JP4338719B2 - Resin composition for gloves made of vinyl chloride resin, and gloves made of vinyl chloride resin using the same - Google Patents
Resin composition for gloves made of vinyl chloride resin, and gloves made of vinyl chloride resin using the same Download PDFInfo
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- JP4338719B2 JP4338719B2 JP2006219588A JP2006219588A JP4338719B2 JP 4338719 B2 JP4338719 B2 JP 4338719B2 JP 2006219588 A JP2006219588 A JP 2006219588A JP 2006219588 A JP2006219588 A JP 2006219588A JP 4338719 B2 JP4338719 B2 JP 4338719B2
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- vinyl chloride
- chloride resin
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 70
- 239000011347 resin Substances 0.000 title claims description 60
- 229920005989 resin Polymers 0.000 title claims description 60
- 239000011342 resin composition Substances 0.000 title claims description 32
- 239000000839 emulsion Substances 0.000 claims description 57
- 238000004519 manufacturing process Methods 0.000 claims description 38
- 239000000178 monomer Substances 0.000 claims description 37
- 229920001296 polysiloxane Polymers 0.000 claims description 31
- 239000000113 methacrylic resin Substances 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 230000000903 blocking effect Effects 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 239000000057 synthetic resin Substances 0.000 description 8
- 229920003002 synthetic resin Polymers 0.000 description 8
- BESKSSIEODQWBP-UHFFFAOYSA-N 3-tris(trimethylsilyloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C BESKSSIEODQWBP-UHFFFAOYSA-N 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000000428 dust Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 125000005395 methacrylic acid group Chemical group 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 210000004247 hand Anatomy 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010410 dusting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 241000156978 Erebia Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 210000003813 thumb Anatomy 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Gloves (AREA)
- Moulding By Coating Moulds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、濡れた手でも着脱が容易で塵の発生しない塩化ビニル樹脂製手袋を、常に安定した品質で製造するための塩化ビニル樹脂製手袋用樹脂組成物、該樹脂組成物を用いた塩化ビニル樹脂製手袋の製造方法、及び該製造方法で得られた塩化ビニル樹脂製手袋に関するものである。 The present invention relates to a vinyl chloride resin glove resin composition for manufacturing a vinyl chloride resin glove that is easy to attach and detach even with wet hands and does not generate dust, and always has a stable quality, and a chloride using the resin composition. The present invention relates to a method for producing a vinyl resin glove, and a vinyl chloride resin glove obtained by the production method.
従来、塩化ビニル樹脂製手袋は、主として家庭用に使用されていたが、近年、精密工業における作業用にも、使用されるようになってきている。しかしながら、塩化ビニル樹脂製手袋には、柔軟性を付与する目的で多量の可塑剤が配合されており、この可塑剤が表面にブリードするため粘着性を示し、手袋製造時における手型からの離型性や、使用時における着脱性に劣るという欠点があった。そこで、手袋内面にパイル植毛や無機物微粉末による打粉処理を施すことが行われているが、この手袋を使用してクリーンルーム内で精密加工を行う場合、植毛繊維や打粉成分が塵の発生原因となるという問題があり、その改善が要望されている。 Conventionally, gloves made of vinyl chloride resin have been mainly used for home use, but in recent years, they are also used for work in the precision industry. However, gloves made of vinyl chloride resin contain a large amount of plasticizer for the purpose of imparting flexibility, and this plasticizer bleeds to the surface, showing adhesiveness, and separating from the hand mold during glove manufacturing. There was a drawback that it was inferior in moldability and detachability during use. Therefore, pile flocking and dusting treatment with inorganic fine powder are performed on the inner surface of the glove, but when precision processing is performed in a clean room using this glove, flocked fibers and dusting components are the cause of dust generation. There is a problem of becoming, and the improvement is demanded.
このような問題を解決する方法として、手型に塩化ビニル樹脂層を形成した後、微粒子シリカを含有する合成樹脂エマルジョンに浸漬処理して製膜し、冷却後、反転脱型する方法が特許文献１に開示されている。また、手型に塩化ビニル樹脂層を形成した後、メチルメタアクリレート樹脂等の硬度の高い樹脂をエマルジョン状態で混合した混合エマルジョン液に浸漬処理して製膜し、反転離型する方法が、特許文献２に開示されている。
さらに、浸漬形成法によって形成した合成樹脂製手袋素体をタルク、炭酸カルシウム、雲母等の粉体含有合成樹脂ラテックス中に浸漬し、引き上げた後、加熱ゲル化する方法が、特許文献３に開示されている。
また、シリコーンオイルを配合し表面凹凸のみの滑性を更に向上させる方法が、特許文献４に開示されている。
As a method for solving such a problem, there is a method in which a vinyl chloride resin layer is formed on a hand mold, immersed in a synthetic resin emulsion containing fine particle silica to form a film, cooled, and then reversely demolded. 1 is disclosed. In addition, after forming a vinyl chloride resin layer on the hand mold, a method of forming a film by immersing it in a mixed emulsion solution in which a resin with high hardness such as methyl methacrylate resin is mixed in an emulsion state, and performing reverse mold release is a patent. It is disclosed in Document 2.
Furthermore, Patent Document 3 discloses a method in which a synthetic resin glove body formed by a dipping method is immersed in a powder-containing synthetic resin latex such as talc, calcium carbonate, mica, and then heated and gelled. Has been.
Further, Patent Document 4 discloses a method of further improving the lubricity of only surface irregularities by blending silicone oil.
