JP7037921B2 - Adhesive for unvulcanized rubber and adhesive for unvulcanized rubber Water dispersion - Google Patents
Adhesive for unvulcanized rubber and adhesive for unvulcanized rubber Water dispersion Download PDFInfo
- Publication number
- JP7037921B2 JP7037921B2 JP2017220877A JP2017220877A JP7037921B2 JP 7037921 B2 JP7037921 B2 JP 7037921B2 JP 2017220877 A JP2017220877 A JP 2017220877A JP 2017220877 A JP2017220877 A JP 2017220877A JP 7037921 B2 JP7037921 B2 JP 7037921B2
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- JP
- Japan
- Prior art keywords
- adhesive
- mass
- unvulcanized rubber
- rubber
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001971 elastomer Polymers 0.000 title claims description 122
- 239000005060 rubber Substances 0.000 title claims description 122
- 239000000853 adhesive Substances 0.000 title claims description 77
- 230000001070 adhesive effect Effects 0.000 title claims description 77
- 239000006185 dispersion Substances 0.000 title claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 32
- 239000000843 powder Substances 0.000 claims description 21
- 239000003945 anionic surfactant Substances 0.000 claims description 16
- 239000002736 nonionic surfactant Substances 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000006353 oxyethylene group Chemical group 0.000 claims description 10
- 239000003223 protective agent Substances 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- 235000013399 edible fruits Nutrition 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- -1 alkaline earth metal carbonates Chemical class 0.000 description 22
- 239000000725 suspension Substances 0.000 description 16
- 239000010408 film Substances 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 229920002857 polybutadiene Polymers 0.000 description 11
- 244000043261 Hevea brasiliensis Species 0.000 description 10
- 239000005062 Polybutadiene Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
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- 239000002518 antifoaming agent Substances 0.000 description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
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- 239000004636 vulcanized rubber Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
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- 235000014113 dietary fatty acids Nutrition 0.000 description 5
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- 238000003756 stirring Methods 0.000 description 5
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- 229910019142 PO4 Inorganic materials 0.000 description 4
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- 125000003342 alkenyl group Chemical group 0.000 description 4
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- 239000005995 Aluminium silicate Substances 0.000 description 2
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- 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
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
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- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229910000275 saponite Inorganic materials 0.000 description 2
- 229910021647 smectite Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical group CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- AYXDJWHRGMGHAY-UHFFFAOYSA-N 3,3,6,6-tetramethyl-4-phenoxyoctan-4-ol Chemical compound CCC(C)(C)CC(O)(C(C)(C)CC)OC1=CC=CC=C1 AYXDJWHRGMGHAY-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- WDQOEAOLRIMQDA-UHFFFAOYSA-N 3-methylbutyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCC(C)C WDQOEAOLRIMQDA-UHFFFAOYSA-N 0.000 description 1
- BMFMQGXDDJALKQ-BYPYZUCNSA-N Argininic acid Chemical class NC(N)=NCCC[C@H](O)C(O)=O BMFMQGXDDJALKQ-BYPYZUCNSA-N 0.000 description 1
- 241000416162 Astragalus gummifer Species 0.000 description 1
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- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
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- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 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 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 125000002958 pentadecyl 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])[H] 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 235000010491 tara gum Nutrition 0.000 description 1
- 239000000213 tara gum Substances 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
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000004846 water-soluble epoxy resin Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、未加硫ゴム用防着剤および未加硫ゴム用防着剤水分散液に関する。 The present invention relates to an adhesive for unvulcanized rubber and an aqueous dispersion of an adhesive for unvulcanized rubber.
天然ゴム（ＮＲ）、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）等のゴムの生産加工の現場においては、シート状等に成形された未加硫ゴムを、次の成形、加硫等の工程に移行するまでの間、積み重ねたり、折り畳んだりして貯蔵することがある。このような貯蔵時において、未加硫ゴム同士が密着し、剥がれなくなることを防止する目的で、未加硫ゴムの表面に防着剤（密着防止剤）を付着させることが行われている。 At the production and processing sites of rubber such as natural rubber (NR), butadiene rubber (BR), and styrene-butadiene rubber (SBR), unvulcanized rubber molded into a sheet or the like is used for the next molding, vulcanization, etc. It may be stacked or folded for storage until the process transitions. During such storage, an adhesive (adhesion preventive agent) is attached to the surface of the unvulcanized rubber for the purpose of preventing the unvulcanized rubbers from adhering to each other and not peeling off.
未加硫ゴム用防着剤（以下、「ゴム用防着剤」または「防着剤」ということがある）が良好な防着性を発揮するためには、ゴム表面への付着性が高いことが必要である。このため、ゴム用防着剤のゴム表面への付着性を高めるための種々の工夫がなされている。例えば、特許文献１～４では、膨潤性の無機粉末に、アルギン酸ナトリウム、ＣＭＣ（カルボキシメチルセルロース）、ポリアクリル酸ナトリウム、ＰＶＡ（ポリビニルアルコール）等の水溶性高分子、キサンタンガム等の水溶性多糖類等を配合して防着剤水分散液の粘度を上昇させ、ゴム表面への防着剤の付着性を向上させている。 In order for an unvulcanized rubber adhesive (hereinafter sometimes referred to as "rubber adhesive" or "adhesive") to exhibit good adhesiveness, it has high adhesion to the rubber surface. It is necessary. Therefore, various measures have been taken to improve the adhesiveness of the rubber adhesive to the rubber surface. For example, in Patent Documents 1 to 4, swellable inorganic powders include water-soluble polymers such as sodium alginate, CMC (carboxymethyl cellulose), sodium polyacrylate and PVA (polyvinyl alcohol), and water-soluble polysaccharides such as xanthan gum. Is compounded to increase the viscosity of the adhesive aqueous dispersion and improve the adhesion of the adhesive to the rubber surface.
特許文献１～４では、前述のとおり、防着剤水分散液の粘度を上昇させることで、ゴム表面への付着性を向上させている。しかし、防着剤水分散液の粘度が高すぎると、乾燥に時間がかかり、未乾燥部分で未加硫ゴム同士が密着して剥がれなくなり、防着性を発揮できないおそれがある。また、この問題があるために、防着剤水分散液の濃度コントロールによって、前記水分散液の粘度を厳しくコントロールする必要がある。 In Patent Documents 1 to 4, as described above, the adhesiveness to the rubber surface is improved by increasing the viscosity of the adhesive aqueous dispersion. However, if the viscosity of the water-bonding agent aqueous dispersion is too high, it takes a long time to dry, and the unvulcanized rubbers may adhere to each other in the undried portion and may not be peeled off, so that the adhesive property may not be exhibited. Further, due to this problem, it is necessary to strictly control the viscosity of the aqueous dispersion by controlling the concentration of the adhesive aqueous dispersion.
そこで、本発明は、水分散液の粘度コントロールに頼ることなく、ゴム表面への付着性を向上可能な未加硫ゴム用防着剤、および未加硫ゴム用防着剤水分散液を提供することを目的とする。 Therefore, the present invention provides an unvulcanized rubber adhesive and an unvulcanized rubber adhesive water dispersion that can improve the adhesion to the rubber surface without relying on the viscosity control of the aqueous dispersion. The purpose is to do.
前記目的を達成するために、本発明の未加硫ゴム用防着剤は、下記成分（Ａ）～（Ｄ）を含むことを特徴とする。
（Ａ）無機粉末
（Ｂ）下記式（１）で表される化合物
（Ｃ）成分（Ｂ）を除くノニオン界面活性剤
（Ｄ）アニオン界面活性剤
Ｒ１は、炭素数４～２０の直鎖または分岐鎖の炭化水素基であり、
ＥＯは、オキシエチレン基であり、
ＰＯは、オキシプロピレン基であり、
ｍは、ＥＯの平均付加モル数を示す０～１０の数であり、
ｎは、ＰＯの平均付加モル数を示す０～１０の数であり、
／は、ＥＯおよびＰＯがランダム付加またはブロック付加のいずれでもよいことを示す。
In order to achieve the above object, the adhesive for unvulcanized rubber of the present invention is characterized by containing the following components (A) to (D).
(A) Inorganic powder (B) Nonionic surfactant (D) Anionic surfactant excluding compound (C) component (B) represented by the following formula (1)
R1 is a straight-chain or branched-chain hydrocarbon group having 4 to 20 carbon atoms.
EO is an oxyethylene group
PO is an oxypropylene group and
m is a number from 0 to 10 indicating the average number of moles of EO added.
n is a number from 0 to 10 indicating the average number of moles of PO added.
/ Indicates that EO and PO may be either random or block-added.
本発明の未加硫ゴム用防着剤水分散液は、
前記本発明の未加硫ゴム用防着剤と、
水と、
を含むことを特徴とする。
The water dispersion of the adhesive for unvulcanized rubber of the present invention is
The adhesive for unvulcanized rubber of the present invention and
water and,
It is characterized by including.
本発明によれば、水分散液の粘度コントロールに頼ることなく、ゴム表面への付着性を向上可能な未加硫ゴム用防着剤、および未加硫ゴム用防着剤水分散液を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, an adhesive for unvulcanized rubber and a water dispersion for unvulcanized rubber, which can improve the adhesion to the rubber surface without relying on the viscosity control of the aqueous dispersion, are provided. can do.
