JP4717434B2 - Silicone emulsion composition and mold release agent - Google Patents
Silicone emulsion composition and mold release agent Download PDFInfo
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- JP4717434B2 JP4717434B2 JP2004376850A JP2004376850A JP4717434B2 JP 4717434 B2 JP4717434 B2 JP 4717434B2 JP 2004376850 A JP2004376850 A JP 2004376850A JP 2004376850 A JP2004376850 A JP 2004376850A JP 4717434 B2 JP4717434 B2 JP 4717434B2
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- 229920001296 polysiloxane Polymers 0.000 title claims description 60
- 239000000839 emulsion Substances 0.000 title claims description 52
- 239000000203 mixture Substances 0.000 title claims description 51
- 239000006082 mold release agent Substances 0.000 title claims description 11
- -1 polyoxyethylene Polymers 0.000 claims description 39
- 239000002280 amphoteric surfactant Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 18
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 229960003237 betaine Drugs 0.000 claims description 9
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- 150000005215 alkyl ethers Chemical class 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000003240 coconut oil Substances 0.000 claims description 5
- 235000019864 coconut oil Nutrition 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000004512 die casting Methods 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims 1
- JNGWKQJZIUZUPR-UHFFFAOYSA-N [3-(dodecanoylamino)propyl](hydroxy)dimethylammonium Chemical group CCCCCCCCCCCC(=O)NCCC[N+](C)(C)[O-] JNGWKQJZIUZUPR-UHFFFAOYSA-N 0.000 claims 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- 239000002518 antifoaming agent Substances 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 12
- 239000003921 oil Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229940117986 sulfobetaine Drugs 0.000 description 5
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 4
- 239000005639 Lauric acid Substances 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 3
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- UWOVWIIOKHRNKU-UHFFFAOYSA-N 2,6-diphenyl-4-(2,4,6-triphenylpyridin-1-ium-1-yl)phenolate Chemical compound [O-]C1=C(C=2C=CC=CC=2)C=C([N+]=2C(=CC(=CC=2C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1C1=CC=CC=C1 UWOVWIIOKHRNKU-UHFFFAOYSA-N 0.000 description 2
- MXVBVDSNBADJOC-UHFFFAOYSA-N 2-(4,5-dihydroimidazol-1-yl)-4-hydroxybutanoic acid;sodium Chemical compound [Na].OCCC(C(O)=O)N1CCN=C1 MXVBVDSNBADJOC-UHFFFAOYSA-N 0.000 description 2
- GDYJHFQRHYNIOU-UHFFFAOYSA-N CCO.CCO.CCO.OS(O)(=O)=O Chemical class CCO.CCO.CCO.OS(O)(=O)=O GDYJHFQRHYNIOU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- JZKFHQMONDVVNF-UHFFFAOYSA-N dodecyl sulfate;tris(2-hydroxyethyl)azanium Chemical compound OCCN(CCO)CCO.CCCCCCCCCCCCOS(O)(=O)=O JZKFHQMONDVVNF-UHFFFAOYSA-N 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- XPALGXXLALUMLE-UHFFFAOYSA-N 2-(dimethylamino)tetradecanoic acid Chemical compound CCCCCCCCCCCCC(N(C)C)C(O)=O XPALGXXLALUMLE-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- DDGPBVIAYDDWDH-UHFFFAOYSA-N 3-[dodecyl(dimethyl)azaniumyl]-2-hydroxypropane-1-sulfonate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC(O)CS([O-])(=O)=O DDGPBVIAYDDWDH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical class N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008406 cosmetic ingredient Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- ONLRKTIYOMZEJM-UHFFFAOYSA-N n-methylmethanamine oxide Chemical compound C[NH+](C)[O-] ONLRKTIYOMZEJM-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、離型剤等の用途に好適なシリコーンエマルジョン組成物およびそれを用いた離型剤に係り、さらに詳しくは、消泡剤添加時の機械的安定性を改善したシリコーンエマルジョン組成物およびそれを用いた離型剤に関する。 The present invention relates to a silicone emulsion composition suitable for use as a mold release agent and the like, and a mold release agent using the same, and more specifically, a silicone emulsion composition having improved mechanical stability upon addition of an antifoaming agent and It relates to a release agent using the same.
金属やゴム・プラスチックなどの製品を成形する際の金型用離型剤として使用するため、オルガノポリシロキサンを乳化剤により水中に均一に分散させたシリコーンエマルジョン組成物が種々提案されている。 Various silicone emulsion compositions in which organopolysiloxane is uniformly dispersed in water using an emulsifier have been proposed for use as a mold release agent for molding products such as metals, rubber and plastics.
例えば特許文献１では、ジメチルポリシロキサンの水性エマルジョンにポリオキシエチレンアルキルフェニルエーテル硫酸ナトリウムを添加した組成物が、また、特許文献２では、環状ジメチルポリシロキサンと乳化剤と水からなるシリコーンエマルジョン組成物が提案されている。 For example, Patent Document 1 discloses a composition obtained by adding sodium polyoxyethylene alkylphenyl ether sulfate to an aqueous emulsion of dimethylpolysiloxane, and Patent Document 2 discloses a silicone emulsion composition composed of cyclic dimethylpolysiloxane, an emulsifier and water. Proposed.