上記従来の方法のうち、特許文献１に開示された微粒子シリカを配合分散させた合成樹脂エマルジョンを用いる方法は、塩化ビニル樹脂層上に極く薄くシリカ粒子分散合成樹脂層が形成されるため、シリカの微細な凹凸が手袋使用時における着脱性を容易にするという利点があるが、シリカの形状が無定形であるために、滑性が低下したり、長時間使用すると、シリカの突起部が擦り取られて塵の発生原因となるという問題があった。
さらに、特許文献３に開示された浸漬形成法によって形成した合成樹脂製手袋素体を粉体含有合成樹脂ラテックス中に浸漬する方法は、シリカに比較して、微細な凹凸を形成することができず、また、３０〜１５０μｍの粉体粒径では手袋着脱時にザラツキ感を与えるという問題があった。また、これらの微粒子を用いて滑性を付与する方法は樹脂液中で微粒子の沈降が起こることにより一定した滑性が得られなかったり、塩化ビニル樹脂層上に塗布し乾燥させる際、樹脂液が溜まり易い部分に微粒子が偏在して濃化し、処理ムラが発生したりするため、手袋製造工程管理に高い技術を要する。
Among the conventional methods described above, the method using the synthetic resin emulsion in which the fine particle silica disclosed in Patent Document 1 is mixed and dispersed forms a silica particle-dispersed synthetic resin layer extremely thinly on the vinyl chloride resin layer. The fine irregularities of silica have the advantage of facilitating attachment / detachment when using gloves, but since the shape of the silica is amorphous, the slipperiness is reduced, or when used for a long time, the silica protrusions There was a problem that it was scraped off to cause dust generation.
Furthermore, the method of immersing the synthetic resin glove body formed by the dip forming method disclosed in Patent Document 3 in the powder-containing synthetic resin latex can form fine irregularities compared to silica. In addition, there is a problem that a grain size of 30 to 150 μm gives a feeling of roughness when attaching and detaching gloves. In addition, the method of imparting lubricity using these fine particles may not provide a constant lubricity due to precipitation of the fine particles in the resin liquid, or may be applied when the resin liquid is applied and dried on the vinyl chloride resin layer. Since the fine particles are unevenly distributed and concentrated in the portion where the water tends to accumulate, processing irregularities are generated, so that high technology is required for management of the glove manufacturing process.
また、特許文献２に開示されたメチルメタアクリレート樹脂等の硬度の高い樹脂をエマルジョン状態で混合した混合エマルジョンを用いる方法は、塩化ビニル樹脂層上に形成された薄膜層には、硬度の高い樹脂の粒子が突出することなく均一に分散されているため、ある程度の滑性を有するが、表面に微細な凹凸が形成されていないために、滑性に限界があり、また内面のブロッキングを引き起こしやすく、より一層着脱容易な手袋をめざす市場のニーズに十分答えられないという問題があった。また、特許文献４に開示されたシリコーンオイルの使用は、手袋表面に付着または透過すると、取り扱う製品、例えば電子部品など油状物の付着を嫌う製品への使用は出来ない。
上記従来の方法で製造したいずれの手袋も、手が水で濡れている場合、滑性の低下が著しく、手袋を容易に着脱することができなくなるという問題があった。
Further, the method using a mixed emulsion obtained by mixing a resin having a high hardness such as methyl methacrylate resin disclosed in Patent Document 2 in an emulsion state has a resin having a high hardness in a thin film layer formed on a vinyl chloride resin layer. The particles are uniformly dispersed without protruding, but have a certain degree of lubricity, but because there are no fine irregularities formed on the surface, there is a limit to the lubricity and it is easy to cause blocking of the inner surface However, there was a problem that it was not possible to sufficiently answer the needs of the market aiming for gloves that were even easier to put on and take off. Further, the use of silicone oil disclosed in Patent Document 4 cannot be used for a product to be handled, for example, a product that dislikes adhesion of an oily substance such as an electronic component when it adheres or permeates the surface of the glove.
Any glove manufactured by the above-described conventional method has a problem that when the hand is wet with water, the slipperiness is remarkably lowered and the glove cannot be easily attached and detached.
本発明の目的は、上記した従来技術における問題点を解決し、濡れた手でも着脱が容易であり、かつ塵の発生しない塩化ビニル樹脂製手袋を安定した品質で製造するための樹脂組成物を提供することにある。 An object of the present invention is to solve the above-mentioned problems in the prior art, and to provide a resin composition for producing a vinyl chloride resin glove with stable quality that is easy to attach and detach even with wet hands and does not generate dust. It is to provide.
本発明の塩化ビニル樹脂製手袋の内面上に設ける塩化ビニル樹脂製手袋用樹脂組成物は、（ａ）メチルメタアクリレートモノマー８８．０〜９９．４重量％と、（ｂ）シリコーン系（メタ）アクリレートモノマー０．１〜１０．０重量％と、さらに（ｃ）（メタ）アクリル酸モノマー０．５〜２．０重量％を共重合してなるメタアクリル樹脂（Ａ）の水性エマルジョンと、該水性エマルジョンの不揮発分１００重量％に対して、水溶性（メタ）アクリル酸系樹脂（Ｂ）の水溶液を、該水溶液の不揮発分が１０〜５０重量％の割合で混合してなることを特徴とする塩化ビニル樹脂製手袋用樹脂組成物である。 The vinyl chloride resin glove resin composition provided on the inner surface of the vinyl chloride resin glove of the present invention comprises (a) 8 to 99.4% by weight of methyl methacrylate monomer, and (b) silicone-based (meth). An aqueous emulsion of a methacrylic resin (A) obtained by copolymerizing 0.1 to 10.0% by weight of an acrylate monomer and 0.5 to 2.0% by weight of (c) a (meth) acrylic acid monomer; A water-soluble (meth) acrylic acid resin (B) aqueous solution is mixed with a non-volatile content of the aqueous emulsion in an amount of 10 to 50% by weight with respect to 100% by weight of the non-volatile content of the aqueous emulsion. This is a resin composition for gloves made of vinyl chloride resin.
