JP6998190B2 - Release agent for tire inner surface, mold release agent for tire inner surface, water dispersion, tire manufacturing method and tire - Google Patents
Release agent for tire inner surface, mold release agent for tire inner surface, water dispersion, tire manufacturing method and tire Download PDFInfo
- Publication number
- JP6998190B2 JP6998190B2 JP2017231833A JP2017231833A JP6998190B2 JP 6998190 B2 JP6998190 B2 JP 6998190B2 JP 2017231833 A JP2017231833 A JP 2017231833A JP 2017231833 A JP2017231833 A JP 2017231833A JP 6998190 B2 JP6998190 B2 JP 6998190B2
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- Prior art keywords
- tire
- release agent
- component
- mass
- mold release
- 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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- 239000006082 mold release agent Substances 0.000 title claims description 42
- 239000003795 chemical substances by application Substances 0.000 title claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 36
- 239000006185 dispersion Substances 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- -1 polyoxyethylene Polymers 0.000 claims description 60
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- 239000004094 surface-active agent Substances 0.000 claims description 15
- 229920001971 elastomer Polymers 0.000 claims description 13
- 239000010445 mica Substances 0.000 claims description 13
- 229910052618 mica group Inorganic materials 0.000 claims description 13
- 238000004073 vulcanization Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
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- 239000004927 clay Substances 0.000 claims description 3
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
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- 238000005286 illumination Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 125000000400 lauroyl group Chemical group O=C([*])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
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- LJZULWUXNKDPCG-UHFFFAOYSA-N nonane-1,2-diol Chemical compound CCCCCCCC(O)CO LJZULWUXNKDPCG-UHFFFAOYSA-N 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- AEIJTFQOBWATKX-UHFFFAOYSA-N octane-1,2-diol Chemical compound CCCCCCC(O)CO AEIJTFQOBWATKX-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- NPKKRSHVJIQBKU-UHFFFAOYSA-N ornogenin Natural products CC(OC(=O)C=Cc1ccccc1)C2(O)CCC3(O)C4(O)CC=C5CC(O)CCC5(C)C4CC(OC(=O)C=Cc6ccccc6)C23C NPKKRSHVJIQBKU-UHFFFAOYSA-N 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- MQOCIYICOGDBSG-UHFFFAOYSA-M potassium;hexadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCC([O-])=O MQOCIYICOGDBSG-UHFFFAOYSA-M 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- 229950006800 prenderol Drugs 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229940080236 sodium cetyl sulfate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- IWIUXJGIDSGWDN-UQKRIMTDSA-M sodium;(2s)-2-(dodecanoylamino)pentanedioate;hydron Chemical compound [Na+].CCCCCCCCCCCC(=O)N[C@H](C([O-])=O)CCC(O)=O IWIUXJGIDSGWDN-UQKRIMTDSA-M 0.000 description 1
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 description 1
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- XLKZJJVNBQCVIX-UHFFFAOYSA-N tetradecane-1,14-diol Chemical compound OCCCCCCCCCCCCCCO XLKZJJVNBQCVIX-UHFFFAOYSA-N 0.000 description 1
- 229940117013 triethanolamine oleate Drugs 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Tires In General (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
- Tyre Moulding (AREA)
Description
本発明は、タイヤ内面用離型剤、タイヤ内面用離型剤水分散液、タイヤの製造方法およびタイヤに関する。 The present invention relates to a tire inner surface mold release agent, a tire inner surface mold release agent water dispersion, a tire manufacturing method, and a tire.
ゴム用離型剤の一種として、タイヤ内面用離型剤がある。例えば、特許文献１には、粉体からなる無機成分（無機粉末）と、シリコーン成分と、界面活性剤と、多価アルコールと、水とを含むタイヤ内面用離型剤が記載されている。 As a kind of release agent for rubber, there is a release agent for the inner surface of a tire. For example, Patent Document 1 describes a tire inner surface mold release agent containing an inorganic component (inorganic powder) composed of powder, a silicone component, a surfactant, a polyhydric alcohol, and water.
タイヤ内面用離型剤は、例えば、つぎのように用いられる。すなわち、タイヤの製造工程において、未加硫生タイヤの加硫成型では、ブラダーと呼ばれるゴム製袋を未加硫生タイヤの内側に配置し、前記ブラダーを温風、熱水または蒸気で膨張させることで、金型内部に前記未加硫生タイヤを押し当て、圧入成型とともに加硫が行われる。この工程を円滑に行うため、生タイヤのインナーライナー面（内面）に、タイヤ内面用離型剤が予めスプレー塗布される。タイヤ内面用離型剤は、加硫後もタイヤ内面に残るため、タイヤ内面への付着部分の外観を黒くすることが好ましい。そのために、カーボンブラック分散液等で着色することがあるが、この方法では、無機粉末の凝集等で白色化し、外観不良となる。これを防止するために、多価アルコールの含有率を高めることがあるが、この方法は、離型性悪化につながる。また、シリコーン成分の含有率を高めることもあるが、この方法は、コストアップとなる。さらに、白くなりやすい無機粉末（マイカである白雲母）を用いない方法もあるが、この方法では、タイヤ内面用離型剤に必要な離型性や滑性が悪化しやすい。 The release agent for the inner surface of the tire is used, for example, as follows. That is, in the tire manufacturing process, in the vulcanization molding of an unvulcanized raw tire, a rubber bag called a bladder is placed inside the unvulcanized raw tire, and the bladder is expanded with warm air, hot water or steam. As a result, the unvulcanized raw tire is pressed against the inside of the mold, and vulcanization is performed together with press-fit molding. In order to smoothly carry out this process, a release agent for the inner surface of the tire is spray-coated in advance on the inner liner surface (inner surface) of the raw tire. Since the mold release agent for the inner surface of the tire remains on the inner surface of the tire even after vulcanization, it is preferable to blacken the appearance of the portion adhered to the inner surface of the tire. Therefore, it may be colored with a carbon black dispersion liquid or the like, but in this method, it becomes white due to aggregation of inorganic powder or the like, resulting in poor appearance. In order to prevent this, the content of the polyhydric alcohol may be increased, but this method leads to deterioration of releasability. In addition, the content of the silicone component may be increased, but this method increases the cost. Further, there is a method that does not use an inorganic powder that tends to whiten (muscovite, which is mica), but this method tends to deteriorate the mold release property and slipperiness required for the mold release agent for the inner surface of the tire.