しかしながら、これらのシリコーンエマルジョン組成物は、機械的安定性に乏しく、機械的剪断力が加わった場合にはそのエマルジョン形態が破壊され易いという欠点があった。すなわち、例えばこれらのシリコーンエマルジョン組成物をアルミニウムダイキャスト成形用離型剤として使用する場合、組成物を数十倍の水で希釈し、この希釈液をギアポンプにより送液して金型内壁に吹き付け、金型内壁表面にオルガノポリシロキサンの油膜を均一に形成させるとともに、余剰の希釈液は回収してギアポンプにより繰り返し送液する方法が一般に採用されているが、この過程でエマルジョン破壊が起こり、金型に均一に塗布することができなくなるという問題があった。また、このように希釈液を循環させて使用する設備においては、エアーの巻き込みによる泡立ちが大きいという問題もあった。 However, these silicone emulsion compositions have a drawback that they have poor mechanical stability, and the emulsion form is easily destroyed when mechanical shearing force is applied. That is, for example, when these silicone emulsion compositions are used as a mold release agent for aluminum die casting, the composition is diluted with several tens of times of water, and this diluted solution is fed by a gear pump and sprayed on the inner wall of the mold. In general, an oil film of organopolysiloxane is uniformly formed on the surface of the inner wall of the mold, and a method of collecting excess dilution liquid and repeatedly feeding it with a gear pump is adopted. There was a problem that it was impossible to uniformly apply to the mold. In addition, the equipment that circulates the diluent as described above has a problem that foaming due to entrainment of air is large.
かかる問題を解決するため、ジメチルポリシロキサンと、ポリオキシエチレン高級アルコールエーテルと、ポリオキシエチレン高級アルコールエーテル硫酸塩および水からなるシリコーンエマルジョン組成物（特許文献３）が提案されているが、機械的安定性はいくらか改善されるものの十分ではなく、一方、泡立ちの問題も改善がみられない。 In order to solve this problem, a silicone emulsion composition (Patent Document 3) comprising dimethylpolysiloxane, polyoxyethylene higher alcohol ether, polyoxyethylene higher alcohol ether sulfate and water has been proposed. Some improvement in stability is not sufficient, while foaming problems do not improve.
泡立ちの問題を解消するには、一般的にシリコーン系消泡剤を離型液浴に添加する手法や離型エマルジョンにあらかじめ添加しておく方法が用いられる。しかし、消泡剤を用いた場合、消泡効果は得られるものの、エマルジョンの破壊を促進してしまう問題を起こす結果となっていた。このため、エマルジョン自体の安定性を向上させても、消泡剤を併用する設備、特に、上記循環型設備の場合、シリコーン系消泡剤が原因で循環液中にスカムが発生したり、エマルジョンが破壊され油膜の生成や循環ポンプのフィルターを目詰まりさせるという問題がある。
上述したように、金型用離型剤に使用するため各種のシリコーンエマルジョン組成物が開発されているが、消泡剤を併用した場合にも、十分な機械的安定性を有するものは未だ得られていない。 As described above, various silicone emulsion compositions have been developed for use in mold release agents. However, even when an antifoaming agent is used in combination, a composition having sufficient mechanical stability is still not available. It is not done.
本発明はこのような従来の事情に対処してなされたもので、消泡剤が添加されてもなおかつ十分な機械的安定性を有する、優れたシリコーンエマルジョン組成物、およびこれを用いた離型剤を提供することを目的としている。 The present invention has been made in response to such a conventional situation, and has an excellent silicone emulsion composition having sufficient mechanical stability even when an antifoaming agent is added, and a mold release using the same. The purpose is to provide an agent.
上記の目的を達成するため、本発明者は鋭意検討した結果、特定の界面活性剤の併用が極めて有効であることを見出し、本発明を完成するに至った。 In order to achieve the above object, the present inventor has intensively studied and found that the combined use of a specific surfactant is extremely effective, and has completed the present invention.
即ち、本発明は、（Ａ）平均重合度が５〜1000のオルガノポリシロキサン100重量部、（Ｂ）ポリオキシエチレンアルキルエーテル１〜50重量部、（Ｃ）アルキル硫酸塩0.1〜20重量部、（Ｄ）両性界面活性剤および／または半極性界面活性剤0.1〜20重量部および（Ｅ）水を含有することを特徴とするシリコーンエマルジョン組成物、およびこれを用いた離型剤である。 That is, the present invention comprises (A) 100 parts by weight of an organopolysiloxane having an average degree of polymerization of 5 to 1000, (B) 1 to 50 parts by weight of polyoxyethylene alkyl ether, (C) 0.1 to 20 parts by weight of alkyl sulfate, (D) A silicone emulsion composition containing 0.1 to 20 parts by weight of an amphoteric surfactant and / or a semipolar surfactant and (E) water, and a mold release agent using the same.
本発明のシリコーンエマルジョン組成物は、消泡剤を添加しても機械的安定性に優れたものとなる。 The silicone emulsion composition of the present invention has excellent mechanical stability even when an antifoaming agent is added.
また、本発明の離型剤は、上記のような消泡剤添加に対しても、安定性に優れるシリコーンエマルジョン組成物を含有するので、アルミニウムダイキャスト成型のように消泡剤を泡消しのため随時添加しながら離型剤を循環させて使用する成形技術の用途にも十分適用することができ、品質の良い成型品を安定に製造することが可能となる。 In addition, since the release agent of the present invention contains a silicone emulsion composition having excellent stability against the addition of the antifoaming agent as described above, the antifoaming agent can be used for defoaming as in aluminum die casting. Therefore, it can be sufficiently applied to the use of a molding technique in which a release agent is circulated while being added as needed, and a molded product with good quality can be stably produced.