本発明の樹脂組成物においては、主体として高硬度の皮膜を形成し、且つ塩化ビニル樹脂に対して接着性を有する合成樹脂の水性エマルジョンを使用しているため塩化ビニル樹脂層上に積層された被膜は堅固に保持され、かつ塵の発生やブロッキングが起こらない。また、メタアクリル樹脂（Ａ）には（ｂ）シリコーン系（メタ）アクリレートモノマーに由来する側鎖シロキサン基が表面に配向しているため、被膜表面の滑性が大幅に改善されており、同時に被膜の撥水性が発現されている。また、滑性付与のための微粒子およびシリコーンオイルなどを使用していないため、組成物の沈降や分離が起こらず常に均一な被膜が得られる。したがって、本発明の樹脂組成物を用いて得られる塩化ビニル樹脂製手袋は、処理ムラがなく、濡れた手での着脱が容易であって、塵の発生しない非常に安定した品質で製造され、産業上極めて有用である。 In the resin composition of the present invention, a high hardness film is formed as a main component, and an aqueous emulsion of a synthetic resin having adhesiveness to the vinyl chloride resin is used. Therefore, the resin composition is laminated on the vinyl chloride resin layer. The coating is held firmly and does not generate dust or block. Further, since the side chain siloxane group derived from the (b) silicone-based (meth) acrylate monomer is oriented on the surface of the methacrylic resin (A), the lubricity of the coating surface is greatly improved. The water repellency of the coating is expressed. Further, since fine particles for imparting lubricity, silicone oil, and the like are not used, the composition does not settle or separate, and a uniform coating is always obtained. Therefore, the vinyl chloride resin glove obtained using the resin composition of the present invention has no processing unevenness, is easy to attach and detach with wet hands, and is manufactured with a very stable quality that does not generate dust, It is extremely useful in industry.
以下、本発明について詳細に説明する。
まず、本発明の塩化ビニル樹脂製手袋用樹脂組成物について説明すると、本発明で用いるメタアクリル酸樹脂（Ａ）の水性エマルジョンは、（ａ）メチルメタアクリレートモノマー８８．０〜９９．４重量％と（ｂ）シリコーン系（メタ）アクリレートモノマー０．１〜１０．０重量％さらに（ｃ）（メタ）アクリル酸モノマー０．５〜２．０重量％を共重合してなるメタアクリル樹脂（Ａ）の水性エマルジョンであり、ここで、（ｂ）シリコーン系（メタ）アクリレートモノマーとは、シリコーン系アクリレート及び／又はシリコーン系メタアクリレートをいい、（ｃ）成分の（メタ）アクリル酸モノマーとは、アクリル酸モノマー及び／又はメタアクリル酸モノマーをいう。
Hereinafter, the present invention will be described in detail.
First, the vinyl chloride resin glove resin composition of the present invention will be described. The aqueous emulsion of the methacrylic acid resin (A) used in the present invention is (a) methyl methacrylate monomer 88.0 to 99.4% by weight. And (b) 0.1 to 10.0% by weight of a silicone-based (meth) acrylate monomer and (c) a methacrylic resin (A) obtained by copolymerizing 0.5 to 2.0% by weight of a (meth) acrylic acid monomer ) Where (b) silicone-based (meth) acrylate monomer refers to silicone-based acrylate and / or silicone-based methacrylate, and (c) component (meth) acrylic acid monomer is An acrylic acid monomer and / or a methacrylic acid monomer.
ここで、（ｂ）シリコーン系（メタ）アクリレートモノマーとしては特に下記の化学式（１）で表されるモノマーであることが好ましい。
共重合体中のメチルメタアクリレートモノマー（ａ）の含有量が８８．０重量％未満であると、得られる被膜の硬度が不足し、手袋内面でのブロッキングが発生する。一方、含有量が９９．４％を超えると、被膜の手袋本体の塩化ビニル樹脂層への密着性が低下する。
上記化学式（１）で表されるシリコーン系（メタ）アクリレートモノマー（ｂ）としては、サイラプレーンＴＭ０７０１Ｔ（チッソ社製：商品名）やＳＩＡ０２１０．０（チッソ社製：商品コード）を例示することができる。これらのモノマーは、上記化学式（１）で表されるように片末端に共重合性の（メタ）アクリル酸反応性基が付いており、もう一端のケイ素原子ひとつにトリメチルシロキサン基が３つ結合している構造を特徴とし、メタアクリル系樹脂中に櫛形の嵩高いシロキサン基を導入することができる。該シリコーン系（メタ）アクリレートモノマー（ｂ）の含有量が０．１重量％未満であると、得られる被膜の表面へ配向するシリコーン量が不十分になり、滑性が低下して着脱が困難となる。また、１０．０重量％を超えると、手袋基材の塩化ビニル樹脂層への濡れ性が低下する。
また、（メタ）アクリル酸モノマー（ｃ）の含有量が０．５重量％未満であると、被膜の塩化ビニル樹脂層への密着性が低下し、２．０重量％を超えると被膜の耐水性が低下する。
When the content of the methyl methacrylate monomer (a) in the copolymer is less than 88.0% by weight, the hardness of the resulting film is insufficient, and blocking on the inner surface of the glove occurs. On the other hand, if the content exceeds 99.4%, the adhesiveness of the coating to the vinyl chloride resin layer of the glove body decreases.
Examples of the silicone-based (meth) acrylate monomer (b) represented by the chemical formula (1) include Silaplane TM0701T (manufactured by Chisso: product name) and SIA0210.0 (manufactured by Chisso: product code). it can. These monomers have a copolymerizable (meth) acrylic acid reactive group at one end as represented by the chemical formula (1), and three trimethylsiloxane groups are bonded to one silicon atom at the other end. The structure is characterized by that comb-like bulky siloxane groups can be introduced into the methacrylic resin. When the content of the silicone-based (meth) acrylate monomer (b) is less than 0.1% by weight, the amount of silicone oriented to the surface of the resulting coating becomes insufficient, the slipperiness decreases, and attachment / detachment is difficult. It becomes. Moreover, when it exceeds 10.0 weight%, the wettability to the vinyl chloride resin layer of a glove base material will fall.
Further, when the content of the (meth) acrylic acid monomer (c) is less than 0.5% by weight, the adhesion of the film to the vinyl chloride resin layer is lowered, and when it exceeds 2.0% by weight, the water resistance of the film is reduced. Sex is reduced.