そこで、本発明は、離型性および滑性を悪化させることなく、外観の向上を実現可能なタイヤ内面用離型剤、およびタイヤ内面用離型剤水分散液を提供することを目的とする。さらに、本発明は、前記タイヤ内面用離型剤水分散液およびタイヤ内面用離型剤を用いたタイヤの製造方法、およびタイヤを提供することを目的とする。 Therefore, an object of the present invention is to provide a release agent for a tire inner surface and a water dispersion liquid for a release agent for a tire inner surface, which can improve the appearance without deteriorating the releasability and slipperiness. .. Furthermore, an object of the present invention is to provide a method for manufacturing a tire using the release agent water dispersion for the inner surface of the tire and the release agent for the inner surface of the tire, and a tire.
前記目的を達成するために、本発明のタイヤ内面用離型剤は、下記成分（Ａ）～（Ｄ）を含むことを特徴とする。
（Ａ）下記成分（Ｄ）以外の無機成分
（Ｂ）シリコーン成分
（Ｃ）界面活性剤
（Ｄ）Ｌ＊値が９０未満であるマイカ
In order to achieve the above object, the tire inner surface mold release agent of the present invention is characterized by containing the following components (A) to (D).
(A) Inorganic component other than the following component (D) (B) Silicone component (C) Surfactant (D) L * Mica with a value of less than 90
本発明のタイヤ内面用離型剤水分散液は、
前記本発明のタイヤ内面用離型剤と、
水と、
を含むことを特徴とする。
The release agent water dispersion for the inner surface of the tire of the present invention is
The mold release agent for the inner surface of the tire of the present invention and
water and,
It is characterized by including.
本発明のタイヤの製造方法は、
未加硫ゴム製生タイヤの内面およびブラダーの外面の少なくとも一方に前記本発明のタイヤ内面用離型剤水分散液を付着させ、さらに水を揮発させる離型用前処理工程と、
前記離型用前処理工程後、成形型内で前記生タイヤに収容された前記ブラダーを膨張させることにより、前記成形型内面に前記生タイヤ外面を押し当て、その状態で前記生タイヤを加熱して加硫する加硫工程と、
を含むことを特徴とする。
The method for manufacturing a tire of the present invention
A mold release pretreatment step of adhering the release agent water dispersion for the inner surface of the tire of the present invention to at least one of the inner surface of the unvulcanized rubber raw tire and the outer surface of the bladder and further volatilizing the water.
After the mold release pretreatment step, the bladder housed in the raw tire is expanded in the mold to press the outer surface of the raw tire against the inner surface of the mold, and the raw tire is heated in that state. Vulcanization process and vulcanization process
It is characterized by including.
本発明のタイヤは、前記本発明のタイヤ内面用離型剤を生タイヤの内面に付着させ、加硫してなることを特徴とする。 The tire of the present invention is characterized in that the release agent for the inner surface of the tire of the present invention is adhered to the inner surface of a raw tire and vulcanized.
また、本発明のタイヤは、タイヤの内面に、前記本発明のタイヤ内面用離型剤が付着していることを特徴とする。 Further, the tire of the present invention is characterized in that the mold release agent for the inner surface of the tire of the present invention is attached to the inner surface of the tire.
本発明のタイヤ内面用離型剤またはタイヤ内面用離型剤水分散液によれば、離型性および滑性を悪化させることなく、外観の向上を実現可能である。 According to the release agent for the inner surface of the tire or the water dispersion of the release agent for the inner surface of the tire of the present invention, it is possible to improve the appearance without deteriorating the releasability and slipperiness.
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.
本発明において、Ｌ＊値は、１９７６年に国際照明委員会（ＣＩＥ）で規格化されたＬ＊ａ＊ｂ＊表色系（ＣＩＥ１９７６（Ｌ＊ａ＊ｂ＊）表色系に基づくものである（ＪＩＳ Ｚ ８７２９参照）。このＬ＊値は、例えば、後述の実施例に記載の方法で測定できる。 In the present invention, the L * value is based on the L * a * b * color system (CIE1976 (L * a * b * ) color system standardized by the International Commission on Illumination (CIE) in 1976. There is (see JIS Z 8729). This L * value can be measured, for example, by the method described in Examples described later.
本発明のタイヤ内面用離型剤およびタイヤ内面用離型剤水分散液は、例えば、前記成分（Ｄ）が、マグネシウムを含有するマイカであってもよい。 The release agent for the inner surface of the tire and the water dispersion of the release agent for the inner surface of the tire of the present invention may be, for example, mica in which the component (D) contains magnesium.
本発明のタイヤ内面用離型剤およびタイヤ内面用離型剤水分散液は、例えば、前記成分（Ａ）が、タルク、クレー、水膨潤性粘土鉱物、炭酸カルシウムおよびゼオライトからなる群から選択される少なくとも一つであってもよい。 In the tire inner surface mold release agent and the tire inner surface mold release agent water dispersion of the present invention, for example, the component (A) is selected from the group consisting of talc, clay, water-swellable clay mineral, calcium carbonate and zeolite. There may be at least one.
本発明のタイヤ内面用離型剤およびタイヤ内面用離型剤水分散液は、例えば、前記成分（Ａ）の質量（Ａｗ）と、前記成分（Ｄ）の質量（Ｄｗ）との比が、Ａｗ／Ｄｗ＝０．１～１０であってもよい。 In the tire inner surface mold release agent and the tire inner surface mold release agent water dispersion liquid of the present invention, for example, the ratio of the mass (Aw) of the component (A) to the mass (Dw) of the component (D) is Aw / Dw = 0.1 to 10 may be set.
［１．タイヤ内面用離型剤］
本発明のタイヤ内面用離型剤における各成分は、特に限定されず、例えば、つぎのとおりである。
[1. Release agent for tire inner surface]
Each component in the tire inner surface mold release agent of the present invention is not particularly limited, and is, for example, as follows.
［１－１．成分（Ａ）］
後述の成分（Ｄ）（Ｌ＊値が９０未満であるマイカ）以外の無機成分（成分（Ａ））は、特に限定されず、例えば、一般的なタイヤ内面用離型剤に用いられている無機成分であってもよい。無機成分（Ａ）としては、例えば、タルク、クレー、水膨潤性粘土鉱物、炭酸カルシウム、ゼオライト、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、スチブンサイト、モンモリロナイトを含有するベントナイト、ケイ酸アルミニウムマグネシウム、無水ケイ酸等が挙げられ、これらは天然物でも良いし合成物でも良い。
[1-1. Ingredient (A)]
The inorganic component (component (A)) other than the component (D) (L * value of less than 90) described later is not particularly limited, and is used, for example, in a general tire inner surface mold release agent. It may be an inorganic component. Examples of the inorganic component (A) include talc, clay, water-swellable clay mineral, calcium carbonate, zeolite, montmorillonite, biderite, nontronite, saponite, hectorite, stibnsite, bentonite containing montmorillonite, and magnesium aluminum silicate. , Anhydrous silicate and the like, and these may be natural products or synthetic products.