以下、本発明の実施の形態について説明する。本発明において使用される（Ａ）成分のオルガノポリシロキサンは、平均重合度が５〜1000、好ましくは30〜300のものであって、基本的に直鎖状のシロキサン骨格を有するものである。若干の分岐を有していてもよいが、分子全体が直鎖状の構造からなるものが好ましい。平均重合度が５未満では、離型剤としての効果が十分でなく、平均重合度が1000を越えると、粘度が大きくなりすぎるために乳化が困難になる。 Embodiments of the present invention will be described below. The organopolysiloxane of component (A) used in the present invention has an average polymerization degree of 5 to 1000, preferably 30 to 300, and basically has a linear siloxane skeleton. Although it may have some branches, it is preferable that the whole molecule has a linear structure. If the average degree of polymerization is less than 5, the effect as a mold release agent is not sufficient, and if the average degree of polymerization exceeds 1000, the viscosity becomes too high and emulsification becomes difficult.
分子中のケイ素原子に結合する有機基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、n-ブチル基、イソブチル基、t-ブチル基、n-ペンチル基、イソペンチル基、n-ヘキシル基、n-オクチル基、2-エチルへキシル基、n-デシル基、イソデシル基、n-ドデシル基、イソドデシル基、n-テトラデシル基、n-ヘキサデシル基、n-オクタデシル基等の炭素数１〜24の直鎖または分岐状のアルキル基、；シクロヘキシル基等の炭素数４〜７のシクロアルキル基；ビニル基、アリル基等の炭素数２〜８のアルケニル基；2-フェニルエチル基、2-フェニルプロピル基等の、アリール基がフェニル基または低級アルキル基（炭素数４以下）置換フェニル基で、アルキル基が低級アルキル（炭素数４以下）基であるアラルキル基；フェニル基、トリル基等の低級アルキル基（炭素数４以下）置換フェニル基等のアリール基；およびこれらの基の炭化水素に結合した水素原子がハロゲン原子、シアノ基、アミノ基等で置換された基、例えばクロロメチル基、3,3,3-トリフルオロプロピル基、シアノメチル基、N-(2-アミノエチル)-3-アミノプロピル基、3-アミノプロピル基等が例示される。また、ケイ素原子に結合するその他の基として、アルコキシ基、水酸基、水素原子等を部分的に含んでいてもよい。なかでも、炭素数１〜18の直鎖もしくは分岐状のアルキル基もしくは2-フェニルプロピル基置換フェニル基の単独もしくは２種以上の混合物が好ましい。 Examples of the organic group bonded to the silicon atom in the molecule include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-butyl group, isobutyl group, t-butyl group, n- Pentyl group, isopentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, isodecyl group, n-dodecyl group, isododecyl group, n-tetradecyl group, n-hexadecyl group, n A linear or branched alkyl group having 1 to 24 carbon atoms such as an octadecyl group; a cycloalkyl group having 4 to 7 carbon atoms such as a cyclohexyl group; an alkenyl group having 2 to 8 carbon atoms such as a vinyl group or an allyl group Aralkyl in which the aryl group is a phenyl group or a lower alkyl group (4 or less carbon atoms) substituted phenyl group, and the alkyl group is a lower alkyl (4 or less carbon atoms) group, such as a 2-phenylethyl group or 2-phenylpropyl group; An aryl group such as a phenyl group, a tolyl group or other lower alkyl group (4 or less carbon atoms) substituted phenyl group; and the hydrogen atom bonded to the hydrocarbon of these groups is substituted with a halogen atom, a cyano group, an amino group, or the like; Examples thereof include chloromethyl group, 3,3,3-trifluoropropyl group, cyanomethyl group, N- (2-aminoethyl) -3-aminopropyl group, 3-aminopropyl group and the like. Moreover, as other groups couple | bonded with a silicon atom, the alkoxy group, a hydroxyl group, a hydrogen atom, etc. may be included partially. Among these, a linear or branched alkyl group having 1 to 18 carbon atoms or a phenyl group substituted with a 2-phenylpropyl group alone or a mixture of two or more types is preferable.
本発明のシリコーンエマルジョン組成物を離型剤として使用する場合、1分子中のケイ素原子に結合する有機基の少なくとも50モル％がメチル基であることが離型性の点で好ましい。 When the silicone emulsion composition of the present invention is used as a release agent, it is preferable from the viewpoint of releasability that at least 50 mol% of organic groups bonded to silicon atoms in one molecule are methyl groups.
（Ａ）成分のオルガノポリシロキサンは、１種を単独で使用してもよく、２種以上を混合して用いてもよい。 (A) The organopolysiloxane of a component may be used individually by 1 type, and 2 or more types may be mixed and used for it.
（Ｂ）成分のポリオキシエチレンアルキルエーテルは、主として（Ａ）成分のオルガノポリシロキサンを水中に均一に分散させるための成分であり、本発明においては、炭素数８〜24のアルキル基（例えば、エチルヘキシル基、ノニル基、デシル基、イソデシル基、ラウリル基、テトラデシル基、セチル基、ステアリル基等）を有し、かつ、エチレンオキサイドの付加モル数が２〜20であるものが好ましく使用される。（Ａ）成分のオルガノポリシロキサンの含有量が多い場合には、組成物の粘度を低下させる観点から、なかでも炭素数８〜14のアルキル基を有するものが好ましい。これらのポリオキシエチレンアルキルエーテルは、１種を単独で使用してもよく、２種以上を混合して使用してもよい。 The (B) component polyoxyethylene alkyl ether is a component mainly for uniformly dispersing the (A) organopolysiloxane in water. In the present invention, an alkyl group having 8 to 24 carbon atoms (for example, An ethylhexyl group, a nonyl group, a decyl group, an isodecyl group, a lauryl group, a tetradecyl group, a cetyl group, a stearyl group, and the like, and an ethylene oxide addition mole number of 2 to 20 is preferably used. When the content of the organopolysiloxane (A) is large, those having an alkyl group having 8 to 14 carbon atoms are preferred from the viewpoint of reducing the viscosity of the composition. These polyoxyethylene alkyl ethers may be used alone or in a combination of two or more.