上記モノマー（ａ）、（ｂ）、及び（ｃ）を共重合してなるメタアクリル樹脂は、通常の乳化重合法によって水性エマルジョンとして得られる。
（Ｂ）成分の水溶性（メタ）アクリル酸系樹脂としては、アクリル酸もしくはメタクリル酸の単独重合物、またはこれらの共重合物が挙げられる。これらの（メタ）アクリル酸系樹脂の配合量は、上記（Ａ）成分の不揮発分１００重量％に対して、１０〜５０重量％の範囲であることが必要である。
（Ｂ）成分の配合量が１０重量％未満であると、処理剤としての水性エマルジョンの液粘度が不足するため浸漬法による被膜形成が困難になる。逆に、５０重量％を超えると、得られる被膜の耐水性が低下する。
上記成分（Ａ）および（Ｂ）以外に、必要に応じて界面活性剤、消泡剤、湿潤剤、防腐剤等の各種添加剤や水に可溶な有機溶剤を添加することができる。
上記各成分を配合した本発明の樹脂組成物である水性エマルジョンとしては、固形分濃度が０．１〜１０重量％、好ましくは１〜５重量％の範囲で、粘度が５〜１００ｍＰａ・ｓ、好ましくは８〜５０ｍＰａ・ｓの範囲のものが使用できる。
The methacrylic resin obtained by copolymerizing the monomers (a), (b), and (c) is obtained as an aqueous emulsion by an ordinary emulsion polymerization method.
Examples of the water-soluble (meth) acrylic acid resin as the component (B) include homopolymers of acrylic acid or methacrylic acid, or copolymers thereof. The blending amount of these (meth) acrylic resins is required to be in the range of 10 to 50% by weight with respect to 100% by weight of the nonvolatile content of the component (A).
When the blending amount of the component (B) is less than 10% by weight, it is difficult to form a film by the dipping method because the liquid viscosity of the aqueous emulsion as the treating agent is insufficient. On the other hand, if it exceeds 50% by weight, the water resistance of the resulting coating is lowered.
In addition to the components (A) and (B), various additives such as surfactants, antifoaming agents, wetting agents, preservatives, and water-soluble organic solvents can be added as necessary.
The aqueous emulsion which is the resin composition of the present invention in which the above components are blended has a solid content concentration of 0.1 to 10% by weight, preferably 1 to 5% by weight, and a viscosity of 5 to 100 mPa · s, The thing of the range of 8-50 mPa * s can be used preferably.
次に、本発明の塩化ビニル樹脂製手袋の製造方法について説明する。
まず、表面に半ゲル状の塩化ビニル樹脂層を形成した手袋用手型は、通常一般に実施されている方法によって製造することができる。即ち、金属製又は陶磁器製の手型を、塩化ビニルペーストレジンに可塑剤、安定剤、顔料、および必要に応じてゲル化剤、希釈剤、充填剤等を添加混練して得られる塩化ビニル樹脂ゾルに浸漬して、手型表面に塩化ビニル樹脂ゾルの薄層を形成させ、次いで、それを、例えば１７０℃前後の温度で３分間程度加熱してゲル化させればよく、それによって手型の表面に半ゲル状の塩化ビニル樹脂層が形成される。
次いで、上記のようにして形成された半ゲル状の塩化ビニル樹脂層が形成された手型を、本発明の樹脂組成物である水性エマルジョン中に０．０５〜５分間浸漬する。水性エマルジョンの液温度は３０〜７０℃の範囲であることが、被膜の形成を促進し、浸漬時間の短縮につながるので好ましい。次いで手型を引き上げて、上記樹脂組成物を半ゲル状の塩化ビニル樹脂層の外面に付着させる。この状態のものを、例えば、２２０℃で３分間加熱した後冷却し、手型表面の塩化ビニル樹脂層上に膜厚０．５〜５μｍの被膜を形成する。得られた複合膜を反転離型することによって本発明の塩化ビニル樹脂製手袋が製造される。
Next, the manufacturing method of the vinyl chloride resin gloves of this invention is demonstrated.
First, a glove hand mold having a semi-gel vinyl chloride resin layer formed on its surface can be produced by a generally practiced method. That is, a vinyl chloride resin obtained by kneading a metal or ceramic hand mold with a plasticizer, stabilizer, pigment, and if necessary, a gelling agent, a diluent, a filler, etc. into a vinyl chloride paste resin A thin layer of a vinyl chloride resin sol is formed on the surface of the hand mold by dipping in the sol, and then it is gelled by heating it at a temperature of, for example, about 170 ° C. for about 3 minutes. A semi-gel vinyl chloride resin layer is formed on the surface.
Next, the hand mold formed with the semi-gel vinyl chloride resin layer formed as described above is immersed in the aqueous emulsion which is the resin composition of the present invention for 0.05 to 5 minutes. The liquid temperature of the aqueous emulsion is preferably in the range of 30 to 70 ° C., since it promotes the formation of a film and shortens the immersion time. Next, the hand mold is pulled up so that the resin composition adheres to the outer surface of the semi-gel vinyl chloride resin layer. In this state, for example, the film is heated at 220 ° C. for 3 minutes and then cooled to form a film having a thickness of 0.5 to 5 μm on the vinyl chloride resin layer on the surface of the hand mold. The resulting composite membrane is inverted and released to produce the vinyl chloride resin glove of the present invention.
以下に本発明を実施例および比較例を挙げて更に具体的に説明するが、本発明はこれら実施例などにより何ら限定されるものではない。
（製造例１）
表１のメタアクリル樹脂水性エマルジョン配合に示す試薬を用いて、通常の乳化重合法によりメタアクリル樹脂水性エマルジョンを得た。表１中の試薬の使用量の単位は重量部である。
まず、表１に示す試薬を用いてプレエマルジョンを製造する。容器にプレエマルジョン用界面活性剤ハイテノールＮＦ−１７（不揮発分９３％、第一工業製薬社製：商品名）７．１１重量部および脱イオン水９６．４３重量部を導入し、ホモジナイザーで攪拌して混合溶解した溶液に、メチルメタアクリレート２２２．５３重量部、アクリル酸２．２５重量部、及び サイラプレーンＴＭ０７０１Ｔ（数平均分子量４２３、チッソ社製：商品名）０．２３重量部からなるモノマーをよく混合してなるモノマー混合物を投入し、５０００ｒｐｍで５分間攪拌混合してプレエマルジョン３２８．５５重量部を得た。
EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples below, but the present invention is not limited to these examples.
