。サブミクロン粒度分布測定装置「コールター Ｎ４ Ｐｌｕｓ」（ベックマン・コールター株式会社製）を使用して、中和後のポリマーエマルションを蒸留水で約３万倍に希釈し、粒子の平均粒径を測定した。測定解析法は、ユニモーダルモードを採用した。結果を表１に示す。
(Average particle size)
The emulsion obtained by the production of the (2) polymer emulsion was neutralized with 25% by mass ammonia water to pH 8-9. Using a submicron particle size distribution measuring device “Coulter N4 Plus” (manufactured by Beckman Coulter, Inc.), the neutralized polymer emulsion was diluted about 30,000 times with distilled water, and the average particle size of the particles was measured. . The unimodal mode was adopted as the measurement analysis method. The results are shown in Table 1.
（機械的安定性）
前記（２）ポリマーエマルションの製造において中和後のエマルション５０ｇをマロン式機械的安定性試験機（株式会社安田精機製作所製）にて、９８Ｎ、１０００ｒ／ｍｉｎの条件で５分間回転させ、生成した凝集物を２００メッシュステンレス金網でろ過し、ろ過残渣を水洗後に、２６．６ｋＰａ、１０５℃で２時間乾燥し、質量を測定して、凝集物量を求めた。使用したポリマーの総量に対する凝集物の質量％で機械的安定性を表した。なお、この値が小さいほど、機械的安定性に優れていることを示す。結果を表１に示す。
(Mechanical stability)
(2) In the production of the polymer emulsion, 50 g of the emulsion after neutralization was produced by rotating for 5 minutes under the conditions of 98 N, 1000 r / min with a Maron mechanical stability tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.). The aggregate was filtered through a 200-mesh stainless wire mesh, and the filtration residue was washed with water, dried at 26.6 kPa and 105 ° C. for 2 hours, and the mass was measured to determine the amount of aggregate. Mechanical stability was expressed in terms of mass% of aggregates based on the total amount of polymer used. In addition, it shows that it is excellent in mechanical stability, so that this value is small. The results are shown in Table 1.
（化学的安定性）
前記（２）ポリマーエマルションの製造において中和後のエマルションにイオン交換水を加え、ポリマー濃度が３質量％になるように希釈し、１０ｍｍｏｌ／Ｌ塩化カルシウム水溶液を滴下した。凝集物が生じる塩化カルシウム濃度を測定し、化学的安定性の指標とした。なお、この値が大きいほど、化学的安定性に優れていることを示す。結果を表１に示す。
(Chemical stability)
In the production of (2) polymer emulsion, ion-exchanged water was added to the neutralized emulsion to dilute the polymer concentration to 3% by mass, and 10 mmol / L calcium chloride aqueous solution was added dropwise. The calcium chloride concentration at which aggregates are formed was measured and used as an index of chemical stability. In addition, it shows that it is excellent in chemical stability, so that this value is large. The results are shown in Table 1.
（３）塗料組成物の製造
ポリエチレン製２５０ｍＬ広口瓶に１ｍｍ径と２ｍｍ径のガラスビーズを各５０ｇ、顔料として「タイペークＲ−６７０」〔二酸化チタン（ルチル型酸化チタン）、石原産業株式会社製、平均粒径約０．２１μｍ〕１５０ｇ、水溶性分散剤「ポイズ５３０」（特殊ポリカルボン酸型界面活性剤、花王株式会社製、４０質量％水溶液）３．７５ｇ、イオン交換水６２ｇを仕込み、ペイントシェーカーで３時間攪拌し、濾過によりガラスビーズを取り除き、顔料固形分が７０質量％である顔料水分散液を調製した。
次に１００ｍＬ三角フラスコに上記顔料水分散液７．１ｇ、前記（２）で得られた各エマルション１１．１ｇ、イオン交換水１．８ｇを秤取り、均一に混合し、仕上がり塗料固形分が５０質量％（ＰＷＣ５０質量％）の塗料を得た。
なお、ＰＷＣとは、下記式によって算出される値である。
ＰＷＣ＝顔料固形分 ÷（顔料固形分＋エマルション固形分）×１００
(3) Manufacture of coating composition 50 g each of 1 mm diameter and 2 mm diameter glass beads in a polyethylene 250 mL wide-mouth bottle, and “PEIKE R-670” as a pigment [titanium dioxide (rutile titanium oxide), manufactured by Ishihara Sangyo Co., Ltd., Average particle size of about 0.21 μm] 150 g, water-soluble dispersant “Poise 530” (special polycarboxylic acid type surfactant, manufactured by Kao Corporation, 40 mass% aqueous solution) 3.75 g, ion-exchanged water 62 g are charged, and paint The mixture was stirred for 3 hours with a shaker, the glass beads were removed by filtration, and a pigment aqueous dispersion having a pigment solid content of 70% by mass was prepared.
Next, 7.1 g of the pigment water dispersion, 11.1 g of each emulsion obtained in the above (2), and 1.8 g of ion-exchanged water are weighed and mixed uniformly in a 100 mL Erlenmeyer flask, and the finished paint solid content is 50 A coating material of mass% (PWC 50 mass%) was obtained.
PWC is a value calculated by the following equation.