（Ｂ）成分のポリオキシエチレンアルキルエーテルの配合量は、（Ａ）成分のオルガノポリシロキサン100重量部に対し、１〜50重量部であり、好ましくは３〜30重量部である。（Ｂ）成分のポリオキシエチレンアルキルエーテルの配合量が１重量部未満では、得られるエマルジョン組成物中に（Ａ）成分のオルガノポリシロキサンを良好に分散させることが困難になったり、保存安定性が低下する。また、50重量部を越えると、（Ａ）成分のオルガノポリシロキサンの特性発現を阻害するおそれが生ずる。 (B) The compounding quantity of the polyoxyethylene alkyl ether of a component is 1-50 weight part with respect to 100 weight part of (A) component organopolysiloxane, Preferably it is 3-30 weight part. When the blending amount of the polyoxyethylene alkyl ether as the component (B) is less than 1 part by weight, it becomes difficult to satisfactorily disperse the organopolysiloxane as the component (A) in the resulting emulsion composition, and storage stability Decreases. On the other hand, when the amount exceeds 50 parts by weight, there is a possibility that the characteristic expression of the organopolysiloxane (A) may be inhibited.
（Ｃ）成分のアルキル硫酸塩は、組成物に優れた機械的安定性を与えるために必須の成分である。アルキル硫酸塩の具体例としては、炭素数８〜22のアルキル基（例えば、エチルヘキシル基、ノニル基、デシル基、ラウリル基、テトラデシル基、セチル基、ステアリル基等）を有するアルカリ金属硫酸塩、アンモニウム硫酸塩、トリエタノール硫酸塩、アルカリ金属酢酸塩、アンモニウム酢酸塩等が挙げられるが、なかでもナトリウム硫酸塩およびトリエタノール硫酸塩が好ましい。 The alkyl sulfate salt of component (C) is an essential component for imparting excellent mechanical stability to the composition. Specific examples of the alkyl sulfate include alkali metal sulfates having a C 8-22 alkyl group (for example, ethylhexyl group, nonyl group, decyl group, lauryl group, tetradecyl group, cetyl group, stearyl group), ammonium Examples thereof include sulfates, triethanol sulfates, alkali metal acetates, ammonium acetates, and among them, sodium sulfate and triethanol sulfate are preferable.
（Ｃ）成分のアルキル硫酸塩の配合量は、（Ａ）成分のオルガノポリシロキサン100重量部に対し、0.1〜20重量部であり、好ましくは0.5〜10重量部である。（Ｃ）成分のアルキル硫酸塩の配合量が0.1重量部未満では、機械的安定性を改善する効果が小さく、また、20重量部を越えると、取り扱い難くなるうえ、組成物の粘度が上昇して流動性が悪くなり、離型剤として使用した場合に金型等へ薄く均一に塗布することが困難になる。 The compounding amount of the alkyl sulfate of component (C) is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of organopolysiloxane of component (A). If the blending amount of the alkyl sulfate salt of component (C) is less than 0.1 parts by weight, the effect of improving the mechanical stability is small, and if it exceeds 20 parts by weight, handling becomes difficult and the viscosity of the composition increases. Thus, the fluidity is deteriorated, and when used as a release agent, it becomes difficult to apply thinly and uniformly to a mold or the like.
（Ｄ）成分の両性界面活性剤およびまたは半極性界面活性剤は、組成に消泡剤に対する安定性、特に機械的安定性を付与するための成分である。両性界面活性剤としてはアミドベタイン型両性界面活性剤、アミドスルホベタイン型両性界面活性剤、ベタイン型両性界面活性剤、アミドスルホベタイン型両性界面活性剤、イミダソリニウム型両性界面活性剤が挙げられ、アミドベタイン型両性界面活性剤としては、ヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン、アミドスルホベタイン型両性界面活性剤としては、ラウリン酸アミドプロピルヒドロキシスルホベタイン、ベタイン型両性界面活性剤としは、ラウリルジメチルアミノ酢酸ベタインが、スルホベタイン型両性界面活性剤としては、ラウリルヒドロキシスルホベタイン、イミダソリニウム型両性界面活性剤としては、２ウンデシル-N,N,N-（ヒドロキシエチルカルボキシメチル）-2-イミダゾリンナトリウムが例示される。また半極性界面活性剤は、第三アミンオキシド型半極性界面活性剤が挙げられラウリルジメチルアミンオキシド、ラウリン酸アミドプロピルアミンオキシドが例示される。なかでも、ヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタインおよびラウリン酸アミドプロピルアミンオキシドが望ましい。 The amphoteric surfactant and / or the semipolar surfactant as the component (D) are components for imparting stability to the antifoaming agent, particularly mechanical stability, to the composition. Examples of amphoteric surfactants include amide betaine type amphoteric surfactants, amide sulfobetaine type amphoteric surfactants, betaine type amphoteric surfactants, amide sulfobetaine type amphoteric surfactants, and imidazolinium type amphoteric surfactants. Betaine-type amphoteric surfactants include coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, amide sulfobetaine-type amphoteric surfactants include lauric acid amidopropylhydroxysulfobetaine, and betaine-type amphoteric surfactants include lauryldimethylamino. Examples of betaine acetate include lauryl hydroxysulfobetaine as a sulfobetaine-type amphoteric surfactant, and 2undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium as an example of an imidazolinium-type amphoteric surfactant Is done. Examples of the semipolar surfactant include tertiary amine oxide type semipolar surfactants such as lauryldimethylamine oxide and lauric acid amidopropylamine oxide. Of these, palm oil fatty acid amidopropyldimethylaminoacetic acid betaine and lauric acid amidopropylamine oxide are desirable.