以下、本発明について、さらに具体的に説明する。ただし、本発明は、以下の説明により限定されない。 Hereinafter, the present invention will be described in more detail. However, the present invention is not limited by the following description.
本発明の未加硫ゴム用防着剤および未加硫ゴム用防着剤水分散液は、例えば、成分（Ｂ）の全体の質量（Ｂａｌｌ）に対して、前記式（１）においてｍ＝０、ｎ＝０である化合物（Ｂ０）の含有率（（Ｂ０／Ｂａｌｌ）×１００）が、１０～１００質量％であってもよい。 The unvulcanized rubber protective agent and the unvulcanized rubber protective agent aqueous dispersion of the present invention are, for example, m in the above formula (1) with respect to the total mass ( Ball ) of the component (B). The content ((B 0 / Ball ) × 100) of the compound (B 0 ) in which = 0 and n = 0 may be 10 to 100% by mass.
［無機粉末（Ａ）］
無機粉末（Ａ）（成分（Ａ））は、特に限定されず、例えば、スメクタイト、カオリン（カオリンクレーともいう）、クレー、タルク、マイカ、アルカリ土類金属炭酸塩等が挙げられる。前記スメクタイトとしては、例えば、モンモリロナイト、バイデライト、ノントロナイト、サポナイト、ヘクトライト、ソーコナイト、スチブンサイト等のスメクタイト、および、モンモリロナイトを含有するベントナイト等が挙げられる。前記アルカリ土類金属炭酸塩としては、例えば、炭酸カルシウム、炭酸マグネシウム等が挙げられる。成分（Ａ）は、無機粉末を１種類のみ含んでいてもよいし、２種類以上の無機粉末を併用してもよい。
[Inorganic powder (A)]
The inorganic powder (A) (component (A)) is not particularly limited, and examples thereof include smectite, kaolin (also referred to as kaolin clay), clay, talc, mica, and alkaline earth metal carbonates. Examples of the smectite include smectites such as montmorillonite, byderite, nontronite, saponite, hectorite, saponite, and stibunsite, and bentonite containing montmorillonite. Examples of the alkaline earth metal carbonate include calcium carbonate, magnesium carbonate and the like. The component (A) may contain only one kind of inorganic powder, or two or more kinds of inorganic powder may be used in combination.
本発明の未加硫ゴム用防着剤中における成分（Ａ）の含有率は、目的に応じて選択可能であり、例えば、前記成分（Ａ）～（Ｄ）の質量の合計に対して、６０質量％以上９８．４質量％以下、６５質量％以上９５質量％以下、または７０質量％以上９０質量％以下であってもよい。本発明の未加硫ゴム用防着剤に付着性向上や高い分散安定性を付与し水中での分離を防止する観点から、前記無機粉末の含有率が低すぎないことが好ましい。また、本発明の未加硫ゴム用防着剤の分散性低下、乾燥性低下を防止する観点から、前記無機粉末の含有率が高すぎないことが好ましい。 The content of the component (A) in the non-vulcanized rubber adhesive of the present invention can be selected according to the purpose, for example, with respect to the total mass of the components (A) to (D). It may be 60% by mass or more and 98.4% by mass or less, 65% by mass or more and 95% by mass or less, or 70% by mass or more and 90% by mass or less. From the viewpoint of improving the adhesiveness and imparting high dispersion stability to the unvulcanized rubber adhesive of the present invention and preventing separation in water, it is preferable that the content of the inorganic powder is not too low. Further, from the viewpoint of preventing a decrease in dispersibility and a decrease in dryness of the non-vulcanized rubber adhesive according to the present invention, it is preferable that the content of the inorganic powder is not too high.
［式（１）で表される化合物（Ｂ）］
化合物（Ｂ）（成分（Ｂ））は、下記式（１）で表される。
Ｒ１は、炭素数４～２０の直鎖または分岐鎖の炭化水素基であり、
ＥＯは、オキシエチレン基であり、
ＰＯは、オキシプロピレン基であり、
ｍは、ＥＯの平均付加モル数を示す０～１０の数であり、
ｎは、ＰＯの平均付加モル数を示す０～１０の数であり、
／は、ＥＯおよびＰＯがランダム付加またはブロック付加のいずれでもよいことを示す。
[Compound (B) represented by the formula (1)]
The compound (B) (component (B)) is represented by the following formula (1).
R1 is a straight-chain or branched-chain hydrocarbon group having 4 to 20 carbon atoms.
EO is an oxyethylene group
PO is an oxypropylene group and
m is a number from 0 to 10 indicating the average number of moles of EO added.
n is a number from 0 to 10 indicating the average number of moles of PO added.
/ Indicates that EO and PO may be either random or block-added.
前記式（１）中、Ｒ１は、前述のとおり、炭素数４～２０の直鎖または分岐鎖の炭化水素基である。成分（Ｂ）は、式（１）で表される２種類以上の化合物の混合物であってもよく、その場合、Ｒ１の炭素数は、前記混合物における平均炭素数である。Ｒ１の炭素数は、例えば、４～１６、４～１２、または４～９であってもよい。前記炭化水素基としては、例えば、飽和または不飽和炭化水素基が挙げられる。前記飽和または不飽和炭化水素基は、例えば、脂肪族飽和または不飽和炭化水素基である。前記脂肪族飽和または不飽和炭化水素基は、例えば、アルキル基、アルケニル基、アルキニル基等であってもよい。 In the formula (1), as described above, R 1 is a straight-chain or branched-chain hydrocarbon group having 4 to 20 carbon atoms. The component (B) may be a mixture of two or more kinds of compounds represented by the formula (1), in which case the carbon number of R1 is the average carbon number in the mixture. The carbon number of R 1 may be, for example, 4 to 16, 4 to 12, or 4 to 9. Examples of the hydrocarbon group include saturated or unsaturated hydrocarbon groups. The saturated or unsaturated hydrocarbon group is, for example, an aliphatic saturated or unsaturated hydrocarbon group. The aliphatic saturated or unsaturated hydrocarbon group may be, for example, an alkyl group, an alkenyl group, an alkynyl group or the like.
前記アルキル基は、特に限定されず、例えば、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、２－エチルヘキシル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基等が挙げられる。 The alkyl group is not particularly limited, and for example, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, and the like. Examples thereof include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and an icosyl group.
前記アルケニル基は、例えば、前記アルキル基において、１個または複数の二重結合を有するもの等が挙げられる。前記アルケニル基としては、例えば、１－ブテニル基、２－ブテニル基、３－ブテニル基、１，３－ブタジニエル基、３－メチル－２－ブテニル基等が挙げられる。 Examples of the alkenyl group include those having one or more double bonds in the alkyl group. Examples of the alkenyl group include 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butaziniel group, 3-methyl-2-butenyl group and the like.
前記アルキニル基は、例えば、前記アルキル基において、１個または複数の三重結合を有するもの等が挙げられる。前記アルキニル基としては、例えば、ブチニル基等が挙げられる。前記アルキニル基は、例えば、さらに、１個または複数の二重結合を有してもよい。 Examples of the alkynyl group include those having one or more triple bonds in the alkyl group. Examples of the alkynyl group include a butynyl group and the like. The alkynyl group may further have, for example, one or more double bonds.
前述のとおり、前記式（１）中、ｍは、ＥＯの平均付加モル数を示す０～１０の数である。ｍは、例えば、０～６、０～４、０～２、または０であってもよい。 As described above, in the formula (1), m is a number of 0 to 10 indicating the average number of added moles of EO. m may be, for example, 0 to 6, 0 to 4, 0 to 2, or 0.
前述のとおり、前記式（１）中、ｎは、ＰＯの平均付加モル数を示す０～１０の数である。ｎは、例えば、０～７、０～６、０～５、または０～３であってもよい。 As described above, in the formula (1), n is a number of 0 to 10 indicating the average number of moles of added PO. n may be, for example, 0 to 7, 0 to 6, 0 to 5, or 0 to 3.
本発明の未加硫ゴム用防着剤によれば、前述の無機粉末（成分（Ａ））に、式（１）において、Ｒ１の炭素数が４～２０、ｍ＝０～１０、かつ、ｎ＝０～１０である化合物（成分（Ｂ））と、後述の成分（Ｃ）（成分（Ｂ）以外のノニオン界面活性剤）および成分（Ｄ）（アニオン界面活性剤）とを配合することで、水分散液の粘度コントロールに頼ることなく、表面張力の調整により、ゴム表面への付着性を向上可能である。 According to the non-vultured rubber adhesive of the present invention, the above-mentioned inorganic powder (component (A)) has 4 to 20 carbon atoms of R1 in the formula (1), m = 0 to 10, and the above-mentioned inorganic powder (component (A)). , N = 0 to 10 (component (B)), and a component (C) (nonionic surfactant other than the component (B)) and a component (D) (anionic surfactant) described later are blended. Therefore, it is possible to improve the adhesiveness to the rubber surface by adjusting the surface tension without relying on the viscosity control of the aqueous dispersion.