本発明のタイヤ内面用離型剤における成分（Ａ）の含有率は、目的に応じて選択可能であり、例えば、タイヤ内面用離型剤の質量全体に対して、２０～９０質量％、２５～８０質量％、または３０～７５質量％であってもよい。 The content of the component (A) in the tire inner surface mold release agent of the present invention can be selected depending on the intended purpose. For example, 20 to 90% by mass, 25, based on the total mass of the tire inner surface mold release agent. It may be -80% by mass, or 30-75% by mass.
［１－２．シリコーン成分（Ｂ）］
シリコーン成分（Ｂ）（成分（Ｂ））は、例えば、離型性向上を担う成分として機能する。シリコーン成分（Ｂ）は、特に限定されず、例えば、オルガノポリシロキサン類が挙げられる。前記オルガノポリシロキサン類は、シリコーンオイル、シリコーンゴム、およびシリコーン樹脂を含む概念である。前記オルガノポリシロキサン類としては、より具体的には、例えば、［１］ジメチルポリシロキサン、ジエチルポリシロキサン、メチルイソプロピルポリシロキサン、メチルドデシルポリシロキサン等のアルキルポリシロキサン、［２］メチルフェニルポリシロキサン、ジメチルシロキサン・メチルフェニルポリシロキサン共重合体、ジメチルシロキサン・ジフェニルシロキサン共重合体等のアルキルフェニルポリシロキサン、［３］メチル（フェニルエチル）ポリシロキサン、メチル（フェニルプロピル）ポリシロキサン等のアルキルアラルキルポリシロキサン、［４］３，３，３－トリフルオロプロピルメチルポリシロキサン等が挙げられる。前記シリコーン成分は、１種類のみ用いてもよいし、複数種類併用してもよい。
[1-2. Silicone component (B)]
The silicone component (B) (component (B)) functions, for example, as a component responsible for improving releasability. The silicone component (B) is not particularly limited, and examples thereof include organopolysiloxanes. The organopolysiloxanes are a concept including silicone oil, silicone rubber, and silicone resin. More specifically, the organopolysiloxanes include, for example, [1] alkyl polysiloxanes such as dimethylpolysiloxane, diethylpolysiloxane, methylisopropylpolysiloxane, and methyldodecylpolysiloxane, and [2] methylphenylpolysiloxane. Alkylphenyl polysiloxanes such as dimethylsiloxane / methylphenylpolysiloxane copolymers, dimethylsiloxane / diphenylsiloxane copolymers, etc. , [4] 3,3,3-trifluoropropylmethylpolysiloxane and the like. Only one kind of the silicone component may be used, or a plurality of kinds may be used in combination.
シリコーン成分（Ｂ）（成分（Ｂ））は、例えば、シリコーン成分と界面活性剤とを含むシリコーン乳化物であってもよい。前記成分（Ｂ）が前記シリコーン乳化物である場合、それに含まれる界面活性剤の含有率は、成分（Ｂ）の含有率には含ませず、後述の成分（Ｃ）の含有率に含ませるものとする。前記シリコーン乳化物において、前記シリコーン成分は、剥離性（離型性）の観点から、分子構造が直鎖状で、重合度が低く常温で流動性を有するシリコーンオイル等が好ましい。前記シリコーン成分の粘度は、特に限定されず、例えば、離型性と製品安定性のバランスの観点から、２５℃において、１０００～１０万ｍＰａ・ｓ、５０００～５万ｍＰａ・ｓである。 The silicone component (B) (component (B)) may be, for example, a silicone emulsion containing a silicone component and a surfactant. When the component (B) is the silicone emulsion, the content of the surfactant contained therein is not included in the content of the component (B), but is included in the content of the component (C) described later. It shall be. In the silicone emulsion, the silicone component is preferably a silicone oil or the like having a linear molecular structure, a low degree of polymerization, and fluidity at room temperature from the viewpoint of releasability (releasability). The viscosity of the silicone component is not particularly limited, and is, for example, 1,000 to 100,000 mPa · s and 5,000 to 50,000 mPa · s at 25 ° C. from the viewpoint of the balance between releasability and product stability.
前記シリコーン乳化物に含まれる前記界面活性剤は、特に限定されず、カチオン界面活性剤、アニオン界面活性剤およびノニオン界面活性剤のいずれでもよいが、アニオン界面活性剤およびノニオン界面活性剤の少なくとも一方を含むことが好ましい。前記アニオン界面活性剤は、特に限定されず、例えば、［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（またはアルケニル）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、［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、［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、［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、等が挙げられる。前記ノニオン界面活性剤も、特に限定されず、例えば、［５］ポリオキシエチレンセチルエーテル、ポリオキシエチレンラウリルエーテル等のポリオキシアルキレンアルキルエーテル、［６］ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル等のポリオキシアルキレンアルキルフェニルエーテル、等が挙げられる。前記界面活性剤は、１種類のみ用いてもよいし、複数種類を併用してもよい。 The surfactant contained in the silicone emulsion is not particularly limited and may be any of a cationic surfactant, an anionic surfactant and a nonionic surfactant, but at least one of the anionic surfactant and the nonionic surfactant. It is preferable to include. The anionic surfactant is not particularly limited, and for example, [1] higher fatty acid salt, alkyl ether carboxylate, polyoxyalkylene ether carboxylate, alkyl (or alkenyl) amide ether carboxylate, acylaminocarboxylic acid. Carboxylic acid type such as salt, [2] higher alcohol sulfate ester salt, polyoxyalkylene higher alcohol sulfate ester salt, alkylphenyl ether sulfate ester salt, polyoxyalkylene alkylphenyl ether sulfate ester salt, glycerin fatty acid ester monosulfate ester salt, etc. Sulfate ester type, [3] Alcan sulfonate, α-olefin sulfonate, linear alkylbenzene sulfonate, α-sulfo fatty acid ester salt, sulfonic acid type such as dialkyl sulfosuccinate, [4] Alkyl phosphate Examples thereof include a phosphate ester type such as an ester salt, a polyoxyalkylene alkyl phosphate ester salt, a polyoxyalkylene alkyl phenyl phosphate ester salt, and a glycerin fatty acid ester monophosphate ester salt. The nonionic surfactant is also not particularly limited, and is, for example, [5] polyoxyalkylene alkyl ether such as polyoxyethylene cetyl ether and polyoxyethylene lauryl ether, [6] polyoxyethylene nonylphenyl ether and polyoxyethylene octyl. Examples thereof include polyoxyalkylene alkyl phenyl ether such as phenyl ether. Only one type of the surfactant may be used, or a plurality of types may be used in combination.