(Production Example 1)
A methacrylic resin aqueous emulsion was obtained by an ordinary emulsion polymerization method using the reagents shown in Table 1 for the methacrylic resin aqueous emulsion formulation. The unit of the amount of reagent used in Table 1 is parts by weight.
First, a pre-emulsion is produced using the reagents shown in Table 1. Into the container, 7.11 parts by weight of pre-emulsion surfactant Hytenol NF-17 (non-volatile content 93%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: trade name) and 96.43 parts by weight of deionized water were introduced and stirred with a homogenizer. A monomer comprising 222.53 parts by weight of methyl methacrylate, 2.25 parts by weight of acrylic acid, and 0.23 parts by weight of Silaplane TM0701T (number average molecular weight 423, manufactured by Chisso Corporation: trade name) A monomer mixture obtained by thoroughly mixing was added and stirred and mixed at 5000 rpm for 5 minutes to obtain 328.55 parts by weight of a pre-emulsion.
次いで、得られたプレエマルジョンの５重量％（１６．４３重量部）と仕込み用界面活性剤ハイテノールＮＦ−１７（不揮発分９３％、第一工業製薬社製：商品名）１．０５重量部および脱イオン水１６７．３４重量部をフラスコへ計量し、反応容器内を窒素ガスで置換した。反応容器内を２００ｒｐｍで攪拌しながら加熱し、反応容器内が７０℃になったら開始剤である過硫酸アンモニウム（ＡＰＳ）０．４５重量部とｐＨ緩衝剤の炭酸水素ナトリウム（ＮａＨＣＯ3 ）０．１７重量部と脱イオン水２．４６重量部からなる水溶液を投入した。開始剤投入１０分後より、残りのプレエマルション３１２．１１重量部を３時間かけて均一に供給し、その間反応容器内を７０℃に保持した。プレエマルション供給終了後より反応容器内の温度を７５℃に上げ、更に９０分間反応させて（メタ）アクリル系樹脂の水性エマルジョン５００．００重量部を得た。得られた水性エマルジョンの不揮発分は４５．０％であった。 Subsequently, 5% by weight (16.43 parts by weight) of the obtained pre-emulsion and 1.05 parts by weight of the surfactant surfactant Hytenol NF-17 (non-volatile content 93%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) And 167.34 parts by weight of deionized water was weighed into the flask, and the inside of the reaction vessel was replaced with nitrogen gas. The inside of the reaction vessel was heated with stirring at 200 rpm, and when the inside of the reaction vessel reached 70 ° C., 0.45 part by weight of ammonium persulfate (APS) as an initiator and 0.17 sodium bicarbonate (NaHCO 3 ) as a pH buffering agent. An aqueous solution consisting of parts by weight and 2.46 parts by weight of deionized water was added. The remaining pre-emulsion 312.11 parts by weight was uniformly supplied over 3 hours from 10 minutes after the introduction of the initiator, and the inside of the reaction vessel was kept at 70 ° C. during that time. After completion of the pre-emulsion supply, the temperature in the reaction vessel was raised to 75 ° C. and further reacted for 90 minutes to obtain 500.00 parts by weight of an aqueous emulsion of (meth) acrylic resin. The non-volatile content of the obtained aqueous emulsion was 45.0%.
（製造例２〜４）
表１に示す配合においてメチルメタアクリレートモノマーの０．５〜２．０重量％（全モノマーに対する重量％、１．１３〜４．５０重量部）を、化学式（１）で表されるシリコーン系（メタ）アクリレートモノマーであるサイラプレーンＴＭ０７０１Ｔ（数平均分子量４２３、チッソ社製：商品名）０．５〜２．０重量％（１．１３〜４．５０重量部）に置き換えた以外は、製造例１と同様の反応を行って、製造例２〜４の水性エマルジョンを得た。
（製造例５）
表１の製造例１に示す配合においてシリコーン系（メタ）アクリレートモノマーであるサイラプレーンＴＭ０７０１Ｔ（数平均分子量４２３、チッソ社製：商品名）をメチルメタアクリレートモノマー１．０重量％（２．２５重量部）に置き換えた以外は、製造例１と同様の反応を行って製造例５の水性エマルジョンを得た。
(Production Examples 2 to 4)
In the formulation shown in Table 1, 0.5 to 2.0% by weight (% by weight based on all monomers, 1.13 to 4.50 parts by weight) of the methyl methacrylate monomer is represented by the silicone system represented by the chemical formula (1) ( Production Example, except that it was replaced with 0.5 to 2.0% by weight (1.13 to 4.50 parts by weight) of Silaplane TM0701T (number average molecular weight 423, manufactured by Chisso Corporation: trade name) which is a meth) acrylate monomer 1 was carried out to obtain aqueous emulsions of Production Examples 2 to 4.
(Production Example 5)
In the formulation shown in Production Example 1 in Table 1, Silaplane TM0701T (number average molecular weight 423, manufactured by Chisso Corporation: trade name), which is a silicone-based (meth) acrylate monomer, was added to 1.0 wt% (2.25 wt%) of methyl methacrylate monomer. A water-based emulsion of Production Example 5 was obtained by carrying out the same reaction as Production Example 1 except that it was replaced with (Part).
（製造例６）
表１の製造例３に示す配合においてシリコーン系（メタ）アクリレートモノマーであるサイラプレーンＴＭ０７０１Ｔ（数平均分子量４２３、チッソ社製：商品名）を次の化学式（２）で表される直鎖型シリコーン系マクロモノマーであるＡＫ−３２（数平均分子量２０，０００、式中ｎ＝２６８、東亞合成社製：商品名）１．０重量％（２．２５重量部）に置き換えた以外は、製造例１と同様の反応を行って製造例６の水性エマルジョンを得た。
（製造例７）
表１の製造例３に示す配合においてシリコーン系（メタ）アクリレートモノマーであるサイラプレーンＴＭ０７０１Ｔ（数平均分子量４２３、チッソ社製：商品名）を下記化学式（２）で表される直鎖型シリコーン系マクロモノマーであるＦＭ−０７２１（数平均分子量５，０００、式中ｎ＝６４、チッソ社製：商品名）１．０重量％（２．２５重量部）に置き換えた以外は、製造例１と同様の反応を行った。
(Production Example 6)
In the formulation shown in Production Example 3 in Table 1, Silaplane TM0701T (number average molecular weight 423, manufactured by Chisso Corporation: trade name), which is a silicone-based (meth) acrylate monomer, is represented by the following chemical formula (2). Production Example, except that it was replaced with 1.0% by weight (2.25 parts by weight) of AK-32 (number average molecular weight 20,000, where n = 268, manufactured by Toagosei Co., Ltd .: trade name), which is a macromonomer 1 was carried out to obtain an aqueous emulsion of Production Example 6.