前記式（１）において、ｍおよびｎの和（ｍ＋ｎ）は、特に限定されず、例えば、０～８、０～６、０～５、または０～３であってもよい。 In the above formula (1), the sum of m and n (m + n) is not particularly limited and may be, for example, 0 to 8, 0 to 6, 0 to 5, or 0 to 3.
前述のとおり、例えば、成分（Ｂ）の全体の質量（Ｂａｌｌ）に対して、前記式（１）においてｍ＝０、ｎ＝０である化合物（Ｂ０）の含有率（（Ｂ０／Ｂａｌｌ）×１００）は、１０～１００質量％であってもよい。成分（Ｂ）に含まれる、前記式（１）においてｍ＝０、ｎ＝０である化合物（Ｂ０）の量は、例えば、一般的に界面活性剤の分析に使用されるＨＰＬＣ（Ｈｉｇｈ Ｐｅｒｆｏｒｍａｎｃｅ Ｌｉｑｕｉｄ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ、高速液体クロマトグラフィー）により定量できる。 As described above, for example, the content of the compound (B 0 ) having m = 0 and n = 0 in the above formula (1) with respect to the total mass (B all ) of the component (B) ((B 0 /). B all ) × 100) may be 10 to 100% by mass. The amount of the compound (B 0 ) contained in the component (B) in which m = 0 and n = 0 in the formula (1) is, for example, HPLC (High Performance) generally used for the analysis of surfactants. It can be quantified by Liquid Chromatography (High Performance Liquid Chromatography).
本発明の未加硫ゴム用防着剤中における成分（Ｂ）の含有率は、目的に応じて選択可能であり、例えば、前記成分（Ａ）～（Ｄ）の質量の合計に対して、０．１質量％以上１０質量％以下、０．３質量％以上８質量％以下、または０．５質量％以上６質量％以下であってもよい。 The content of the component (B) in the non-vulcanized rubber adhesive of the present invention can be selected according to the intended purpose. For example, with respect to the total mass of the components (A) to (D). It may be 0.1% by mass or more and 10% by mass or less, 0.3% by mass or more and 8% by mass or less, or 0.5% by mass or more and 6% by mass or less.
本発明の未加硫ゴム用防着剤の調製において、成分（Ｂ）は、例えば、市販品を使用することができる。前記市販品は、例えば、前記式（１）におけるＥＯの付加モル数およびＰＯの付加モル数が、それぞれ、分布を有し、平均付加モル数で示されていることが一般的である。このため、例えば、前記式（１）と平均付加モル数（０～１０）を満たす市販品を使用すれば、調製された組成物（未加硫ゴム用防着剤）中に、成分（Ｂ）を含有させることができる。 In the preparation of the adhesive for unvulcanized rubber of the present invention, for example, a commercially available product can be used as the component (B). In the commercially available product, for example, the number of added moles of EO and the number of added moles of PO in the formula (1) have distributions, respectively, and are generally represented by the average number of added moles. Therefore, for example, if a commercially available product satisfying the above formula (1) and the average number of moles of substance (0 to 10) is used, the component (B) is contained in the prepared composition (adhesive agent for unvulcanized rubber). ) Can be contained.
［成分（Ｂ）を除くノニオン界面活性剤（Ｃ）］
本発明の未加硫ゴム用防着剤において、成分（Ｃ）は、前述のとおり、成分（Ｂ）を除く（すなわち、成分（Ｂ）以外の）ノニオン界面活性剤である。ノニオン界面活性剤（Ｃ）は、例えば、未加硫ゴム用防着剤に濡れ性および水への分散性を付与する働きをする。ノニオン界面活性剤（Ｃ）（成分（Ｃ））としては、特に限定されず、例えば、ポリオキシアルキレンアルキルエーテル型のノニオン界面活性剤等が挙げられる。ノニオン界面活性剤（Ｃ）は、ノニオン界面活性剤を１種類のみ用いてもよいし、２種類以上併用してもよい。
[Nonion surfactant (C) excluding component (B)]
In the non-vulcanized rubber adhesive of the present invention, the component (C) is a nonionic surfactant excluding the component (B) (that is, other than the component (B)) as described above. The nonionic surfactant (C) serves, for example, to impart wettability and dispersibility in water to an unvulcanized rubber adhesive. The nonionic surfactant (C) (component (C)) is not particularly limited, and examples thereof include a polyoxyalkylene alkyl ether type nonionic surfactant. As the nonionic surfactant (C), only one type of nonionic surfactant may be used, or two or more types may be used in combination.
ノニオン界面活性剤（Ｃ）は、特に限定されず、本発明では、例えば、下記式（２）で表されるノニオン界面活性剤のうち成分（Ｂ）を除くノニオン界面活性剤を用いることができる。下記式（２）のノニオン界面活性剤は、後述のアニオン界面活性剤（成分（Ｄ））とともに、防着剤懸濁液（水分散液）の未加硫ゴムの表面に対する表面張力を低下させるのに加えて、防着剤の未加硫ゴムの表面への付着性を効果的に高める作用を奏するものと推測される。ただし、この推測は、本発明をなんら限定しない。
ＲＯ－（ＡＯ）ｘ－Ｈ ・・・（２）
The nonionic surfactant (C) is not particularly limited, and in the present invention, for example, a nonionic surfactant excluding the component (B) among the nonionic surfactants represented by the following formula (2) can be used. .. The nonionic surfactant of the following formula (2), together with the anionic surfactant (component (D)) described later, lowers the surface tension of the adhesive suspension (aqueous dispersion) on the surface of the unsulfurized rubber. In addition to this, it is presumed that it has the effect of effectively enhancing the adhesion of the adhesive to the surface of the unsulfided rubber. However, this guess does not limit the present invention in any way.
RO- (AO) x -H ... (2)
前記式（２）中、Ｒは、炭素数が８～１８の脂肪族炭化水素基を示す。前記脂肪族炭化水素基は、直鎖状でも分岐鎖状でもよい。また、飽和、不飽和のいずれであってもよい。Ｒの炭素数は、成分（Ａ）の分散性に優れる点から、好ましくは１２～１６であり、１２～１３がさらに好ましい。
ＡＯは、炭素数２～４のオキシアルキレン基を示し、ｘは、ＡＯの平均付加モル数である。
ｘは、例えば、１～３０、１～２５、または１～２０であってもよい。具体的には、界面活性能が低下し、成分（Ａ）の分散性が低下することを防止する観点から、ｘは、１以上（すなわち、０ではない）が好ましい。また、親水性が高くなりすぎることによる付着性低下を防止する観点から、ｘは、３０以下が好ましく、２５以下がより好ましく、２０以下がさらに好ましい。ｘが、好ましくは１～３０の範囲、より好ましくは１～２５の範囲、さらに好ましくは１～２０の範囲であれば、成分（Ａ）の分散性がさらに向上し、かつ、未加硫ゴム表面の疎水性が高い場合にも、被覆に充分な粘弾性を与えることで付着性を向上させるものと推測される。ただし、この推測は、本発明をなんら限定しない。
In the formula (2), R represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms. The aliphatic hydrocarbon group may be linear or branched. Further, it may be saturated or unsaturated. The carbon number of R is preferably 12 to 16, and more preferably 12 to 13 from the viewpoint of excellent dispersibility of the component (A).
AO represents an oxyalkylene group having 2 to 4 carbon atoms, and x is the average number of moles of AO added.
x may be, for example, 1 to 30, 1 to 25, or 1 to 20. Specifically, x is preferably 1 or more (that is, not 0) from the viewpoint of preventing the surface active ability from being lowered and the dispersibility of the component (A) from being lowered. Further, from the viewpoint of preventing deterioration of adhesiveness due to excessively high hydrophilicity, x is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less. When x is preferably in the range of 1 to 30, more preferably in the range of 1 to 25, still more preferably in the range of 1 to 20, the dispersibility of the component (A) is further improved, and the unvulcanized rubber is further improved. Even when the surface is highly hydrophobic, it is presumed that the adhesion is improved by imparting sufficient viscoelasticity to the coating. However, this guess does not limit the present invention in any way.