前記シリコーン乳化物（シリコーンエマルジョン）は、例えば、前記シリコーン成分を、前記界面活性剤を用いて水中に分散させ、乳化させて製造してもよい。分散および乳化方法は、特に限定されず、一般的な分散および乳化方法を用いてよい。例えば、まず、シリコーン成分に、ノニオン界面活性剤およびアニオン界面活性剤の少なくとも一方を混合する。一方、予め乳化機を設置した容器に規定量の水を入れる。つぎに、前記水を前記乳化機により撹拌しながら、前記シリコーン成分と前記界面活性剤との混合液を、少しずつ（例えば、１時間かけて）投入し、分散させる。さらに、乳化するまで撹拌することにより、前記シリコーン乳化物（シリコーンエマルジョン）を製造する。前記乳化機は、特に限定されず、一般的な乳化機でもよく、例えば、ホモミキサー、ホモディスパー等が挙げられる。また、前記シリコーン乳化物は、例えば、市販のシリコーン乳化物（シリコーンエマルジョン）をそのまま用いてもよい。前記市販のシリコーン乳化物（シリコーンエマルジョン）としては、例えば、信越化学工業株式会社製の商品名ＫＭ－８６２Ｔ、東レ・ダウコーニング株式会社製の商品名ＦＺ－４１５７等が挙げられる。前記シリコーン乳化物は、１種類のみ用いてもよいし、複数種類を併用してもよい。 The silicone emulsion (silicone emulsion) may be produced, for example, by dispersing the silicone component in water using the surfactant and emulsifying the silicone component. The dispersion and emulsification methods are not particularly limited, and general dispersion and emulsification methods may be used. For example, first, at least one of a nonionic surfactant and an anionic surfactant is mixed with the silicone component. On the other hand, a specified amount of water is put into a container in which an emulsifier is installed in advance. Next, while stirring the water with the emulsifier, the mixed solution of the silicone component and the surfactant is added little by little (for example, over 1 hour) and dispersed. Further, the silicone emulsion is produced by stirring until emulsification. The emulsifying machine is not particularly limited and may be a general emulsifying machine, and examples thereof include a homomixer and a homodisper. Further, as the silicone emulsion, for example, a commercially available silicone emulsion (silicone emulsion) may be used as it is. Examples of the commercially available silicone emulsion (silicone emulsion) include trade name KM-862T manufactured by Shin-Etsu Chemical Co., Ltd., trade name FZ-4157 manufactured by Toray Dow Corning Co., Ltd., and the like. Only one type of the silicone emulsion may be used, or a plurality of types may be used in combination.
なお、特に限定するものではないが、前記シリコーン乳化物を１２０℃で１時間乾燥した後の残渣質量は、前記乾燥前の前記シリコーン乳化物の質量全体に対して、例えば、２０～８０質量％、３０～７０質量％、または３０～６５質量％であってもよい。 Although not particularly limited, the residual mass after drying the silicone emulsion at 120 ° C. for 1 hour is, for example, 20 to 80% by mass with respect to the total mass of the silicone emulsion before drying. , 30-70% by mass, or 30-65% by mass.
本発明のタイヤ内面用離型剤における成分（Ｂ）の含有率は、目的に応じて選択可能であり、例えば、タイヤ内面用離型剤の質量全体に対して、１～３０質量％、２～２０質量％、または５～１５質量％であってもよい。 The content of the component (B) in the release agent for the inner surface of the tire of the present invention can be selected according to the intended purpose. It may be up to 20% by mass, or 5 to 15% by mass.
［１－３．界面活性剤（Ｃ）］
界面活性剤（Ｃ）（成分（Ｃ））は、例えば、乳化安定性付与を担う成分として機能する。なお、前記「乳化安定性」は、本発明のタイヤ内面用離型剤が乳化物である場合における、前記乳化物の安定性をいう。前記乳化物は、前記成分（Ａ）～（Ｄ）が、水の中に分散された乳化物であることが好ましい。このような乳化物は、すなわち、水中油滴型の乳化物（エマルジョン）である。なお、本発明のタイヤ内面用離型剤は、油中水滴型の乳化物でもよいが、スプレー性、付着性、離型性等の観点から、水中油滴型の乳化物であることが好ましい。
[1-3. Surfactant (C)]
The surfactant (C) (component (C)) functions, for example, as a component responsible for imparting emulsion stability. The "emulsification stability" refers to the stability of the emulsion when the release agent for the inner surface of the tire of the present invention is an emulsion. The emulsion is preferably an emulsion in which the components (A) to (D) are dispersed in water. Such an emulsion is, that is, an oil-in-water emulsion. The mold release agent for the inner surface of the tire of the present invention may be a water-in-oil emulsion, but is preferably an oil-in-water emulsion from the viewpoint of sprayability, adhesion, mold release, and the like. ..