両性界面活性剤としては、特に、下記一般式（ＩＩ）〜（ＶＩ）で表される化合物からなる群より選ばれる１種または２種以上が好ましく用いられる。 As the amphoteric surfactant, one or more selected from the group consisting of compounds represented by the following general formulas (II) to (VI) are particularly preferably used.
一般式（ＩＩ） Formula (II)
で表されるアミドベタイン型両性界面活性剤。 Amidobetaine-type amphoteric surfactant represented by
一般式（ＩＩＩ） Formula (III)
で表されるアミドスルホベタイン型両性界面活性剤。 Amidosulfobetaine-type amphoteric surfactant represented by
一般式（ＩＶ） Formula (IV)
で表されるベタイン型両性界面活性剤。 Betaine amphoteric surfactant represented by
一般式（Ｖ） General formula (V)
で表されるスルホベタイン型両性界面活性剤。 A sulfobetaine type amphoteric surfactant represented by the formula:
一般式（ＶＩ） Formula (VI)
で表されるイミダゾリニウム型両性界面活性剤。 An imidazolinium type amphoteric surfactant represented by
なお、上記一般式（ＩＩ）〜（ＶＩ）中、Ｒ7は炭素原子数９〜２１のアルキル基またはアルケニル基を表し、上記炭素原子数は、より好ましくは１〜１７であり、最も好ましくは１１〜１３である。炭素原子数が９未満では親水性が強すぎ複合体を形成し難く、一方、炭素原子数が２１を超えると水への溶解性が悪くなり、複合体を形成し難い。 In the general formulas (II) to (VI), R 7 represents an alkyl group or alkenyl group having 9 to 21 carbon atoms, and the number of carbon atoms is more preferably 1 to 17, and most preferably. 11-13. If the number of carbon atoms is less than 9, the hydrophilicity is too strong to form a complex. On the other hand, if the number of carbon atoms exceeds 21, the solubility in water becomes poor and it is difficult to form a complex.
Ｒ8、Ｒ9は、それぞれ独立に炭素原子数１０〜１８のアルキル基またはアルケニル基を表し、ｐは２〜４の整数を、ｑは０〜３の整数を表し、ｓは１または２の整数を表す。 R 8 and R 9 each independently represents an alkyl or alkenyl group having 10 to 18 carbon atoms, p represents an integer of 2 to 4, q represents an integer of 0 to 3, and s represents 1 or 2 Represents an integer.
ここで、上記一般式（ＩＩ）で表されるアミドベタイン型両性界面活性剤としては、例えばヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン等が挙げられ、「レボン２０００」（三洋化成（株）製）、「アノンＢＤＦ」（日本油脂（株）製）等が市販品として例示される。 Here, examples of the amide betaine-type amphoteric surfactant represented by the above general formula (II) include coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine and the like, and “LEBON 2000” (manufactured by Sanyo Chemical Co., Ltd.). “Anon BDF” (manufactured by NOF Corporation) is exemplified as a commercial product.
上記一般式（ＩＩＩ）で表されるアミドスルホベタイン型両性界面活性剤としては、「ロンザイン−ＣＳ」（ロンザ（株）製）、「ミラタインＣＢＳ」（ミラノール（株）製）等が市販品として例示される。 As amide sulfobetaine type amphoteric surfactants represented by the above general formula (III), “Lonzain-CS” (manufactured by Lonza Co., Ltd.), “Miratine CBS” (manufactured by Milanol Co., Ltd.) and the like are commercially available products. Illustrated.
上記一般式（ＩＶ）で表されるベタイン型両性界面活性剤としては、例えばラウリルジメチルアミノ酢酸ベタイン等が挙げられ、「アノンＢＬ］（日本油脂（株）製）、「デハイントンＡＢ−３０」（ヘンケル（株）製）等が市販品として例示される。 Examples of the betaine-type amphoteric surfactant represented by the general formula (IV) include lauryldimethylaminoacetic acid betaine and the like, and “Anon BL” (manufactured by NOF Corporation), “Dehington AB-30” ( Henkel Co., Ltd.) is exemplified as a commercial product.
上記一般式（Ｖ）で表されるスルホベタイン型両性界面活性剤としては、「ロンザイン−１２ＣＳ」（ロンザ（株）製）等が市販品として例示される。 As a sulfobetaine type | mold amphoteric surfactant represented by the said general formula (V), "Lonzaine-12CS" (made by Lonza Co., Ltd.) etc. are illustrated as a commercial item.
さらに、上記一般式（ＶＩ）で表されるイミダゾリニウム型両性界面活性剤としては、例えば２−ウンデシル−Ｎ，Ｎ，Ｎ−（ヒドロキシエチルカルボキシメチル）−２−イミダゾリンナトリウム等が挙げられ、「オバゾリン６６２−Ｎ」（東邦化学（株）製）、「アノンＧＬＭ」（日本油脂（株）製）等が市販品として例示される。 Furthermore, examples of the imidazolinium type amphoteric surfactant represented by the general formula (VI) include 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, “Obazoline 662-N” (manufactured by Toho Chemical Co., Ltd.), “Anon GLM” (manufactured by NOF Corporation) and the like are exemplified as commercial products.