(Production Example 7)
In the formulation shown in Production Example 3 in Table 1, Silaplane TM0701T (number average molecular weight 423, manufactured by Chisso Corporation: trade name), which is a silicone-based (meth) acrylate monomer, is represented by the following chemical formula (2). Except that the macromonomer FM-0721 (number average molecular weight 5,000, where n = 64, manufactured by Chisso Corporation: trade name) 1.0 wt% (2.25 parts by weight) was replaced with Production Example 1 A similar reaction was performed.
（実施例１）
表２の塩化ビニル樹脂製手袋用樹脂組成物配合例に示す配合で常法により、塩化ビニル樹脂製手袋処理剤である水性エマルジョンを得た。
即ち、製造例１で作製したメタアクリル樹脂エマルジョン１８．９重量部にアンチフォーム０１３Ａ（不揮発分５６％、東レ・ダウコーニング社製：商品名）０．２重量部を投入し、２００ｒｐｍで１０分間攪拌した。次いで攪拌速度を４００ｒｐｍに上げ、水溶性アクリル酸系樹脂の水溶液であるジュリマーＳＨ−８（不揮発分８％、日本純薬社製：商品名）、シリコーン系界面活性剤ポリフローＫＬ−２４５（不揮発分１００％、共栄社化学社製：商品名）の順に投入し、それぞれの投入後２０分間ずつ攪拌し粘度９〜１２ｍＰａ・ｓの水性エマルジョンである塩化ビニル製手袋用樹脂組成物を得た。
(Example 1)
A water-based emulsion that is a vinyl chloride resin glove treating agent was obtained by a conventional method with the formulation shown in Table 2 in the resin composition formulation examples for vinyl chloride resin gloves.
That is, 0.2 part by weight of Antifoam 013A (non-volatile content: 56%, manufactured by Toray Dow Corning Co., Ltd .: trade name) was added to 18.9 parts by weight of the methacrylic resin emulsion prepared in Production Example 1, and 10 minutes at 200 rpm. Stir. Next, the stirring speed was increased to 400 rpm, Julimer SH-8 (nonvolatile content: 8%, manufactured by Nippon Pure Chemical Co., Ltd .: trade name) which is an aqueous solution of a water-soluble acrylic resin, silicone surfactant Polyflow KL-245 (nonvolatile content) 100%, manufactured by Kyoeisha Chemical Co., Ltd .: trade name) and stirred for 20 minutes after each addition to obtain a vinyl chloride glove resin composition which is an aqueous emulsion having a viscosity of 9 to 12 mPa · s.
（実施例２〜４）
実施例１において用いた製造例１の水性エマルジョンに替えて、製造例２〜４で得られたシリコーン系メタアクリレートモノマーであるサイラプレーンＴＭ０７０１Ｔの添加量の異なるメタアクリル樹脂水性エマルジョンを用いた以外は、実施例１と同様の操作を行って水性エマルジョンである塩化ビニル製手袋用樹脂組成物を得た。
（比較例１）
実施例１において用いた製造例１の水性エマルジョンに替えて、製造例５で得られたシリコーン系メタアクリレートモノマーを含有していないメタアクリル樹脂水性エマルジョンを用いた以外は、実施例１と同様の操作を行って水性エマルジョンである塩化ビニル製手袋用樹脂組成物を得た。
(Examples 2 to 4)
Instead of the aqueous emulsion of Production Example 1 used in Example 1, a methacrylic resin aqueous emulsion having a different addition amount of Silaplane TM0701T, which is the silicone-based methacrylate monomer obtained in Production Examples 2 to 4, was used. Then, the same operation as in Example 1 was performed to obtain a vinyl chloride glove resin composition as an aqueous emulsion.
(Comparative Example 1)
In place of the aqueous emulsion of Production Example 1 used in Example 1, the same methacrylic resin aqueous emulsion containing no silicone methacrylate monomer obtained in Production Example 5 was used. The operation was performed to obtain a vinyl chloride glove resin composition which is an aqueous emulsion.
（比較例２）
実施例１において用いた製造例１の水性エマルジョンに替えて、製造例６で得られたシシリコーン系メタアクリレートモノマーＡＫ−３２（東亞合成社製：商品名）を含有しているメタアクリル樹脂水性エマルジョンを用いた以外は、実施例１と同様の操作を行って水性エマルジョンである塩化ビニル製手袋用樹脂組成物を得た。
（比較例３）
実施例１において用いた製造例１の水性エマルジョンに替えて、製造例７で得られたシリコーン系メタアクリレートモノマーＦＭ−０７２１（チッソ社製：商品名）を含有しているメタアクリル樹脂水性エマルジョンを用いた以外は、実施例１と同様の操作を行って水性エマルジョンである塩化ビニル製手袋用樹脂組成物を得た。
(Comparative Example 2)
In place of the aqueous emulsion of Production Example 1 used in Example 1, a methacrylic resin aqueous solution containing the silicone-based methacrylate monomer AK-32 (manufactured by Toagosei Co., Ltd .: trade name) obtained in Production Example 6 Except that the emulsion was used, the same operation as in Example 1 was performed to obtain a vinyl chloride glove resin composition as an aqueous emulsion.
(Comparative Example 3)
Instead of the aqueous emulsion of Production Example 1 used in Example 1, a methacrylic resin aqueous emulsion containing the silicone-based methacrylate monomer FM-0721 (manufactured by Chisso: trade name) obtained in Production Example 7 was used. Except that it was used, the same operation as in Example 1 was performed to obtain a vinyl chloride glove resin composition as an aqueous emulsion.