前記界面活性剤は、特に限定されず、カチオン界面活性剤でも、ノニオン界面活性剤でも、アニオン界面活性剤でもよいが、ノニオン界面活性剤およびアニオン界面活性剤の少なくとも一方が好ましい。前記ノニオン界面活性剤としては、例えば、［１］ポリオキシエチレンセチルエーテル、ポリオキシエチレンラウリルエーテル等のポリオキシアルキレンアルキルエーテル、［２］ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル等のポリオキシアルキレンアルキルフェニルエーテル、［３］ポリオキシエチレンモノラウレート、ポリオキシエチレンモノオレエート等のポリオキシアルキレン脂肪酸エステル、［４］ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタンモノオレエート等のポリオキシアルキレンソルビタン脂肪酸エステル、［５］ポリオキシアルキレン硬化ひまし油、［６］ポリオキシアルキレンソルビトール脂肪酸エステル、［７］ポリグリセリン脂肪酸エステル、［８］アルキルグリセリンエーテル、［９］ポリオキシアルキレンコレステリルエーテル、［１０］アルキルポリグルコシド、［１１］ショ糖脂肪酸エステル、［１２］ポリオキシアルキレンアルキルアミン、［１３］オキシエチレン－オキシプロピレンブロックポリマー、等が挙げられる。前記アニオン界面活性剤としては、例えば、［１］オレイン酸ナトリウム、パルミチン酸カリウム、オレイン酸トリエタノールアミン等の脂肪酸塩、［２］ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム、ステアリル硫酸ナトリウム、セチル硫酸ナトリウム等のアルキル硫酸エステル塩、［３］ポリオキシエチレントリデシルエーテル酢酸ナトリウム等のポリオキシアルキレンアルキルエーテル酢酸塩、［４］ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩、［５］ポリオキシアルキレンアルキルエーテル硫酸塩、［６］ステアロイルメチルタウリンＮａ、ラウロイルメチルタウリンＮａ、ミリストイルメチルタウリンＮａ、パルミトイルメチルタウリンＮａ等の高級脂肪酸アミドスルホン酸塩、［７］ラウロイルサルコシンナトリウム等のＮ－アシルサルコシン塩、［８］モノステアリルリン酸ナトリウム等のアルキルリン酸塩、［９］ポリオキシエチレンオレイルエーテルリン酸ナトリウム、ポリオキシエチレンステアリルエーテルリン酸ナトリウム等のポリオキシアルキレンアルキルエーテルリン酸エステル塩、［１０］ジ－２－エチルヘキシルスルホコハク酸ナトリウム、ジオクチルスルホコハク酸ナトリウム等の長鎖スルホコハク酸塩、［１１］Ｎ－ラウロイルグルタミン酸モノナトリウム、Ｎ－ステアロイル－Ｌ－グルタミン酸ジナトリウム等の長鎖Ｎ－アシルグルタミン酸塩、等が挙げられる。成分（Ｃ）は、界面活性剤を１種類のみ含んでもよいし、２種類以上の界面活性剤を併用してもよい。 The surfactant is not particularly limited, and may be a cationic surfactant, a nonionic surfactant, or an anionic surfactant, but at least one of a nonionic surfactant and an anionic surfactant is preferable. Examples of the nonionic surfactant include [1] polyoxyalkylene alkyl ethers such as polyoxyethylene cetyl ether and polyoxyethylene lauryl ether, and [2] polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether. Polyoxyalkylene alkyl phenyl ether, [3] polyoxyethylene fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monooleate, [4] polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate and the like. Polyoxyalkylene sorbitan fatty acid ester, [5] polyoxyalkylene cured castor oil, [6] polyoxyalkylene sorbitol fatty acid ester, [7] polyglycerin fatty acid ester, [8] alkyl glycerin ether, [9] polyoxyalkylene cholesteryl ether. , [10] Alkyl polyglucoside, [11] Sucrose fatty acid ester, [12] Polyoxyalkylene alkylamine, [13] Oxyethylene-oxypropylene block polymer, and the like. Examples of the anionic surfactant include [1] fatty acid salts such as sodium oleate, potassium palmitate, and triethanolamine oleate, and [2] sodium lauryl sulfate, ammonium lauryl sulfate, sodium stearyl sulfate, and sodium cetyl sulfate. Alkyl sulfate ester salt, [3] Polyoxyalkylene alkyl ether acetate such as sodium polyoxyethylene tridecyl ether acetate, [4] Alkylbenzene sulfonate such as sodium dodecylbenzene sulfonate, [5] Polyoxyalkylene alkyl ether sulfate Salts, [6] higher fatty acid amide sulfonates such as stearoylmethyl taurine Na, lauroylmethyl taurine Na, myristylmethyl taurine Na, palmitoyl methyl taurine Na, [7] N-acylsarcosine salts such as lauroyl sarcosin sodium, [8] Alkyl phosphates such as sodium monostearyl phosphate, [9] polyoxyalkylene alkyl ether phosphates such as sodium polyoxyethylene oleyl ether phosphate, sodium polyoxyethylene stearyl ether phosphate, [10] di-2. -Long-chain sulfosuccinates such as sodium ethylhexyl sulfosuccinate and sodium dioctyl sulfosuccinate, long-chain N-acylglutamates such as [11] monosodium N-lauroylglutamate, disodium N-stearoyl-L-glutamate, etc. Be done. The component (C) may contain only one type of surfactant, or may contain two or more types of surfactant in combination.
本発明のタイヤ内面用離型剤における成分（Ｃ）の含有率は、目的に応じて選択可能であり、例えば、タイヤ内面用離型剤の質量全体に対して、０．２～２０質量％、１～１０質量％、または２～６質量％であってもよい。タイヤ内面用離型剤の乳化安定性の観点、および、生タイヤ若しくはブラダーへの濡れ性が低下しハジキが発生する現象を防止する観点から、前記成分（Ｃ）の含有率は、０．２質量％以上が好ましい。また、タイヤ内面用離型剤の付着性および離型性の観点、並びに、タイヤの貼り合せ部に離型剤が入り込んで接着阻害を起こす現象を防止する観点から、前記成分（Ｃ）の含有率は、２０質量％以下が好ましい。 The content of the component (C) in the tire inner surface mold release agent of the present invention can be selected according to the intended purpose, for example, 0.2 to 20% by mass with respect to the total mass of the tire inner surface mold release agent. It may be 1 to 10% by mass, or 2 to 6% by mass. The content of the component (C) is 0.2 from the viewpoint of the emulsification stability of the mold release agent for the inner surface of the tire and from the viewpoint of preventing the phenomenon that the wettability to the raw tire or the bladder is lowered and repelling is generated. It is preferably mass% or more. Further, from the viewpoint of the adhesiveness and releasability of the mold release agent for the inner surface of the tire, and from the viewpoint of preventing the phenomenon that the mold release agent enters the bonded portion of the tire and causes adhesion inhibition, the component (C) is contained. The rate is preferably 20% by mass or less.
［１－４．Ｌ＊値が９０未満であるマイカ（Ｄ）］
Ｌ＊値が９０未満であるマイカ（成分（Ｄ））としては、例えば、黒雲母、金雲母、イライト、カラーマイカ等が挙げられる。黒雲母、金雲母およびイライトの化学構造式の一例および後述の実施例に記載の方法で測定したＬ＊値は、下記表１に示すとおりである。
[1-4. L * Mica (D) whose value is less than 90]
Examples of mica (component (D)) having an L * value of less than 90 include biotite, phlogopite, illite, and color mica. The L * values measured by the methods described in Examples of the chemical structural formulas of biotite, phlogopite and illite and the examples described later are as shown in Table 1 below.