PWC = pigment solid content / (pigment solid content + emulsion solid content) × 100
（４）ポリマー塗膜の製造
前記（３）で得られた塗料組成物をバーコーターＮｏ．８（株式会社安田精機製作所製）で、基材としてポリプロピレンフィルム及びアクリル板上にそれぞれ塗工し、塗工後、室温で一昼夜乾燥しポリマー塗膜を得た。
(4) Production of polymer coating film The coating composition obtained in (3) above was applied to a bar coater no. 8 (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) was coated on a polypropylene film and an acrylic plate as a base material, and after coating, the polymer coating film was obtained by drying overnight at room temperature.
＜ポリマー塗膜の評価方法＞
（塗膜光沢の測定）
前記（４）で得られた、基材としてポリプロピレンフィルム上に形成したポリマー塗膜の表面光沢を光沢計「ＧＭ−６０」（コニカミノルタ株式会社製）で、入射角度６０°の条件で測定した。結果を表１に示す。
<Evaluation method of polymer coating film>
(Measurement of film gloss)
The surface gloss of the polymer coating film formed on the polypropylene film as the base material obtained in the above (4) was measured with a gloss meter “GM-60” (manufactured by Konica Minolta Co., Ltd.) at an incident angle of 60 °. . The results are shown in Table 1.
（塗膜密着性（碁盤目試験））
前記（４）で得られた、基材としてアクリル板上に形成したポリマー塗膜を用いて、ＪＩＳ Ｋ５６００−５−６に規定されたクロスカット法に従って切込みを入れ、マス目を１００個形成した。「Ｓｃｏｔｃｈメンディングテープ」（住友スリーエム株式会社製、幅：１８ｍｍ）を十分に指でこすり貼り付けた後２分間放置し、１０ｍｍ／秒で垂直方向に剥離したときの塗膜に残るマス目の個数を計測した。結果を表１に示す。
(Coating adhesion (cross cut test))
Using the polymer coating film formed on the acrylic plate as the base material obtained in the above (4), incisions were made in accordance with the cross-cut method defined in JIS K5600-5-6 to form 100 squares. . “Scotch Mending Tape” (manufactured by Sumitomo 3M Ltd., width: 18 mm) is thoroughly rubbed with fingers and left for 2 minutes, and then left on the coating film when peeled off vertically at 10 mm / second. The number was counted. The results are shown in Table 1.
上記表１から明らかなように、実施例１〜１２は、比較例１〜３及び比較例５〜６と比べて、良好な重合安定性及び良好なエマルション粒径を維持しつつ、優れた機械的安定性、化学的安定性、塗膜光沢、及び塗膜密着性を示した。なお、比較例４は安定な乳化状態を保持できなかったためエマルションが不安定で、乳化重合を行うことができなかった。
実施例３，７〜１０を比較すると、炭素数が１８である実施例３が、重合安定性、機械的安定性、化学的安定性、塗膜光沢、及び塗膜密着性にも優れていた。
炭素数が１８である実施例１〜６を比較すると、（ｃ）成分の含有量が１．５質量％である実施例３が、良好な重合安定性及び良好なエマルション粒径を維持しつつ、機械的安定性、化学的安定性、塗膜光沢、及び塗膜密着性にも優れていた。
炭素数が１８である実施例３，５〜６を比較すると、（ａ）成分と（ｂ）成分の質量比〔（ａ）成分／（ｂ）成分〕が５．２５である実施例３が、良好な重合安定性及び良好なエマルション粒径を維持しつつ、機械的安定性、化学的安定性、塗膜光沢、及び塗膜密着性にも優れていた。
As is clear from Table 1 above, Examples 1 to 12 are superior to Comparative Examples 1 to 3 and Comparative Examples 5 to 6 while maintaining good polymerization stability and good emulsion particle size. Stability, chemical stability, film gloss, and film adhesion. In Comparative Example 4, since a stable emulsified state could not be maintained, the emulsion was unstable and emulsion polymerization could not be performed.
When comparing Examples 3 and 7 to 10, Example 3 having 18 carbon atoms was excellent in polymerization stability, mechanical stability, chemical stability, coating gloss, and coating adhesion. .
Comparing Examples 1 to 6 having 18 carbon atoms, Example 3 in which the content of component (c) is 1.5% by mass maintains good polymerization stability and good emulsion particle size. It was also excellent in mechanical stability, chemical stability, coating gloss, and coating adhesion.
Comparing Examples 3 and 6 having 18 carbon atoms, Example 3 in which the mass ratio of the component (a) to the component (b) [component (a) / component (b)] is 5.25 is as follows. While maintaining good polymerization stability and good emulsion particle size, it was excellent in mechanical stability, chemical stability, coating film gloss, and coating film adhesion.
本発明の乳化重合用アニオン性界面活性剤組成物は、塗料、接着剤、紙加工、繊維加工、プラスチック、ゴム等の分野に有用である。 The anionic surfactant composition for emulsion polymerization of the present invention is useful in the fields of paints, adhesives, paper processing, fiber processing, plastics, rubbers and the like.
Claims (7)
該原料内部オレフィンが天然油脂由来の炭素数１２以上２２以下の脂肪族アルコールの脱水反応により得られるものである、請求項１又は２に記載の乳化重合用アニオン性界面活性剤組成物。 An anionic surfactant composition for emulsion polymerization containing components (a) to (c) obtained by sulfonating a raw material internal olefin having 12 to 22 carbon atoms, neutralizing and then hydrolyzing. And
The anionic surfactant composition for emulsion polymerization according to claim 1 or 2, wherein the raw internal olefin is obtained by a dehydration reaction of an aliphatic alcohol having 12 to 22 carbon atoms derived from natural fats and oils.
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