（比較例４）
実施例１において用いた製造例１の水性エマルジョンに替えて、製造例５で得られたシリコーン系メタアクリレートモノマーを含有していないメタアクリル樹脂水性エマルジョン１４．４重量部、加えて架橋有機微粒子アートパールＪ−５Ｐ（不揮発分３０％、根上工業社製：商品名）６．３重量部、および滑り性を付与する添加剤としてシリコーン系エマルジョンであるＳＭ８７０１ＥＸ（不揮発分３０％、東レ・ダウコーニング社製：商品名）０．４重量部を添加した以外は、実施例１と同様の操作を行って水性エマルジョンである塩化ビニル製手袋用樹脂組成物を得た。
（比較例５）
実施例１において用いた製造例１の水性エマルジョンに替えて、製造例５で得られたシリコーン系メタアクリレートモノマーを含有していないメタアクリル樹脂水性エマルジョン１８．６重量部、滑り性を付与する添加剤としてシリコーン系エマルジョンであるＳＭ８７０１ＥＸ（不揮発分３０％、東レ・ダウコーニング社製：商品名）０．４重量部を添加した以外は、実施例１と同様の操作を行って水性エマルジョンである塩化ビニル製手袋用樹脂組成物を得た。
(Comparative Example 4)
Instead of the aqueous emulsion of Production Example 1 used in Example 1, 14.4 parts by weight of the aqueous methacrylic resin emulsion containing no silicone-based methacrylate monomer obtained in Production Example 5, plus the crosslinked organic fine particle art Pearl J-5P (non-volatile content: 30%, manufactured by Negami Kogyo Co., Ltd .: 6.3 parts by weight), and SM8701EX (non-volatile content: 30%, Toray Dow Corning Co., Ltd.), which is a silicone emulsion as an additive that imparts slipperiness Product: Trade name) Except for adding 0.4 parts by weight, the same operation as in Example 1 was performed to obtain a vinyl chloride glove resin composition made of an aqueous emulsion.
(Comparative Example 5)
In place of the aqueous emulsion of Production Example 1 used in Example 1, 18.6 parts by weight of a methacrylic resin aqueous emulsion not containing the silicone-based methacrylate monomer obtained in Production Example 5 was added to impart slipperiness. The same procedure as in Example 1 was carried out except that 0.4 part by weight of SM8701EX (non-volatile content 30%, manufactured by Toray Dow Corning Co., Ltd .: trade name), which is a silicone-based emulsion, was used as an agent. A resin composition for vinyl gloves was obtained.
〔塩化ビニル製手袋製造例〕
常法に従って、塩化ビニルペーストレジン（重合度１６００）１００重量部、ジオクチルフタレート８０重量部、安定剤：Ｌ−１０Ｐ（堺化学工業社製：商品名）３重量部、安定剤；ＡＤＫサイザーＯ−１３０Ｐ（アデカアーガス社製：商品名）３重量部、顔料：ピグメントスカーレットＳＬ（山陽色素社製：商品名）１重量部を配合することによって得られた塩化ビニル樹脂ペースト（粘度５０００ｍＰａ・ｓ）中に、陶磁器製手型を０．１分間浸漬し、引き上げた後、雰囲気温度１７０℃の加熱炉に入れて３分間加熱し、手型上に半ゲル状の塩化ビニル樹脂層を形成した。
次に、塩化ビニル製手袋用樹脂組成物の配合例、実施例１〜４および比較例１〜５で得られた塩化ビニル製手袋用樹脂組成物である水性エマルジョン希釈液中に、上記半ゲル状の塩化ビニル樹脂層が形成された手型を０．１分間浸漬した。その後、手型を引上げ、雰囲気温度２２０℃の加熱炉内で３分間保持した。次いで空気中で冷却し、手型上に形成された複合膜を手型から反転離型させて塩化ビニル樹脂製手袋を得た。
[Example of manufacturing vinyl chloride gloves]
According to a conventional method, 100 parts by weight of vinyl chloride paste resin (polymerization degree 1600), 80 parts by weight of dioctyl phthalate, stabilizer: 3 parts by weight of L-10P (manufactured by Sakai Chemical Industry Co., Ltd .: trade name), stabilizer: ADK Sizer O- In a vinyl chloride resin paste (viscosity 5000 mPa · s) obtained by blending 3 parts by weight of 130P (manufactured by Adeka Argus: trade name) and 1 part by weight of pigment: Pigment Scarlet SL (manufactured by Sanyo Pigment: trade name) Then, the ceramic hand mold was dipped for 0.1 minutes and pulled up, and then placed in a heating furnace having an atmospheric temperature of 170 ° C. and heated for 3 minutes to form a semi-gel vinyl chloride resin layer on the hand mold.
Next, the above-mentioned half-gel is added to the aqueous emulsion dilution liquid which is the resin composition for vinyl chloride gloves obtained in Examples 1 to 4 and Comparative Examples 1 to 5 of the resin composition for vinyl chloride gloves. The hand mold on which the vinyl chloride resin layer was formed was immersed for 0.1 minute. Thereafter, the hand mold was pulled up and held in a heating furnace having an atmospheric temperature of 220 ° C. for 3 minutes. Subsequently, it was cooled in the air, and the composite film formed on the hand mold was reversed and released from the hand mold to obtain a vinyl chloride resin glove.
実施例１〜４、比較例１〜５で得られた塩化ビニル製手袋用樹脂組成物の配合例、およびそれらを用いて製造された塩化ビニル樹脂製手袋上に形成された被膜の密着性、耐水性、耐ブロッキング性、滑性、湿潤滑性について評価した結果を表３に示す。
各項目の評価方法と評価基準は以下の通りである。
（密着性）
塩化ビニル製手袋上に形成された被膜にセロハンテープ（ニチバン社製ＣＴ−１２：商品名）を貼り、一気に剥がした時の、被膜剥離の有無を目視で確認して下記基準で判定した。
○：剥離なし
△：部分的に剥離あり
×：全て剥離
Examples 1-4, formulation examples of resin compositions for vinyl chloride gloves obtained in Comparative Examples 1-5, and adhesion of coatings formed on vinyl chloride resin gloves produced using them, Table 3 shows the evaluation results of water resistance, blocking resistance, lubricity and wet lubricity.