成分（Ｄ）は、Ｌ＊値が９０未満であるマイカを１種類のみ含んでもよいし、２種類以上のマイカの併用により、Ｌ＊値が９０未満であってもよい。 The component (D) may contain only one type of mica having an L * value of less than 90, or may have an L * value of less than 90 by using two or more types of mica in combination.
本発明のタイヤ内面用離型剤における成分（Ｄ）の含有率は、目的に応じて選択可能であり、例えば、タイヤ内面用離型剤の質量全体に対して、１～６０質量％、２～５０質量％、または５～４０質量％であってもよい。 The content of the component (D) in the tire inner surface mold release agent of the present invention can be selected according to the intended purpose. For example, 1 to 60% by mass, 2 It may be up to 50% by mass, or 5 to 40% by mass.
本発明のタイヤ内面用離型剤によれば、Ｌ＊値が９０未満であるマイカ（成分（Ｄ））を用いたことで、離型性および滑性を悪化させることなく、外観を向上可能である。 According to the mold release agent for the inner surface of the tire of the present invention, the appearance can be improved without deteriorating the mold release property and the slipperiness by using mica (component (D)) having an L * value of less than 90. Is.
前記成分（Ｄ）のＬ＊値は、例えば、８６未満、８３以下、または７５以下であってもよい。前記Ｌ＊値の下限は、特に限定されず、例えば、５以上、１０以上、または１５以上であってもよい。 The L * value of the component (D) may be, for example, less than 86, 83 or less, or 75 or less. The lower limit of the L * value is not particularly limited and may be, for example, 5 or more, 10 or more, or 15 or more.
前述のとおり、前記成分（Ｄ）は、例えば、マグネシウムを含有するマイカであってもよい。前述の黒雲母、金雲母がこれに該当し、前記表１に示した化学構造式の一例には表れていないが、前述のイライトも、マグネシウムを含有することがある。前記成分（Ｄ）がマグネシウムを含有するマイカであれば、例えば、外観をより向上可能である。 As described above, the component (D) may be, for example, magnesium-containing mica. The above-mentioned biotite and phlogopite correspond to this, and although they do not appear in the example of the chemical structural formula shown in Table 1, the above-mentioned illite may also contain magnesium. If the component (D) is magnesium-containing mica, for example, the appearance can be further improved.
本発明のタイヤ内面用離型剤において、前記成分（Ａ）の質量（含有率Ａｗ）と、前記成分（Ｄ）の質量（含有率Ｄｗ）との比（Ａｗ／Ｄｗ）は、特に限定されず、例えば、０．１～１０、０．５～５、または２～５であってもよい。 In the tire inner surface mold release agent of the present invention, the ratio (Aw / Dw) of the mass (content rate Aw) of the component (A) to the mass (content rate Dw) of the component (D) is particularly limited. However, it may be, for example, 0.1 to 10, 0.5 to 5, or 2 to 5.
［１－５．任意成分］
本発明のタイヤ内面用離型剤は、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。前記任意成分としては、例えば、透明性向上に寄与し得る多価アルコール、水、シリコーン系消泡剤、鉱物油系消泡剤等の各種消泡剤、各種防腐剤等が挙げられる。
[1-5. Optional ingredient]
The release agent for the inner surface of the tire of the present invention may or may not contain any component other than the components (A) to (D). Examples of the optional component include polyhydric alcohol, water, various defoaming agents such as silicone-based defoaming agents and mineral oil-based defoaming agents, and various preservatives that can contribute to the improvement of transparency.
前記多価アルコールとしては、特に限定されず、例えば、［１］ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ペンタエチレングリコール、ヘキサエチレングリコール等のポリエチレングリコール類、［２］ジプロピレングリコール、トリプロピレングリコール、テトラプロピレングリコール、ペンタプロピレングリコール、ヘキサプロピレングリコール等のポリプロピレングリコール類、［３］ジブチレングリコール、トリブチレングリコール、テトラブチレングリコール、ペンタブチレングリコール、ヘキサブチレングリコール等のポリブチレングリコール類、［４］エチレングリコール、１，２－プロピレングリコール、１，３－プロピレングリコール、１，２－ブタンジオール、１，４－ブタンジオール、１，２－ペンタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、１，２－ヘキサンジオール、１，５－ヘキサンジオール、２，５－ヘキサンジオール、１，７－へプタンジオール、１，８－オクタンジオール、１，２－オクタンジオール、１，９－ノナンジオール、１，２－ノナンジオール、１，１０－デカンジオール、１，２－デカンジオール、１，１２－ドデカンジオール、１，２－ドデカンジオール、１，１４－テトラデカンジオール、１，２－テトラデカンジオール、１，１６－ヘキサデカンジオール、１，２－ヘキサデカンジオール、２－メチル－２，４－ペンタンジオール、３－メチル－１，５－ペンタンジオール、２－メチル－２，４－ペンタンジオール、３－メチル－１，５－ペンタンジオール、２－メチル－２－プロピル－１，３－プロパンジオール、２，４－ジメチル－２，４－ジメチルペンタンジオール、２，２－ジエチル－１，３－プロパンジオール、２，２，４－トリメチル－１，３－ペンタンジオール、ジメチロールオクタン、２－エチル－１，３－ヘキサンジオール、２，５－ジメチル－２，５－ヘキサンジオール、２－メチル－１，８－オクタンジオール、２－ブチル－２－エチル－１，３－プロパンジオール、２，４－ジエチル－１、５－ペンタンジオール、１，２－シクロヘキサンジオール、１，４－シクロヘキサンジオール、１，４－シクロヘキサンジメタノール、１，２－シクロへプタンジオール、トリシクロデカンジメタノール、グリセリン、トリメチロールプロパン、１，２，６－ヘキサントリオール、３－メチルペンタン－１，３，５－トリオール、ヒドロキシメチルヘキサンジオール、トリメチロールオクタン、およびこれらの２種類以上の共重合体等が挙げられる。これらの多価アルコールは、１種類のみ用いてもよいし、複数種類を併用してもよい。 The polyvalent alcohol is not particularly limited, and is, for example, [1] polyethylene glycols such as [1] diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, and hexaethylene glycol, and [2] dipropylene glycol and tripropylene glycol. , Polybutylene glycols such as tetrapropylene glycol, pentapropylene glycol, hexapropylene glycol, [3] polybutylene glycols such as dibutylene glycol, tributylene glycol, tetrabutylene glycol, pentabutylene glycol, hexabutylene glycol, [4] Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexane Glycol, 1,2-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonan Glycol, 1,2-nonanediol, 1,10-decanediol, 1,2-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,14-tetradecanediol, 1,2-tetradecanediol , 1,16-Hexadecanediol, 1,2-Hexadecanediol, 2-Methyl-2,4-Pentanediol, 3-Methyl-1,5-Pentanediol, 2-Methyl-2,4-Pentanediol, 3- Methyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-dimethylpentanediol, 2,2-diethyl-1,3-propanediol , 2,2,4-trimethyl-1,3-pentanediol, dimethylol octane, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-methyl-1, 8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4 -Cyclohexanedimethanol, 1,2-cycloheptanediol, tricyclodecanedimethanol, glycerin, trimethylolpropane, 1,2,6-hexanetriol, 3 -Methylpentane-1,3,5-triol, hydroxymethylhexanediol, trimethyloloctane, and copolymers of two or more of these can be mentioned. Only one kind of these polyhydric alcohols may be used, or a plurality of kinds may be used in combination.