本発明で用いられる半極性界面活性剤としては、特に下記一般式（ＶＩＩ） As the semipolar surfactant used in the present invention, in particular, the following general formula (VII)
（式中、Ｒ9は炭素原子数１０〜１８のアルキル基またはアルケニル基を表す）で表される第三級アミンオキシド型半極性界面活性剤が最も好適に用いられる。 A tertiary amine oxide type semipolar surfactant represented by the formula (wherein R 9 represents an alkyl group or alkenyl group having 10 to 18 carbon atoms) is most preferably used.
上記一般式（ＶＩＩ）で表される第三級アミンオキシド型半極性界面活性剤としては、例えばラウリルジメチルアミンオキシド、ラウリン酸アミドプロピルジメチルアミンオキシド等が挙げられ、「ユニセーフＡ−ＬＭ］（日本油脂（株）製）、「マックアミンＬＡＯ」（Ｍｃｌｎｔｙｒｅ（株）製）等が市販品として例示される。 Examples of the tertiary amine oxide type semipolar surfactant represented by the general formula (VII) include lauryl dimethylamine oxide, lauric acid amidopropyl dimethylamine oxide, and the like. “Unisafe A-LM” (Japan) (Oil and Fat Co., Ltd.), “McAmin LAO” (Mcntyre Co., Ltd.) and the like are exemplified as commercial products.
（Ｄ）成分の両性界面活性剤およびまたは半極性界面活性剤の配合量は、（Ａ）成分のオルガノポリシロキサン100重量部に対し、0.1〜20重量部であり、好ましくは0.5〜10重量部である。（Ｄ）成分の両性界面活性剤およびまたは半極性界面活性剤の配合量が、0.1重量部未満では、消泡剤が添加された溶液において機械的安定性を改善する効果が小さく、また、20重量部を越えると、取り扱い難くなるうえ、組成物の粘度が上昇して流動性が悪くなり、離型剤として使用した場合に金型等へ薄く均一に塗布することが困難になる。 The blending amount of the amphoteric surfactant and / or semipolar surfactant of component (D) is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of organopolysiloxane of component (A). It is. When the blending amount of the amphoteric surfactant and / or the semipolar surfactant as the component (D) is less than 0.1 parts by weight, the effect of improving the mechanical stability in the solution to which the antifoaming agent is added is small. If it exceeds the parts by weight, it becomes difficult to handle, the viscosity of the composition increases and the fluidity becomes poor, and when used as a release agent, it becomes difficult to apply thinly and uniformly to a mold or the like.
本発明においては、分散媒として（Ｅ）成分の水を配合する。これは、（Ａ）成分のオルガノポリシロキサンやその他の成分を分散または溶解することによって、均一なエマルジョン組成物を得るためのものである。 In the present invention, (E) component water is blended as a dispersion medium. This is for obtaining a uniform emulsion composition by dispersing or dissolving the component (A) organopolysiloxane and other components.
この（Ｅ）成分の水の配合量は、（Ａ）成分のオルガノポリシロキサンの含有量が組成物全体の0.5〜60重量％となる範囲が好ましく、前記範囲より少ない場合には、疎水性油である（Ａ）成分のオルガノポリシロキサンの量が多すぎてエマルジョンがＷ／Ｏ型からＯ／Ｗ型へ転相せず、水が連続層とならない場合があり、また、たとえ転相した場合であっても、取り扱いが困難になるうえ、組成物の粘度が上昇して流動性が悪くなり、離型剤として使用した場合に金型等へ薄く均一に塗布することが困難になる。一方、水の配合量が前記範囲より多くなると、（Ａ）成分のオルガノポリシロキサンの濃度が低すぎるために、離型剤として使用した場合に金型等への塗布効率が低下する。 The amount of water of component (E) is preferably in the range where the content of organopolysiloxane of component (A) is 0.5 to 60% by weight of the total composition. When the amount of the organopolysiloxane of the component (A) is too large, the emulsion may not change phase from W / O type to O / W type, and water may not become a continuous layer. However, handling becomes difficult, the viscosity of the composition increases and fluidity becomes poor, and when used as a mold release agent, it is difficult to apply it thinly and uniformly to a mold or the like. On the other hand, when the amount of water exceeds the above range, the concentration of the organopolysiloxane of the component (A) is too low, so that the application efficiency to a mold or the like is lowered when used as a release agent.
本発明のシリコーンエマルジョン組成物には、上記（Ａ）〜（E）成分の他、この種のシリコーンエマルジョン組成物に通常配合される成分、例えば防腐剤；防黴剤；防錆剤；着色剤；鉱物油；パルミチン酸、ステアリン酸等の高級脂肪酸；増粘剤；アルミニウム粉末、黒鉛等の無機粉末等を、本発明の効果を阻害しない範囲で適宜配合することができる。 In the silicone emulsion composition of the present invention, in addition to the components (A) to (E) described above, components usually incorporated in this type of silicone emulsion composition, such as antiseptics; antifungal agents; rust inhibitors; Mineral oil; higher fatty acids such as palmitic acid and stearic acid; thickeners; inorganic powders such as aluminum powder and graphite, and the like can be appropriately blended within a range that does not impair the effects of the present invention.
本発明のシリコーンエマルジョン組成物は、上記各成分を、ホモミキサー、コロイドミル、ラインミキサー、ホモジナイザー等の乳化機を用いて乳化することにより製造することができる。 The silicone emulsion composition of the present invention can be produced by emulsifying the above components using an emulsifier such as a homomixer, a colloid mill, a line mixer, or a homogenizer.