炭素数２～４のオキシアルキレン基とは、例えば、炭素数２～４のアルキレンオキサイドの付加重合により形成される重合単位である。炭素数２～４のオキシアルキレン基としては、具体的には、エチレンオキサイドが付加して形成されるオキシエチレン基（ＥＯ）、プロピレンオキサイドが付加して形成されるオキシプロピレン基（ＰＯ）、および、ブチレンオキサイドが付加して形成されるオキシブチレン基（ＢＯ）がある。（ＡＯ）ｘは、その構造中に、少なくともオキシエチレン基（ＥＯ）を含み、オキシエチレン基（ＥＯ）のみでもよいし、オキシエチレン基（ＥＯ）とさらに他のオキシアルキレン基とを含んでもよい。（ＡＯ）ｘが、オキシエチレン基（ＥＯ）と、オキシプロピレン基（ＰＯ）と、オキシブチレン基（ＢＯ）とのうち複数種類を含む場合、これらの基は、ブロック状に配列していても、ランダムに配列していてもよい。（ＡＯ）ｘは、例えば、親水性、疎水性のバランスに優れる点から、オキシエチレン基（ＥＯ）のみからなることが好ましい。 The oxyalkylene group having 2 to 4 carbon atoms is, for example, a polymerization unit formed by addition polymerization of an alkylene oxide having 2 to 4 carbon atoms. Specific examples of the oxyalkylene group having 2 to 4 carbon atoms include an oxyethylene group (EO) formed by adding ethylene oxide, an oxypropylene group (PO) formed by adding propylene oxide, and an oxypropylene group (PO) formed by adding propylene oxide. , There is an oxybutylene group (BO) formed by the addition of butylene oxide. (AO) x may contain at least an oxyethylene group (EO) in its structure and may contain only an oxyethylene group (EO), or may contain an oxyethylene group (EO) and another oxyalkylene group. .. (AO) When x contains a plurality of types of an oxyethylene group (EO), an oxypropylene group (PO), and an oxybutylene group (BO), these groups may be arranged in a block shape. , May be randomly arranged. (AO) x is preferably composed of only an oxyethylene group (EO), for example, from the viewpoint of excellent balance between hydrophilicity and hydrophobicity.
本発明の未加硫ゴム用防着剤中におけるノニオン界面活性剤（Ｃ）の含有率は、目的に応じて選択可能であり、例えば、前記成分（Ａ）～（Ｄ）の質量の合計に対して、１質量％以上２０質量％以下、３質量％以上１８質量％以下、または３質量％以上１５質量％以下であってもよい。ノニオン界面活性剤（Ｃ）の含有率が前記下限値以上であれば、ゴムに対する防着液（防着剤水分散液）の濡れ性が不足することにより、ハジキが発生する等の問題が起こりにくく、前記上限値以下であれば、起泡が多くなり使用の際に設備からオーバーフローするという問題が起こりにくい。 The content of the nonionic surfactant (C) in the non-vulcanized rubber adhesive of the present invention can be selected according to the intended purpose, and is, for example, the total mass of the components (A) to (D). On the other hand, it may be 1% by mass or more and 20% by mass or less, 3% by mass or more and 18% by mass or less, or 3% by mass or more and 15% by mass or less. If the content of the nonionic surfactant (C) is equal to or higher than the lower limit, problems such as repelling may occur due to insufficient wettability of the adhesive liquid (adhesive agent water dispersion) to rubber. It is difficult, and if it is not more than the upper limit value, the problem that foaming increases and overflows from the equipment during use is unlikely to occur.
［成分（Ｄ）］
本発明の未加硫ゴム用防着剤において、アニオン界面活性剤（Ｄ）（成分（Ｄ））は、例えば、未加硫ゴム用防着剤に濡れ性および水への分散性を付与する働きをする。アニオン界面活性剤（Ｄ）（成分（Ｄ））としては、特に限定されず、例えば、下記（１）～（４）等が挙げられる。また、アニオン界面活性剤（Ｄ）は、アニオン界面活性剤を１種類のみ用いてもよいし、２種類以上併用してもよい。
（１）高級脂肪酸塩、アルキルエーテルカルボン酸塩、ポリオキシアルキレンエーテルカルボン酸塩、アルキル（又はアルケニル）アミドエーテルカルボン酸塩、アシルアミノカルボン酸塩等のカルボン酸型アニオン界面活性剤
（２）高級アルコール硫酸エステル塩、ポリオキシアルキレン高級アルコール硫酸エステル塩、アルキルフェニルエーテル硫酸エステル塩、ポリオキシアルキレンアルキルフェニルエーテル硫酸エステル塩、グリセリン脂肪酸エステルモノ硫酸エステル塩等の硫酸エステル型アニオン界面活性剤
（３）アルカンスルホン酸塩、α－オレフィンスルホン酸塩、直鎖アルキルベンゼンスルホン酸塩、α－スルホ脂肪酸エステル塩、ジアルキルスルホコハク酸塩等のスルホン酸型アニオン界面活性剤
（４）アルキルリン酸エステル塩、ポリオキシアルキレンアルキルリン酸エステル塩、ポリオキシアルキレンアルキルフェニルリン酸エステル塩、グリセリン脂肪酸エステルモノリン酸エステル塩等のリン酸エステル型アニオン界面活性剤
[Component (D)]
In the adhesive for unvulcanized rubber of the present invention, the anionic surfactant (D) (component (D)) imparts wettability and dispersibility in water to, for example, the adhesive for unvulcanized rubber. To work. The anionic surfactant (D) (component (D)) is not particularly limited, and examples thereof include the following (1) to (4). Further, as the anionic surfactant (D), only one type of anionic surfactant may be used, or two or more types may be used in combination.
(1) Sulfonic acid type anionic surfactants such as higher fatty acid salts, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, and acylaminocarboxylates (2) Higher Sulfonate-type anionic surfactants such as alcohol sulfate, polyoxyalkylene higher alcohol sulfate, alkylphenyl ether sulfate, polyoxyalkylene alkylphenyl ether sulfate, glycerin fatty acid ester monosulfate (3) Sulfonic acid type anionic surfactants such as alkane sulfonate, α-olefin sulfonate, linear alkylbenzene sulfonate, α-sulfo fatty acid ester salt, dialkyl sulfosuccinate (4) Alkyl phosphate ester salt, polyoxy Phosphate-type anionic surfactants such as alkylene alkyl phosphate ester salts, polyoxyalkylene alkylphenyl phosphate ester salts, and glycerin fatty acid ester monophosphate ester salts.
アニオン界面活性剤の対イオンは、特に限定されず、ナトリウム、カリウム等のアルカリ金属、モノエタノールアミン、ジエタノールアミン等のアルカノールアミンが好ましい。これらは、１種のみを単独で使用してもよく、２種以上を併用してもよい。 The counterion of the anionic surfactant is not particularly limited, and alkali metals such as sodium and potassium, and alkanolamines such as monoethanolamine and diethanolamine are preferable. These may be used alone or in combination of two or more.
アニオン界面活性剤としては、未加硫ゴムの表面との濡れ性により優れる防着剤懸濁液（水分散液）が得られることから、α－オレフィンスルホン酸塩、ジアルキルスルホコハク酸塩が好ましく、α－オレフィンスルホン酸塩としてはα－オレフィンスルホン酸Ｎａ塩「リポラン（登録商標）ＬＢ－８４０」（ライオン・スペシャリティ・ケミカルズ株式会社製）、ジアルキルスルホコハク酸塩としては、ジオクチルスルホサクシネートＮａ塩がより好ましい。 As the anionic surfactant, α-olefin sulfonate and dialkylsulfosuccinate are preferable because an adhesive suspension (aqueous dispersion) having excellent wettability with the surface of unsulfided rubber can be obtained. The α-olefin sulfonic acid salt is α-olefin sulfonic acid Na salt "Liporan (registered trademark) LB-840" (manufactured by Lion Specialty Chemicals Co., Ltd.), and the dialkylsulfosuccinate is dioctylsulfosuccinate Na salt. More preferred.
本発明の未加硫ゴム用防着剤中におけるアニオン界面活性剤（Ｄ）の含有率は、目的に応じて選択可能であり、例えば、前記成分（Ａ）～（Ｄ）の質量の合計に対して、０．５質量％以上１０質量％以下、０．８質量％以上８質量％以下、または１質量％以上５質量％以下であってもよい。アニオン界面活性剤（Ｄ）の含有率が前記下限値以上であれば、ゴムに対する防着液（防着剤水分散液）の濡れ性が不足することにより、ハジキが発生する等の問題が起こりにくく、前記上限値以下であれば、起泡が多くなり使用の際に設備からオーバーフローするという問題が起こりにくい。 The content of the anionic surfactant (D) in the non-vulcanized rubber adhesive of the present invention can be selected according to the intended purpose, and is, for example, the total mass of the components (A) to (D). On the other hand, it may be 0.5% by mass or more and 10% by mass or less, 0.8% by mass or more and 8% by mass or less, or 1% by mass or more and 5% by mass or less. If the content of the anionic surfactant (D) is equal to or higher than the lower limit, problems such as repelling may occur due to insufficient wettability of the adhesive liquid (water-bonding agent water dispersion) to rubber. It is difficult, and if it is not more than the upper limit value, the problem that foaming increases and overflows from the equipment during use is unlikely to occur.
［任意成分］
本発明の未加硫ゴム用防着剤は、成分（Ａ）～（Ｄ）以外の任意成分を含んでいてもよいし、含んでいなくてもよい。本発明の未加硫ゴム用防着剤には、必要に応じて、例えば、任意成分として、消泡剤、濡れ性補助剤、粘性補助剤、異物低減補助剤等の添加剤等が含まれていてもよい。
[Arbitrary ingredient]
The adhesive for unvulcanized rubber of the present invention may or may not contain arbitrary components other than the components (A) to (D). The adhesive for unvulcanized rubber of the present invention contains, for example, as an optional component, an additive such as a defoaming agent, a wettability auxiliary agent, a viscosity auxiliary agent, and a foreign matter reduction auxiliary agent, if necessary. May be.