本発明のタイヤ内面用離型剤の製造方法は、特に限定されず、例えば、一般的な乳化機を用いて、本発明のタイヤ内面用離型剤の各成分を乳化することにより製造してもよい。前記乳化機も、特に限定されず、例えば、一般的な攪拌機、ホモミキサー、ホモディスパー等が挙げられる。 The method for producing the release agent for the inner surface of the tire of the present invention is not particularly limited, and for example, it is produced by emulsifying each component of the release agent for the inner surface of the tire of the present invention using a general emulsifier. May be good. The emulsifying machine is also not particularly limited, and examples thereof include a general stirrer, a homomixer, and a homodisper.
本発明のタイヤ内面用離型剤の形態は、特に限定されず、例えば、前記成分（Ａ）～（Ｄ）が、水の中に分散された乳化物（水分散液）であることが好ましい。 The form of the mold release agent for the inner surface of the tire of the present invention is not particularly limited, and for example, it is preferable that the components (A) to (D) are emulsions (aqueous dispersion liquid) dispersed in water. ..
本発明のタイヤ内面用離型剤水分散液の製造（調製）方法も、特に限定されず、例えば、水に前記本発明のタイヤ内面用離型剤を混合して分散させるのみで良い。本発明のタイヤ内面用離型剤水分散液において、前記本発明のタイヤ内面用離型剤の濃度は、特に限定されず、例えば、２０～７５質量％、３０～７０質量％、または３０～６５質量％であってもよい。 The method for producing (preparing) the release agent for the inner surface of the tire of the present invention is not particularly limited, and for example, the release agent for the inner surface of the tire of the present invention may be simply mixed and dispersed in water. In the tire inner surface mold release agent water dispersion liquid of the present invention, the concentration of the tire inner surface mold release agent of the present invention is not particularly limited, and is, for example, 20 to 75% by mass, 30 to 70% by mass, or 30 to 30 to. It may be 65% by mass.
本発明のタイヤ内面用離型剤の使用方法も、特に限定されず、例えば、一般的なタイヤ内面用離型剤と同様でよい。具体的には、例えば、本発明のタイヤ内面用離型剤を、原液の状態で、または水に希釈した状態で、スプレーを用いて、未加硫ゴム製生タイヤの内面およびブラダー外面の少なくとも一方に塗布して用いればよい。 The method of using the release agent for the inner surface of the tire of the present invention is not particularly limited, and may be the same as that of a general release agent for the inner surface of the tire, for example. Specifically, for example, the mold release agent for the inner surface of the tire of the present invention is used in a stock solution or diluted with water using a spray to at least the inner surface and the outer surface of the bladder of an unvulcanized rubber raw tire. It may be applied to one side and used.
本発明のタイヤ内面用離型剤は、前述のとおり、乳化物（エマルジョン、水分散液）であってもよい。前記乳化物の平均粒子径は、特に限定されず、例えば、５０～２０００ｎｍ、１００～１５００ｎｍ、または１５０～１３００ｎｍであってもよい。界面活性剤の必要配合量が増大することによる付着性低下および離型性低下防止の観点、並びに、貼り合せ部に離型剤が入り込んだ際の接着阻害防止の観点から、前記乳化物の平均粒子径は、５０ｎｍ以上が好ましい。また、乳化粒子のクリーミングおよび合一防止の観点、並びに、水溶成分と油溶成分が分離し製品安定性が不良となることを防止し得る観点から、前記乳化物の平均粒子径は、２０００ｎｍ以下が好ましい。なお、本発明において、前記乳化物の平均粒子径は、例えば、ＢＥＣＫＭＡＮ社製のサブミクロン粒子アナライザー（レーザー回折／散乱法）を用いて乳化粒子の体積分布を測定し、測定した前記乳化粒子の体積分布に基づいて、前記平均粒子径を算出することができる。ただし、この測定方法は、例示であり、本発明は、この測定方法により限定されない。 As described above, the mold release agent for the inner surface of the tire of the present invention may be an emulsion (emulsion, aqueous dispersion). The average particle size of the emulsion is not particularly limited and may be, for example, 50 to 2000 nm, 100 to 1500 nm, or 150 to 1300 nm. The average of the emulsions from the viewpoint of preventing deterioration of adhesion and mold release due to an increase in the required blending amount of the surfactant, and from the viewpoint of preventing adhesion inhibition when the mold release agent enters the bonding portion. The particle size is preferably 50 nm or more. Further, from the viewpoint of preventing creaming and coalescence of the emulsified particles, and from the viewpoint of preventing the water-soluble component and the oil-soluble component from separating from each other and impairing product stability, the average particle size of the emulsion is 2000 nm or less. Is preferable. In the present invention, the average particle size of the emulsion is determined by measuring the volume distribution of the emulsified particles using, for example, a submicron particle analyzer (laser diffraction / scattering method) manufactured by BECKMAN. The average particle size can be calculated based on the volume distribution. However, this measuring method is an example, and the present invention is not limited to this measuring method.