本発明のシリコーンエマルジョン組成物は、機械的安定性、特に消泡剤が添加された場合の機械的安定性に優れており、また、金型等に塗布した場合に離型後の成形品に付着残留することがほとんどないため、そのままで、あるいは水で希釈して金型用離型剤として有効に使用されるが、その他、電線の芯線の引抜きやアイロン掛けの際の潤滑剤、ゴム・プラスチック製品あるいは家具などの艶出剤、繊維に撥水性や柔軟性などを付与するための繊維処理剤、塗料成分、化粧料成分、医薬品成分などの用途にも適宜使用することができる。なお、適用できる製品の形態としては、固形状、ゲル状、液状、ペースト状のものが例示される。 The silicone emulsion composition of the present invention is excellent in mechanical stability, especially when an antifoaming agent is added, and when applied to a mold or the like, it can be used as a molded product after release. Since there is almost no adhesion residue, it can be used effectively as it is or as a mold release agent by diluting with water, but other lubricants, rubber, It can also be used as appropriate for applications such as polish products for plastic products or furniture, fiber treatment agents for imparting water repellency and flexibility to fibers, paint components, cosmetic ingredients, and pharmaceutical ingredients. Applicable product forms include solid, gel, liquid, and paste.
本発明を実施例によりさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下の記載において「部」及び「％」はそれぞれ「重量部」及び「重量％」を意味し、また、粘度は25℃における測定値である。
実施例１
下記式で表されるオルガノポリシロキサン（粘度700mPa、シリコーンオイルAと表記）51.5部に、ポリオキシエチレン(3)デシルエーテル1.6部、ポリオキシエチレン(15)デシルエーテル3.2部及び水5.5部を添加し均一に混合した後、コロイドミル乳化器を用いて乳化し、さらにポリオキシエチレン(2)ラウリルエーテル硫酸ナトリウム27%aq. 1.1部、ラウリル硫酸トリエタノールアミン40%aq. 5部、ヤシ油脂肪酸アミドプロピルジメチル酢酸ベタイン30%aq. 5部及び水37.1部を添加し均一に混合して、シリコーンエマルジョン組成物を得た。
実施例２
下記式で表されるオルガノポリシロキサン（粘度1500mPa、シリコーンオイルBと表記）51.5部に、ポリオキシエチレン(3)デシルエーテル1.6部、ポリオキシエチレン(15)デシルエーテル3.2部及び水5.5部を添加し均一に混合した後、コロイドミル乳化器を用いて乳化し、さらにポリオキシエチレン(2)ラウリルエーテル硫酸ナトリウム27%aq. 1.1部、ラウリル硫酸トリエタノールアミン40%aq. 5部、ヤシ油脂肪酸アミドプロピルジメチル酢酸ベタイン30%aq. 5部及び水37.1部を添加し均一に混合して、シリコーンエマルジョン組成物を得た。
Examples The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following description, “parts” and “%” mean “parts by weight” and “% by weight”, respectively, and the viscosity is a measured value at 25 ° C.
Example 1
Polyoxyethylene (3) decyl ether 1.6 parts, polyoxyethylene (15) decyl ether 3.2 parts and water 5.5 parts are added to 51.5 parts of an organopolysiloxane (viscosity 700 mPa, expressed as silicone oil A) represented by the following formula And uniformly mixed, and then emulsified using a colloid mill emulsifier, and further polyoxyethylene (2) sodium lauryl ether sulfate 27% aq. 1.1 parts, lauryl sulfate triethanolamine 40% aq. 5 parts, coconut oil fatty acid A silicone emulsion composition was obtained by adding 5 parts of amidopropyldimethylacetate betaine 30% aq. And 37.1 parts of water and mixing uniformly.
Example 2
Polyoxyethylene (3) decyl ether 1.6 parts, polyoxyethylene (15) decyl ether 3.2 parts and water 5.5 parts are added to 51.5 parts of the organopolysiloxane (viscosity 1500 mPa, silicone oil B) represented by the following formula And uniformly mixed, and then emulsified using a colloid mill emulsifier, and further polyoxyethylene (2) sodium lauryl ether sulfate 27% aq. 1.1 parts, lauryl sulfate triethanolamine 40% aq. 5 parts, coconut oil fatty acid A silicone emulsion composition was obtained by adding 5 parts of amidopropyldimethylacetate betaine 30% aq. And 37.1 parts of water and mixing uniformly.
以下、実施例３〜８及び、比較例１〜12のシリコーンエマルジョン組成物も同様にして調製した。シリコーンエマルジョン組成物の詳しい組成は表２〜４に記載する。 Hereinafter, the silicone emulsion compositions of Examples 3 to 8 and Comparative Examples 1 to 12 were similarly prepared. The detailed composition of the silicone emulsion composition is listed in Tables 2-4.
実施例１及び2のシリコーンエマルジョン組成物に関して、一般特性を調べた。また防錆性、ペインタブル性、離型性は下記方法により評価した。結果を表１に示す。
・防錆性
150mlのガラス瓶にシリコーンエマルジョン組成物を130ml入れ、長さ3cm、直径2.5mmの軟鉄製の釘3本を沈め、50℃オーブンに48時間静置し、次のように防錆性をチェックした。
○：全く錆びの発生無し。
△：部分的に錆びの発生がやや認められる。
×：ほぼ全面に錆びの発生があり、錆びの沈降もある。
・ペインタブル性
シリコーンエマルジョン組成物を、水で50倍に希釈し、簡易型スプレーガンを用いてクレーコート紙に均一に吹き付け、室温で乾燥後、油性の太書き用マジックインキで定規を使って等間隔で紙を引き、線のかすれた具合いを、次のように判定した。
○：線のかすれは全く無く均一にマジックインキが付着している。
△：部分的に僅かに線のかすれがあり、やや不均一なマジックインキの付着となっている。
×：マジックインキのかすれが大。
・離型性
内径5cm×5cm、深さ5mmであり、底を鏡面仕上した金型に、水で5倍希釈したシリコーンエマルジョン組成物を吹き付け、約350℃に予熱し、電気炉で約750℃で熔融させたアルミニウムの湯を該金型に注ぎ込み、除冷後、金型からアルミニウム片を引きはがし、はがれ程度で離型性を評価した。
○：型汚れ性良好
△：やや型汚れ性が悪い
×：型離れが困難
The general properties were investigated for the silicone emulsion compositions of Examples 1 and 2. Moreover, rust prevention property, paintability, and releasability were evaluated by the following methods. The results are shown in Table 1.