消泡剤としては、特に限定されず、例えば、ヒマシ油、ゴマ油、アマニ油、動植物油等の油脂系消泡剤；ステアリン酸イソアミル、コハク酸ジステアリル、エチレングリコールジステアレート、ステアリン酸ブチル等の脂肪酸エステル系消泡剤；ポリオキシアルキレンモノハイドリックアルコールジ－ｔ－アミルフェノキシエタノール等のアルコール系消泡剤；ジ－ｔ－アミルフェノキシエタノール３－ヘプチルセロソルブノニルセロソルブ３－ヘプチルカルビトール等のエーテル系消泡剤；トリブチルオスフェート、トリス（ブトキシエチル）フォスフェート等のリン酸エステル系消泡剤；ジアミルアミン等のアミン系消泡剤；ポリアルキレンアミド、アシレートポリアミン等のアミド系消泡剤；鉱物油；シリコーン油；等が挙げられる。前記消泡剤は、１種類のみ用いてもよいし、２種類以上併用してもよい。 The defoaming agent is not particularly limited, and is, for example, an oil-based defoaming agent such as castor oil, sesame oil, flaxseed oil, animal and vegetable oil; isoamyl stearate, distearyl succinate, ethylene glycol distearate, butyl stearate and the like. Defoamer based on fatty acid ester; alcohol-based defoaming agent such as polyoxyalkylene monohydric alcohol di-t-amylphenoxyethanol; Defoaming agent; Phosphate-based defoaming agent such as tributyl osfate, Tris (butoxyethyl) phosphate; Amine-based defoaming agent such as diamilamine; Amid-based defoaming agent such as polyalkylene amide and acylate polyamine; Mineral Oil; silicone oil; and the like. Only one type of the defoaming agent may be used, or two or more types may be used in combination.
濡れ性補助剤としては、特に限定されず、例えば、アルコール類が挙げられ、より具体的には、例えば、メタノール、エタノール、グリセリン、１，３－ブタンジオール、プロピレングリコール、ジプロピレングリコール、ペンチレングリコール、ヘキシレングリコール、ソルビトール、マルチトール、スクロース、エリスリトール、キシリトール、ポリエチレングリコール、ポリプロピレングリコール、多価アルコールのエチレンオキサイドやプロピレンオキサイドの付加物等が挙げられる。前記濡れ性補助剤は、１種類のみ用いてもよいし、２種類以上併用してもよい。 The wetting aid is not particularly limited, and examples thereof include alcohols, and more specifically, for example, methanol, ethanol, glycerin, 1,3-butanediol, propylene glycol, dipropylene glycol, and pentylene. Glycol, hexylene glycol, sorbitol, martitol, sucrose, erythritol, xylitol, polyethylene glycol, polypropylene glycol, polyhydric alcohols such as ethylene oxide and propylene oxide adducts can be mentioned. Only one type of the wetting aid may be used, or two or more types may be used in combination.
粘性補助剤としては、特に限定されず、例えば、水溶性高分子類が挙げられ、より具体的には、例えば、蛋白類、ポリアクリル酸、ポリアクリル酸ナトリウム、ポリアクリルアミド、ポリビニルアルコール、ポリビニルピロリドン、ポリエチレングリコール、ポリエチレンオキシド、水溶性ウレタン樹脂、水溶性メラミン樹脂、水溶性エポキシ樹脂、水溶性ブタジエン樹脂、水溶性フェノール樹脂等の合成水溶性高分子；キサンタンガム、グアーガム、ウェランガム、ローカストビーンガム、ダイユータンガム、タマリンドガム、タマリンドシードガム、トラガントガム、アラビアガム、カラギーナン、ラムザンガム、サクシノグリカン、タラガム、ジェランガム、カラヤガム、ペクチン、アルギン酸誘導体、セルロースエーテル類等の天然水溶性高分子が挙げられる。前記粘性補助剤は、１種類のみ用いてもよいし、２種類以上併用してもよい。 The viscosity aid is not particularly limited, and examples thereof include water-soluble polymers, and more specifically, for example, proteins, polyacrylic acid, sodium polyacrylic acid, polyacrylamide, polyvinyl alcohol, and polyvinylpyrrolidone. , Polyethylene glycol, polyethylene oxide, water-soluble urethane resin, water-soluble melamine resin, water-soluble epoxy resin, water-soluble butadiene resin, water-soluble phenol resin and other synthetic water-soluble polymers; Examples thereof include natural water-soluble polymers such as tan gum, tamarind gum, tamarind seed gum, tragant gum, arabic gum, carrageenan, lambzan gum, succinoglycan, tara gum, gellan gum, karaya gum, pectin, arginic acid derivative, and cellulose ethers. Only one kind of the viscosity auxiliary agent may be used, or two or more kinds thereof may be used in combination.
また、本発明の未加硫ゴム用防着剤には、例えば、その粉体流動を抑制する等の目的で、水を含有させてもよい。その場合、水の含有率は、特に限定されず、例えば、２～３質量％程度である。 Further, the adhesive for unvulcanized rubber of the present invention may contain water for the purpose of suppressing the powder flow thereof, for example. In that case, the content of water is not particularly limited, and is, for example, about 2 to 3% by mass.
［未加硫ゴム用防着剤、未加硫ゴム用水分散液および防着処理済み未加硫ゴム］
本発明の未加硫ゴム用防着剤は、前述のとおり、無機粉末（成分（Ａ））を含有する。無機粉末は、防着性を担う成分であるため、良好な防着性を得るためには、前述のとおり、防着剤中の含有率が前記下限値以上であることが好ましい。一方、防着剤中の含有率が前記上限値以下であれば、防着剤乾燥固化物硬度の低減効果がより有効に得られ、より良好な異物抑制効果を得ることができるため好ましい。なお、無機粉末には、水を含んだ状態で流通するものもあるが、本明細書において無機粉末の含有率といった場合、該含有率は、水の量を含まない値である。
[Anti-vulcanizing agent for unvulcanized rubber, water dispersion for unvulcanized rubber, and unvulcanized rubber with anti-vulcanization treatment]
As described above, the adhesive for unvulcanized rubber of the present invention contains an inorganic powder (component (A)). Since the inorganic powder is a component responsible for the adhesive property, it is preferable that the content of the inorganic powder in the adhesive is at least the above lower limit value in order to obtain good adhesive property. On the other hand, when the content in the adhesive is not more than the upper limit, the effect of reducing the hardness of the dry solidified material of the adhesive can be obtained more effectively, and a better effect of suppressing foreign substances can be obtained, which is preferable. Although some inorganic powders are distributed in a state of containing water, the content of the inorganic powder in the present specification is a value not including the amount of water.
本発明の未加硫ゴム用防着剤の製造方法は、特に限定されず、例えば、未加硫ゴム用防着剤の全ての成分、すなわち、成分（Ａ）～（Ｄ）と、必要に応じて配合される任意成分とを混合することにより製造できる。混合に用いる装置としては、例えば、撹拌羽根を容器内に備えた構成の装置等を使用できる。具体的には、例えば、リボン型混合機、垂直スクリュー型混合機等の揺動撹拌または撹拌を行える粉体混合機を挙げることができる。また、撹拌装置が複数組み合わされたスーパーミキサー（株式会社カワタ製）、ハイスピードミキサー（株式会社アーステクニカ製）、ニューグラムマシン（株式会社セイシン企業製）、ＳＶミキサー（株式会社神鋼環境ソリューション社製）等の多機能粉体混合機等も使用できる。また、ジョークラッシャー、ジャイレトリークラッシャー、コーンクラッシャー、ロールクラッシャー、インパクトクラッシャー、ハンマークラッシャー、ロッドミル、ボールミル、振動ロッドミル、振動ボールミル、円盤型ミル、ジェットミル、サイクロンミル等の乾式粉砕機を用いてもよい。 The method for producing the adhesive for unvulcanized rubber of the present invention is not particularly limited, and for example, all the components of the adhesive for unvulcanized rubber, that is, the components (A) to (D) are required. It can be produced by mixing it with an arbitrary component which is appropriately blended. As the device used for mixing, for example, a device having a stirring blade inside the container can be used. Specifically, for example, a powder mixer capable of rocking stirring or stirring such as a ribbon type mixer and a vertical screw type mixer can be mentioned. In addition, a super mixer (manufactured by Kawata Co., Ltd.), a high-speed mixer (manufactured by EarthTechnica Co., Ltd.), a new gram machine (manufactured by Seishin Enterprise Co., Ltd.), and an SV mixer (manufactured by Kobelco Eco-Solutions Co., Ltd.), which are a combination of multiple stirrers. ) And other multifunctional powder mixers can also be used. You can also use a dry crusher such as a jaw crusher, gyre crusher, cone crusher, roll crusher, impact crusher, hammer crusher, rod mill, ball mill, vibrating rod mill, vibrating ball mill, disc type mill, jet mill, cyclone mill, etc. good.