The evaluation methods and evaluation criteria for each item are as follows.
(Adhesion)
Cellophane tape (CT-12 manufactured by Nichiban Co., Ltd .: trade name) was applied to the film formed on the vinyl chloride glove, and the presence or absence of film peeling was checked visually and judged according to the following criteria.
○: No peeling △: Partial peeling ×: All peeling
（耐水性）
塩化ビニル製手袋上に形成された被膜を脱イオン水で濡らした親指で１０往復強く擦り、被膜剥離の有無を目視で確認して下記基準で判定した。
○：剥離なし
△：部分的に剥離あり
×：全て剥離
（耐ブロッキング性）
塩化ビニル製手袋の内面が樹脂組成物で形成された被膜になるように置き、直径１．５ｃｍの金属板上から２００Ｎの荷重を３秒間かけ、荷重を開放した時の被膜同士のブロッキングの有無を目視で確認して下記基準で判定した。
○：ブロッキングなし
△：部分的にブロッキングあり
×：荷重を掛けた面の全てブロッキング
(water resistant)
The film formed on the vinyl chloride gloves was rubbed strongly 10 times with a thumb wet with deionized water, and the presence or absence of film peeling was visually confirmed and judged according to the following criteria.
○: No peeling △: Partial peeling ×: All peeling (blocking resistance)
Place the inner surface of the vinyl chloride glove to be a film formed of a resin composition, apply a load of 200 N from a metal plate with a diameter of 1.5 cm for 3 seconds, and whether there is blocking between the films when the load is released Was visually confirmed and judged according to the following criteria.
○: No blocking △: Partial blocking
X: Blocking of all surfaces with load applied
（滑性）
被膜上に直径２ｃｍの研磨したアルミ板を乗せ１００ｇの荷重をかけながら、２０ｃｍ／ｍｉｎ．の速度で引っ張った時の動摩擦係数と振幅を１０Ｎのロードセルを装備した引っ張り試験機（オリエンテック社製、テンシロン万能試験機ＲＴＥ−１２１０：商品名）で測定した。
（湿潤滑性）
上記滑性の測定と同様にして、被膜とアルミ板の間に脱イオン水１滴を落とした状態で測定を行った。
（液安定性）
実施例２と比較例４で得られた水性エマルジョンである塩化ビニル製手袋用樹脂組成物の希釈液を室温で１〜３日静置したものを攪拌せずに用いて、塩化ビニル製手袋製造例に従って塩化ビニル製手袋上に被膜を形成したものの、滑性を測定した。
(Lubricity)
A polished aluminum plate having a diameter of 2 cm is placed on the coating, and a load of 100 g is applied, while 20 cm / min. The dynamic friction coefficient and the amplitude when pulled at a speed of 10 mm were measured with a tensile tester (Orientec Corp., Tensilon Universal Tester RTE-1210: trade name) equipped with a 10N load cell.
(Wet lubricity)
In the same manner as the above-described lubricity measurement, the measurement was performed with one drop of deionized water dropped between the coating and the aluminum plate.
(Liquid stability)
Manufacture of vinyl chloride gloves using the aqueous solution obtained in Example 2 and Comparative Example 4, which is a diluted solution of a resin composition for vinyl chloride gloves, which is allowed to stand at room temperature for 1 to 3 days without stirring. According to the example, a film was formed on a vinyl chloride glove, and the slipperiness was measured.
表３に示した塩化ビニル製手袋上に形成された被膜の試験結果を考察すると、比較例４は静置日数に伴い滑性が低下しているのに対し、実施例２は静置後も滑性が変化せず、液の安定性が向上していることがわかる。また比較例１のシリコーン系メタアクリルモノマーを添加していないものの滑性に比べ、実施例１〜４のシリコーン系メタアクリルモノマーを添加したものは滑性が顕著に向上しており、シリコーン系メタアクリルモノマーの滑性への効果が確認できる。比較例４の微粒子とシリコーンエマルジョンの添加によって滑性を付与しているものと比較しても実施例１〜４の滑性は向上している。一方、比較例５のシリコーンエマルジョンを添加剤として添加したものや比較例２および３のシリコーン系メタアクリルモノマーが直鎖型であるものは滑性への効果が認められず、シリコーン系メタアクリルモノマーの構造が化学式１で表されるものが有効であることがわかる。湿潤時の滑性は、いずれの場合も乾燥時と比較して動摩擦係数値が上昇しているが、シリコーン系メタアクリルモノマーを添加したもの（特に実施例２）は比較的低い値を維持していた。 Considering the test results of the coatings formed on the vinyl chloride gloves shown in Table 3, Comparative Example 4 showed a decrease in slipperiness with the standing days, whereas Example 2 remained after standing. It can be seen that the lubricity does not change and the stability of the liquid is improved. In addition, compared with the slipperiness of Comparative Example 1 in which the silicone-based methacrylic monomer was not added, those in which the silicone-based methacrylic monomer of Examples 1 to 4 were added had a significantly improved slipperiness. The effect on the lubricity of the acrylic monomer can be confirmed. Even if it compares with the thing which provided the lubricity by addition of the microparticles | fine-particles of the comparative example 4, and a silicone emulsion, the lubricity of Examples 1-4 is improving. On the other hand, when the silicone emulsion of Comparative Example 5 was added as an additive or when the silicone methacrylic monomers of Comparative Examples 2 and 3 were linear, no effect on lubricity was observed, and the silicone methacrylic monomer It can be seen that the structure represented by Chemical Formula 1 is effective. As for the slipperiness at the time of wetness, the value of the dynamic friction coefficient is higher than that at the time of dryness in all cases. It was.
本発明の塩化ビニル樹脂製手袋用樹脂組成物は、塩化ビニル樹脂製手袋、およびその製造分野において、手袋の内面処理剤として優位に用いられる。 The resin composition for gloves made of vinyl chloride resin of the present invention is used preferentially as an inner surface treating agent for gloves in vinyl chloride resin gloves and the field of production thereof.
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