・ Rust prevention
130 ml of the silicone emulsion composition was put in a 150 ml glass bottle, 3 soft iron nails having a length of 3 cm and a diameter of 2.5 mm were submerged and allowed to stand in an oven at 50 ° C. for 48 hours, and the antirust property was checked as follows.
○: No rusting.
Δ: Some rusting is slightly observed.
X: Rust is generated almost on the entire surface, and there is also rust settling.
・ Paintable The silicone emulsion composition is diluted 50 times with water, sprayed evenly on clay-coated paper using a simple spray gun, dried at room temperature, and then using a ruler with oil-based thick ink magic ink. Paper was drawn at intervals, and the degree of faint lines was determined as follows.
○: There is no fading of the lines at all and the magic ink is uniformly attached.
(Triangle | delta): There is a slight blur of a line partially, and it has adhered slightly non-uniform magic ink.
×: The fading of the magic ink is large.
・ Releasability Inner diameter 5cm × 5cm, depth 5mm, mold with a mirror finish on the bottom, sprayed with 5 times diluted silicone emulsion composition with water, preheated to about 350 ℃, about 750 ℃ in an electric furnace The molten aluminum was poured into the mold, and after cooling, the aluminum piece was peeled off from the mold, and the releasability was evaluated by the degree of peeling.
○: Good mold stain △: Slightly poor mold stain ×: Difficult to separate
また全ての実施例、比較例について下記に示す方法により機械安定性を評価した。
・機械安定性
シリコーンエマルジョン組成物を有効成分濃度が1.0%になるように水で希釈し、次いで、この希釈液300gを500mlビーカーに入れ、ホモミキサーを用い8000rpmの回転速度で10分間撹拌した。その間、希釈液の泡立ちに伴い、ジーイー東芝シリコーン（株）製消泡剤TSA772（下記式で表されるシリコーンオイルC、シリコーンオイルD及び二酸化珪素粉をベースとする有効成分25%のシリコーンエマルジョン）もしくはTSA732（ポリジメチルシロキサン及び二酸化珪素粉をベースとする有効成分25%のシリコーンエマルジョン）を添加し（添加量：市水で２倍に希釈した液を希釈液300gに対して40ppmもしくは80ppm量）、泡消しを行った。その後、希釈液表面の泡が完全に消えるまでビーカーを静置し、泡が消えた時点のエマルジョンの状態を目視にて測定し、以下に示す判断基準により評価した。
Moreover, mechanical stability was evaluated by the method shown below about all the Examples and the comparative examples.
-Mechanical stability The silicone emulsion composition was diluted with water so that the active ingredient concentration was 1.0%, and then 300 g of this diluted solution was placed in a 500 ml beaker and stirred for 10 minutes at a rotation speed of 8000 rpm using a homomixer. Meanwhile, anti-foaming agent TSA772 manufactured by GE Toshiba Silicone Co., Ltd. (silicone emulsion of 25% active ingredient based on silicone oil C, silicone oil D and silicon dioxide powder represented by the following formula) with the foaming of the diluent Alternatively, TSA732 (25% active ingredient silicone emulsion based on polydimethylsiloxane and silicon dioxide powder) is added (added amount: 40 ppm or 80 ppm amount of diluted solution with 300 g of city water to 300 g of diluted solution) The foam was erased. Thereafter, the beaker was allowed to stand until the bubbles on the surface of the diluent completely disappeared, and the state of the emulsion when the bubbles disappeared was visually measured and evaluated according to the following criteria.
（評価基準）
５：エマルジョン表面に干渉膜やオイル浮きが全く認められなかった。
４：エマルジョン表面に僅かな干渉膜もしくは僅かなオイルスポットが発生していた。
３：エマルジョン表面一部に干渉膜もしくはオイルスポットが発生していた。
２：エマルジョン表面全体に干渉膜が発生し、表面大半に顕著なオイルスポットが発生していた。
１：エマルジョン表面全体にオイルが浮遊していた。
(Evaluation criteria)
5: No interference film or oil floating was observed on the emulsion surface.
4: A slight interference film or a slight oil spot was generated on the emulsion surface.
3: An interference film or an oil spot was generated on a part of the emulsion surface.
2: An interference film was generated on the entire emulsion surface, and a noticeable oil spot was generated on most of the surface.
1: Oil floated over the entire emulsion surface.
機械安定性試験の結果をシリコーンエマルジョン組成物の組成とともに表２〜４に示す。 The results of the mechanical stability test are shown in Tables 2 to 4 together with the composition of the silicone emulsion composition.
表から明らかなように各実施例のシリコーンエマルジョン組成物は消泡剤添加に対して優れた機械安定性を示す事が分かった。 As is clear from the table, it was found that the silicone emulsion composition of each example exhibited excellent mechanical stability with respect to the addition of the antifoaming agent.
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