また、未加硫ゴム用防着剤の全ての成分のうち、液体成分を少なくとも１種使用する場合には、例えば、未加硫ゴム用防着剤の製造のために、前記液体成分を液体成分以外の混合物に対して吹付けたり散布したりするスプレー装置、シャワー装置等を併用してもよい。 Further, when at least one liquid component is used among all the components of the unvulcanized rubber protective agent, for example, the liquid component is liquid for the production of the unvulcanized rubber protective agent. A spray device, a shower device, or the like that sprays or sprays a mixture other than the components may be used in combination.
粉末状の未加硫ゴム用防着剤とする場合、粉末防着剤全体に対する成分（Ａ）～（Ｄ）の質量の合計の割合は１００質量％でもよい。また、水および／またはその他の前記任意成分を含む場合、成分（Ａ）～（Ｄ）の質量の合計の割合は特に限定されず、例えば、未加硫ゴム用防着剤の質量全体に対し、例えば、８０質量％以上、８５質量％以上９７質量％以下、または８５質量％以上９５質量％以下である。 In the case of a powdery unvulcanized rubber adhering agent, the total ratio of the masses of the components (A) to (D) to the entire powder adhering agent may be 100% by mass. Further, when water and / or the other optional component is contained, the ratio of the total mass of the components (A) to (D) is not particularly limited, and for example, with respect to the total mass of the unvulcanized rubber adhesive. For example, 80% by mass or more, 85% by mass or more and 97% by mass or less, or 85% by mass or more and 95% by mass or less.
本発明の未加硫ゴム用防着剤は、例えば、前記本発明の未加硫ゴム用防着剤水分散液として用いることができる。本発明の未加硫ゴム用防着剤水分散液の製造方法は、特に限定されない。例えば、前述のように、本発明の未加硫ゴム用防着剤の全ての成分を混合し、本発明の未加硫ゴム用防着剤を製造した後に、それを水中に分散させて、本発明の未加硫ゴム用防着剤水分散液としてもよい。また、例えば、本発明の未加硫ゴム用防着剤の各成分を、それぞれ水中に溶解または分散させ、水中で混合することにより、本発明の未加硫ゴム用防着剤水分散液としてもよい。前記各成分を溶解または分散させる方法も特に限定されず、例えば、粉末状の未加硫ゴム用防着剤を、攪拌槽内で所定量の水に分散させればよい。本発明の未加硫ゴム用防着剤水分散液中における、前記成分（Ａ）、成分（Ｂ）、成分（Ｃ）、および成分（Ｄ）の含有率は、特に限定されず、例えば、本発明の未加硫ゴム用防着剤水分散液全体の質量に対し、０．５質量％以上１０質量％以下、０．５質量％以上８質量％以下、０．５質量％以上６質量％以下、または０．５質量％以上４質量％以下である。 The adhesive for unvulcanized rubber of the present invention can be used, for example, as the aqueous dispersion of the adhesive for unvulcanized rubber of the present invention. The method for producing the water dispersion of the adhesive for unvulcanized rubber of the present invention is not particularly limited. For example, as described above, all the components of the non-vulcanized rubber adhering agent of the present invention are mixed to produce the unvulcanized rubber adhering agent of the present invention, which is then dispersed in water. The adhesive aqueous dispersion for unvulcanized rubber of the present invention may be used. Further, for example, by dissolving or dispersing each component of the adhesive for unvulcanized rubber of the present invention in water and mixing in water, the aqueous dispersion of the adhesive for unvulcanized rubber of the present invention can be obtained. May be good. The method for dissolving or dispersing each of the above components is not particularly limited, and for example, a powdery unvulcanized rubber adhering agent may be dispersed in a predetermined amount of water in a stirring tank. The contents of the component (A), the component (B), the component (C), and the component (D) in the water dispersion of the non-vulture rubber adhesive of the present invention are not particularly limited, and are not particularly limited, for example. 0.5% by mass or more and 10% by mass or less, 0.5% by mass or more and 8% by mass or less, 0.5% by mass or more and 6% by mass with respect to the total mass of the non-vulture rubber protective agent aqueous dispersion of the present invention. % Or less, or 0.5% by mass or more and 4% by mass or less.
未加硫ゴム用防着剤水分散液とする場合、前記未加硫ゴム用防着剤水分散液中における水以外の成分の質量の合計に対する成分（Ａ）～（Ｄ）の合計の含有率は、例えば、９０質量％以上１００質量％以下、９０質量％以上９９質量％以下、または９３質量％以上９８質量％以下である。 In the case of a non-vultured rubber protective agent water dispersion, the total content of the components (A) to (D) with respect to the total mass of the components other than water in the unvulverized rubber protective agent water dispersion is contained. The rate is, for example, 90% by mass or more and 100% by mass or less, 90% by mass or more and 99% by mass or less, or 93% by mass or more and 98% by mass or less.
このように未加硫ゴム用防着剤水分散液として製造した場合、そのまま後述のウェット法等により未加硫ゴム表面に塗布して使用することもできる。 When it is produced as a water dispersion of an adhesive for unvulcanized rubber as described above, it can be directly applied to the surface of unvulcanized rubber by a wet method or the like described later and used.
本発明の未加硫ゴム用防着剤を用いた防着処理済み未加硫ゴムの製造方法は、例えば、前記本発明の未加硫ゴム用防着剤を未加硫ゴムの表面に付着させて防着処理する防着処理工程を有する。このようにして製造された防着処理済み未加硫ゴムは、積み重ねたり、折り畳んだりして貯蔵されても、例えば、未加硫ゴム同士が密着し、剥がれなくなるのを防止できる。 In the method for producing an unvulcanized unvulcanized rubber using the unvulcanized rubber adsorbent of the present invention, for example, the unvulcanized rubber adhering agent of the present invention is attached to the surface of the unvulcanized rubber. It has an anti-adhesion treatment step of vulcanizing and anti-adhesion treatment. Even if the unvulcanized rubber that has been subjected to the adhesion treatment produced in this manner is stacked or folded and stored, for example, it is possible to prevent the unvulcanized rubbers from coming into close contact with each other and not peeling off.
前記防着処理工程は、例えば、前記本発明の未加硫ゴム用防着剤水分散液を前記未加硫ゴムの表面に付着させ、さらに水を揮発させることにより、前記未加硫ゴムの表面に前記本発明の未加硫ゴム用防着剤を付着させる工程であってもよい。より具体的には、前記防着処理工程は、前記本発明の未加硫ゴム用防着剤水分散液（防着剤懸濁液）を未加硫ゴムの表面に付着させる懸濁液付着工程（水分散液付着工程）と、未加硫ゴムの表面の前記防着剤懸濁液を乾燥して、防着剤からなる被膜を未加硫ゴムの表面に形成する乾燥工程とを有することが好ましい。このような防着処理工程を、例えば、ウェット法という。 In the anti-vulcanization treatment step, for example, the unvulcanized rubber adhering agent water dispersion of the present invention is adhered to the surface of the unvulcanized rubber, and water is further volatilized to obtain the unvulcanized rubber. It may be a step of adhering the adhesive for unvulcanized rubber of the present invention to the surface. More specifically, in the depositioning treatment step, the suspension adhering to adhere the unvulcanized rubber adhering agent water dispersion liquid (depositing agent suspension) of the present invention to the surface of the unvulcanized rubber. It has a step (a step of adhering an aqueous dispersion) and a drying step of drying the adhesive suspension on the surface of the unvulcanized rubber to form a film made of the adhesive on the surface of the unvulcanized rubber. Is preferable. Such an anti-adhesion treatment step is referred to as, for example, a wet method.
本発明の防着処理済み未加硫ゴムの製造方法において、前記ウェット法は、特に限定されず、例えば、一般的な未加硫ゴム用防着剤におけるウェット法と同様にして行うことも可能である。前記防着剤懸濁液（水分散液）中における前記本発明の未加硫ゴム用防着剤の濃度は、特に限定されず、任意に調整可能であり、例えば、前述のとおりであり、より具体的には、例えば、２～３質量％とすることができる。 In the method for producing an unvulcanized unvulcanized rubber of the present invention, the wet method is not particularly limited, and for example, it can be performed in the same manner as the wet method in a general adhesive for unvulcanized rubber. Is. The concentration of the adhesive for unvulcanized rubber of the present invention in the adhesive suspension (aqueous dispersion) is not particularly limited and can be arbitrarily adjusted, and is, for example, as described above. More specifically, it can be, for example, 2 to 3% by mass.
前記懸濁液付着工程では、例えば、シート状等に成形された時の熱により高温状態（例えば、８０～１５０℃程度）にある未加硫ゴムに対して、防着剤懸濁液を付着させることが好ましい。 In the suspension attachment step, for example, the adhesive suspension is attached to the unvulcanized rubber which is in a high temperature state (for example, about 80 to 150 ° C.) due to the heat when it is formed into a sheet or the like. It is preferable to let it.
前記懸濁液付着工程の具体的方法としては、例えば、防着剤懸濁液を未加硫ゴムにシャワー装置で散布する方法、防着剤懸濁液の入った槽に未加硫ゴムを短時間浸漬するディップ法が挙げられる。また、塗布装置を用いて防着剤懸濁液を未加硫ゴムに塗布する方法等を採用してもよく、これらの方法を適宜併用してもよい。 Specific methods of the suspension adhering step include, for example, a method of spraying the unvulcanized rubber on the unvulcanized rubber with a shower device, and a method of spraying the unvulcanized rubber in a tank containing the anti-vulcanized rubber. A dip method of immersing for a short time can be mentioned. Further, a method of applying the adhesive suspension to the unvulcanized rubber using a coating device may be adopted, or these methods may be used in combination as appropriate.
本発明によれば、水分散液の粘度コントロールに頼ることなく、ゴム表面への付着性を向上できる。本発明の未加硫ゴム用防着剤が適用可能なゴム種は、特に制限されず、未加硫のゴムであればよい。前記ゴム種としては、例えば、天然ゴム（ＮＲ）、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、ＩＩＲ（ブチルゴム）、ＥＰＤＭ（エチレンプロピレンゴム）等のゴムや、これらのうちの複数種が混合されたゴムが挙げられる。 According to the present invention, the adhesiveness to the rubber surface can be improved without relying on the viscosity control of the aqueous dispersion. The rubber type to which the adhesive for unvulcanized rubber of the present invention can be applied is not particularly limited, and may be any unvulcanized rubber. Examples of the rubber type include rubbers such as natural rubber (NR), butadiene rubber (BR), styrene butadiene rubber (SBR), IIR (butyl rubber), and EPDM (ethylene propylene rubber), and a plurality of these. Examples include mixed rubber.
［実施例１～１６および比較例１～３］
下記表１および２に示す重量（質量）比率で、各成分を混練して、均一粉体からなる各例の防着剤を調製した。そして、得られた防着剤を水道水に撹拌しながら加え、防着剤の濃度が２質量％である防着剤懸濁液を調製した。実施例１～１６は、下記表１に示すとおり、（Ａ）～（Ｄ）成分を全て配合した。これに対し、下記表２に示すとおり、比較例１は、成分（Ａ）、（Ｃ）、（Ｄ）を配合したが、成分（Ｂ）を配合せず、比較例２は、成分（Ａ）、（Ｂ）、（Ｄ）を配合したが、成分（Ｃ）を配合せず、比較例３は、成分（Ａ）、（Ｂ）、（Ｃ）を配合したが、成分（Ｄ）を配合しなかった。なお、下記表１および２に記載された各成分の製品名（商品名）および製造元を、下記表３に示す。また、下記表１～３に記載された成分（Ｂ）および成分（Ｃ）におけるオキシエチレン基（ＥＯ）の付加モル数は、平均付加モル数である。
[Examples 1 to 16 and Comparative Examples 1 to 3]
Each component was kneaded at the weight (mass) ratios shown in Tables 1 and 2 below to prepare an adhesive for each example consisting of a uniform powder. Then, the obtained adhesive was added to tap water with stirring to prepare an adhesive suspension having a concentration of the inhibitor of 2% by mass. In Examples 1 to 16, all the components (A) to (D) were blended as shown in Table 1 below. On the other hand, as shown in Table 2 below, Comparative Example 1 contained the components (A), (C), and (D), but did not contain the component (B), and Comparative Example 2 contained the component (A). ), (B), (D) were blended, but the component (C) was not blended, and in Comparative Example 3, the components (A), (B), and (C) were blended, but the component (D) was blended. Did not mix. The product names (trade names) and manufacturers of the components listed in Tables 1 and 2 below are shown in Table 3 below. The number of added moles of the oxyethylene group (EO) in the components (B) and the components (C) shown in Tables 1 to 3 below is the average number of added moles.
表１および２に記載の実施例１～１６および比較例１～３の各防着剤懸濁液（水分散液、濃度２質量％）を用いて、下記の評価を行った。 The following evaluations were performed using the adhesive suspensions (aqueous dispersion, concentration 2% by mass) of Examples 1 to 16 and Comparative Examples 1 to 3 shown in Tables 1 and 2.
＜評価＞
各種評価には、評価用ゴムとして下記の未加硫ＮＲ／ＢＲゴムを用いた。
<Evaluation>
For various evaluations, the following unvulcanized NR / BR rubber was used as the evaluation rubber.
（未加硫ＮＲ／ＢＲゴム）
ＮＲ（ＲＳＳ♯３）７０質量部とＢＲ（ＪＳＲ（株）製、商品名「ＢＲ－０１」）３０質量部の合計１００質量部に対して、ホワイトカーボン（東ソー・シリカ（株）製、商品名「ニップシールＶＮ－３」）１０質量部と、ＩＳＡＦブラック（東海カーボン（株）製、商品名「シースト６」）３０質量部と、ＪＳＲＡＲＯＭＡ（プロセスオイル）（日本サン石油（株）製、商品名「アロマ７９０」）１５質量部と、亜鉛華（ハクスイテック（株）製、亜鉛華２種）３質量部と、ステアリン酸（日油（株）製、椿）１質量部と、６ＰＰＤ（大内新興化学工業（株）製、商品名「ノクラック６Ｃ」）１質量部と、ＣＢＳ（大内新興化学工業（株）製、商品名「ノクセラーＣＺ－Ｇ」）１質量部と、硫黄（鶴見化学（株）製）１．５質量部とを配合した（合計１６２．５質量部）未加硫ＮＲ／ＢＲゴム。
(Unvulcanized NR / BR rubber)
White carbon (manufactured by Toso Silica Co., Ltd., product) for a total of 100 parts by mass of 70 parts by mass of NR (RSS # 3) and 30 parts by mass of BR (manufactured by JSR Co., Ltd., trade name "BR-01"). Name "Nipseal VN-3") 10 parts by mass, ISAF Black (manufactured by Tokai Carbon Co., Ltd., trade name "Seast 6") 30 parts by mass, JSRAROMA (process oil) (manufactured by Nippon Sun Oil Co., Ltd., product) 15 parts by mass of name "Aroma 790"), 3 parts by mass of Zinchua (manufactured by Hakusui Tech Co., Ltd., 2 types of Zinchua), 1 part by mass of stearic acid (manufactured by Nichiyu Co., Ltd., camellia), 6PPD (large) 1 part by mass of CBS (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., trade name "Noxeller CZ-G") and 1 part by mass of sulfur (Tsurumi) Unsulfurized NR / BR rubber blended with 1.5 parts by mass (manufactured by Chemical Co., Ltd.) (162.5 parts by mass in total).
（１）付着性の評価
上記の未加硫ゴム（未加硫ＮＲ／ＢＲゴム）を温度８０～１２０℃のオープンロールで練り出してゴムシート（厚さ：５～８ｍｍ、６０ｃｍ×１５ｃｍ）とし、繰り出された直後の前記ゴムシートを、実施例１～１６および比較例１～３の各例で得られた防着剤懸濁液（温度４０℃）１Ｌに約１秒間浸漬した。その後、前記ゴムシートをすばやく垂直に引き上げ、室温下で静置した。前記ゴムシートの表面積を１００％とした際の、防着剤乾燥被膜（防着剤乾燥固化物の被膜）の均質性、被膜の厚み（一様の膜厚で覆われている）を目視にて確認し、下記１～５の５段階で判定した。
１：ハジキが発生している。
２：被膜が縦縞状やマダラ状被膜である。
３：被膜が縦縞状やマダラ状でない薄い均質被膜である。
４：被膜が縦縞状やマダラ状でない均質被膜である。
５：被膜が縦縞状やマダラ状でないやや厚い均質被膜である。
(1) Evaluation of Adhesiveness The above unvulcanized rubber (unvulcanized NR / BR rubber) is kneaded with an open roll at a temperature of 80 to 120 ° C. to form a rubber sheet (thickness: 5 to 8 mm, 60 cm × 15 cm). The rubber sheet immediately after being unwound was immersed in 1 L of the adhesive suspension (temperature 40 ° C.) obtained in each of Examples 1 to 16 and Comparative Examples 1 to 3 for about 1 second. Then, the rubber sheet was quickly pulled up vertically and allowed to stand at room temperature. Visually check the homogeneity of the adhesive dry film (film of the adhesive dry solidified film) and the thickness of the film (covered with a uniform film thickness) when the surface area of the rubber sheet is 100%. And judged in the following 5 stages from 1 to 5.
1: Hajiki is occurring.
2: The film is a vertical stripe-like or madara-like film.
3: The film is a thin homogeneous film that is not vertical stripes or madara.
4: The film is a homogeneous film that is not vertical stripes or madara.
5: The film is a slightly thick homogeneous film that is not vertical stripes or madara.
上記のように、８０～１２０℃のオープンロールで繰り出され、表面が高温状態にあるゴムを、防着剤懸濁液にごく短時間（約１秒間）浸漬させただけで、付着した防着剤懸濁液から水分が急速に蒸発しても、縦縞状、マダラ状等のムラがない均一な薄膜状態で、防着剤がゴム表面に残存できる付着状態が好ましい。 As described above, the rubber that has been unwound by an open roll at 80 to 120 ° C. and whose surface is in a high temperature state is dipped in the adhesive suspension for a very short time (about 1 second), and the adhered rubber is attached. Even if the water content evaporates rapidly from the agent suspension, it is preferable that the adhesive can remain on the rubber surface in a uniform thin film state without unevenness such as vertical stripes and madara.
本発明の実施例１～１６については、いずれも均質被膜（評価５）が得られた。一方、比較例１および２については、マダラ状の被膜（評価２）となった。また、比較例３については、ハジキが発生した。 For Examples 1 to 16 of the present invention, a homogeneous coating (evaluation 5) was obtained. On the other hand, in Comparative Examples 1 and 2, a cod-like film (evaluation 2) was obtained. Further, in Comparative Example 3, repelling occurred.
（２）防着性の評価
上記の未加硫ゴム（未加硫ＮＲ／ＢＲゴム）を温度８０～１２０℃のオープンロールで練り出してゴムシート（厚さ：５～８ｍｍ、６０ｃｍ×１５ｃｍ）とし、繰り出された直後の前記ゴムシートを、実施例１～１６および比較例１～３の各例で得られた防着剤懸濁液（温度４０℃）１Ｌに約１秒間浸漬した。その後、前記ゴムシートをすばやく垂直に引き上げ、室温下において垂直状態で静置し、自然乾燥した。
(2) Evaluation of adhesion resistance The above unvulcanized rubber (unvulcanized NR / BR rubber) is kneaded with an open roll at a temperature of 80 to 120 ° C. and a rubber sheet (thickness: 5 to 8 mm, 60 cm × 15 cm). The rubber sheet immediately after being unwound was immersed in 1 L of the adhesive suspension (temperature 40 ° C.) obtained in each of Examples 1 to 16 and Comparative Examples 1 to 3 for about 1 second. Then, the rubber sheet was quickly pulled up vertically, allowed to stand in a vertical state at room temperature, and air-dried.
その後、前記ゴムシートを６ｃｍ×１５ｃｍにカットし、２枚を重ね合わせて積層状態の試験片とした。前記試験片に対して、一方の面から垂直方向に１ｔ／ｍ２の荷重をかけ、６０℃、１２時間放置した。 Then, the rubber sheet was cut into a size of 6 cm × 15 cm, and the two sheets were overlapped to form a laminated test piece. A load of 1 t / m 2 was applied to the test piece in the vertical direction from one surface, and the test piece was left at 60 ° C. for 12 hours.
その後、前記試験片を室温に戻し、引張り試験機〔ＡＧＳ－５００Ｄ型、ＳＨＩＭＡＤＺＵ〕を用いて１８０°剥離試験を行い、引っ張り速度３００ｍｍ／ｍｉｎで剥離抗力（Ｎ／ｃｍ）を測定した。 Then, the test piece was returned to room temperature, a 180 ° peeling test was conducted using a tensile tester [AGS-500D type, SHIMADZU], and the peeling drag (N / cm) was measured at a tensile speed of 300 mm / min.
剥離抗力が２．０Ｎ／ｃｍ以下の場合、大きな負荷なくゴムシートを剥がすことができ、防着性能は良好であると判断できる。剥離抗力が２．０Ｎ／ｃｍ超の場合、ゴムシートを剥がす時の負荷が大きく、防着性能は不良であると判断できる。さらに剥離抗力が３．０Ｎ／ｃｍ超の場合、ゴムシートは密着しており、通常の作業現場での剥離は困難であると判断できる。 When the peeling drag is 2.0 N / cm or less, the rubber sheet can be peeled off without a large load, and it can be judged that the adhesion performance is good. When the peeling drag is more than 2.0 N / cm, it can be judged that the load when peeling the rubber sheet is large and the adhesion performance is poor. Further, when the peeling drag is more than 3.0 N / cm, the rubber sheets are in close contact with each other, and it can be judged that peeling at a normal work site is difficult.
本発明の実施例１～１６については、いずれも剥離抗力が２．０Ｎ／ｃｍ以下の良好な防着性能が得られた。一方、比較例１～３については、いずれも剥離抗力が２．０Ｎ／ｃｍを超える不良の結果となった。 For Examples 1 to 16 of the present invention, good adhesion performance with a peeling drag of 2.0 N / cm or less was obtained. On the other hand, in all of Comparative Examples 1 to 3, the result was that the peeling drag exceeded 2.0 N / cm.
Claims (3)
下記成分（Ｂ）の含有率が下記成分（Ａ）～（Ｄ）の質量の合計に対して、０．１質量％以上１０質量％以下であり、
下記成分（Ｃ）の含有率が下記成分（Ａ）～（Ｄ）の質量の合計に対して、１質量％以上２０質量％以下であり、
下記成分（Ｂ）の全体の質量（Ｂａｌｌ）に対して、下記式（１）においてｍ＝０である化合物（Ｂ０）の含有率（（Ｂ０／Ｂａｌｌ）×１００）が、１０～１００質量％である、
ことを特徴とする未加硫ゴム用防着剤。
（Ａ）無機粉末
（Ｂ）下記式（１）で表される化合物
（Ｃ）下記式（２）で表される化合物のうち成分（Ｂ）を除くノニオン界面活性剤
（Ｄ）アニオン界面活性剤
Ｒ１は、炭素数４～２０の直鎖または分岐鎖の炭化水素基であり、
ＥＯは、オキシエチレン基であり、
ｍは、ＥＯの平均付加モル数を示す０～１０の数である。
Ｒ－Ｏ－（ＡＯ）ｘ－Ｈ ・・・（２）
前記式（２）中、
Ｒは、炭素数が１２～１６の脂肪族炭化水素基であり、
ＡＯは、炭素数２～４のオキシアルキレン基であり、
ｘは、ＡＯの平均付加モル数を示す１～３０の数である。 Including the following components (A) to (D)fruit,
The content of the following component (B) is 0.1% by mass or more and 10% by mass or less with respect to the total mass of the following components (A) to (D).
The content of the following component (C) is 1% by mass or more and 20% by mass or less with respect to the total mass of the following components (A) to (D).
The content ((B0 / Ball) × 100) of the compound (B0) having m = 0 in the following formula (1) is 10 to 100% by mass with respect to the total mass (Ball) of the following component (B). Is,
A protective agent for unvulcanized rubber.
(A) Inorganic powder
(B) A compound represented by the following formula (1)
(C)Among the compounds represented by the following formula (2)Nonionic surfactant excluding component (B)
(D) Anionic surfactant
R1Is a straight-chain or branched-chain hydrocarbon group having 4 to 20 carbon atoms.
EO is an oxyethylene group,
m is a number from 0 to 10 indicating the average number of moles of substance added to EO.Ru..
RO- (AO) x-H ... (2)
In the formula (2),
R is an aliphatic hydrocarbon group having 12 to 16 carbon atoms.
AO is an oxyalkylene group having 2 to 4 carbon atoms.
x is a number of 1 to 30 indicating the average number of moles of AO added.
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| JP2013001720A (en) | 2011-06-13 | 2013-01-07 | Matsumoto Yushi Seiyaku Co Ltd | Anti-adhesion agent for unvulcanized rubber |
| JP2013124292A (en) | 2011-12-14 | 2013-06-24 | Matsumoto Yushi Seiyaku Co Ltd | Anti-adhesion agent for unvulcanized rubber |
| WO2013133207A1 (en) | 2012-03-06 | 2013-09-12 | 一方社油脂工業株式会社 | Anti-tack agent for unvulcanized rubbers, and method for producing anti-tack-treated unvulcanized rubber |
| JP2017088686A (en) | 2015-11-06 | 2017-05-25 | 松本油脂製薬株式会社 | Adhesion preventive agent for unvulcanized rubber and use thereof |
| WO2017164171A1 (en) | 2016-03-24 | 2017-09-28 | ライオン・スペシャリティ・ケミカルズ株式会社 | Anti-tack agent for unvulcanized rubber and aqueous dispersion of anti-tack agent for unvulcanized rubber |
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| JP2013001720A (en) | 2011-06-13 | 2013-01-07 | Matsumoto Yushi Seiyaku Co Ltd | Anti-adhesion agent for unvulcanized rubber |
| JP2013124292A (en) | 2011-12-14 | 2013-06-24 | Matsumoto Yushi Seiyaku Co Ltd | Anti-adhesion agent for unvulcanized rubber |
| WO2013133207A1 (en) | 2012-03-06 | 2013-09-12 | 一方社油脂工業株式会社 | Anti-tack agent for unvulcanized rubbers, and method for producing anti-tack-treated unvulcanized rubber |
| JP2013213202A (en) | 2012-03-06 | 2013-10-17 | Ipposha Oil Industries Co Ltd | Adhesion-preventive agent for unvulcanized rubber, and method for producing adhesion prevention-treated unvulcanized rubber |
| JP2017088686A (en) | 2015-11-06 | 2017-05-25 | 松本油脂製薬株式会社 | Adhesion preventive agent for unvulcanized rubber and use thereof |
| WO2017164171A1 (en) | 2016-03-24 | 2017-09-28 | ライオン・スペシャリティ・ケミカルズ株式会社 | Anti-tack agent for unvulcanized rubber and aqueous dispersion of anti-tack agent for unvulcanized rubber |
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