［２．タイヤの製造方法およびタイヤ］
本発明のタイヤの製造方法およびタイヤについては、前述のとおりである。これらについても、特に限定はなく、例えば、一般的なタイヤ内面用離型剤（水分散液の形態であるタイヤ内面用離型剤）に代えて、前記本発明のタイヤ内面用離型剤水分散液またはタイヤ内面用離型剤を用いること以外は、一般的なタイヤの製造方法およびタイヤと同様でよい。本発明のタイヤの製造方法において、前記成形型としては、例えば、金型等が挙げられる。本発明のタイヤの製造方法は、前述の剥離用前処理工程および加硫工程に加えて、加硫タイヤと前記ブラダーとの間、および、加硫タイヤと前記成形型との間を離型処理する離型処理工程を有してもよい。
[2. Tire manufacturing method and tire]
The method for manufacturing the tire and the tire of the present invention are as described above. These are also not particularly limited, and for example, instead of a general tire inner surface mold release agent (a tire inner surface mold release agent in the form of a water dispersion), the tire inner surface mold release agent water of the present invention is used. It may be the same as a general tire manufacturing method and tire except that a dispersion liquid or a mold release agent for the inner surface of the tire is used. In the method for manufacturing a tire of the present invention, examples of the molding die include a mold and the like. In the tire manufacturing method of the present invention, in addition to the above-mentioned peeling pretreatment step and vulcanization step, a mold release treatment is performed between the vulcanized tire and the bladder and between the vulcanized tire and the molding die. It may have a mold release processing step.
［実施例１～１０、比較例１および２］
下記表２および３に記載された各成分（原料）を、市販の電動コンパクトミル（容量５００ｍＬ）中に、順次撹拌しながら添加し、その後、３分間撹拌し、粉末状のタイヤ内面用離型剤を製造した。実施例１～１０は、下記表２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３に示すとおり、比較例１は、成分（Ａ）、（Ｂ）、（Ｃ）を配合したが、成分（Ｄ）に代えて、Ｌ＊値が９０である白雲母を配合し、比較例２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２および３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４に示す。また、下記表２および３における成分（Ｄ）または白雲母のＬ＊値は、下記方法により測定した。
（成分（Ｄ）または白雲母のＬ＊値の測定方法）
表２および３に記載の実施例１～１０および比較例１における各成分（Ｄ）または白雲母をガラスセルに入れ、Ｃｏｌｏｒ ｍｅｔｅｒ ＺＥ６０００（日本電色工業（株）製）にて反射モードでＬ＊値を３回測定し、平均値を算出した。
[Examples 1 to 10, Comparative Examples 1 and 2]
Each component (raw material) shown in Tables 2 and 3 below is added to a commercially available electric compact mill (capacity 500 mL) with stirring in sequence, and then stirred for 3 minutes to release the powdery tire inner surface. Manufactured the agent. In Examples 1 to 10, all the components (A) to (D) were blended as shown in Table 2 below. On the other hand, as shown in Table 3 below, in Comparative Example 1, the components (A), (B), and (C) were blended, but instead of the component (D), muscovite having an L * value of 90. In Comparative Example 2, the components (A), (B), and (C) were blended, but the component (D) was not blended. The product names (trade names) and manufacturers of the components listed in Tables 2 and 3 below are shown in Table 4 below. The L * value of the component (D) or muscovite in Tables 2 and 3 below was measured by the following method.
(Measuring method of L * value of component (D) or muscovite)
Each component (D) or muscovite in Examples 1 to 10 and Comparative Example 1 shown in Tables 2 and 3 is placed in a glass cell, and L in a reflection mode with Colormeter ZE6000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.). * The value was measured 3 times and the average value was calculated.
表２および３に記載の実施例１～１０、比較例１および２の各タイヤ内面用離型剤水分散液を用いて、下記の評価を行った。各例のタイヤ内面用離型剤水分散液の製造方法は、つぎのとおりである。すなわち、まず、２Ｌガラスビーカーに水道水４５０ｇを仕込んだ後、直径５ｃｍの３枚のプロペラ羽を備えた攪拌機で２０ｒｐｍの速度で撹拌した。前記水中に、撹拌しながら、各例で製造した粉末状のタイヤ内面用離型剤５５０ｇを投入し、３０分間撹拌して分散させることで、各例のタイヤ内面用離型剤水分散液を製造した。 The following evaluations were performed using the release agent water dispersions for the inner surfaces of the tires of Examples 1 to 10 and Comparative Examples 1 and 2 shown in Tables 2 and 3. The method for producing the release agent water dispersion for the inner surface of the tire in each example is as follows. That is, first, 450 g of tap water was charged into a 2 L glass beaker, and then the mixture was stirred at a speed of 20 rpm with a stirrer equipped with three propeller blades having a diameter of 5 cm. While stirring, 550 g of the powder release agent for the inner surface of the tire produced in each example is put into the water, and the mixture is stirred and dispersed for 30 minutes to disperse the water release agent for the inner surface of the tire of each example. Manufactured.
（塗布面外観）
前記各タイヤ内面用離型剤水分散液に市販のカーボンブラック分散液（御国色素（株）製、固形分４０％）０．５％を配合したものを、４ｃｍ×７ｃｍ×０．２ｃｍの未加硫インナーライナーゴムシートに、乾燥後塗布量が１０ｇ／ｍ２となるようにスプレー塗布した。つぎに、この未加硫ゴムシートを、卓上型テストプレス機にセットし、金型温度１８０℃、圧力２０ｋｇ／ｃｍ２で２０分間加圧し、加硫した後の外観を目視により評価した。塗布面外観は、外観が灰色で白色の斑点のないものを○、白色の斑点が塗布面積の０．５％以上あるものを△、白色の斑点が塗布面積の１％以上あるものを×と評価した。
(Appearance of coated surface)
A mixture of 0.5% of a commercially available carbon black dispersion (manufactured by Mikuni Color Co., Ltd., solid content 40%) with the release agent water dispersion for the inner surface of each tire is 4 cm × 7 cm × 0.2 cm. The vulcanized inner liner rubber sheet was spray-coated so that the coating amount after drying was 10 g / m 2 . Next, this unvulcanized rubber sheet was set in a tabletop test press machine, pressed at a mold temperature of 180 ° C. and a pressure of 20 kg / cm 2 for 20 minutes, and the appearance after vulcanization was visually evaluated. As for the appearance of the coated surface, those with a gray appearance and no white spots are marked with ○, those with white spots of 0.5% or more of the coated area are marked with △, and those with white spots of 1% or more of the coated area are marked with ×. evaluated.
（離型性）
前記各タイヤ内面用離型剤水分散液を、４ｃｍ×７ｃｍ×０．２ｃｍの未加硫インナーライナーゴムシートに、乾燥後塗布量が１０ｇ／ｍ２となるようにスプレー塗布した。つぎに、この未加硫ゴムシートに同じ大きさのブラダーゴムシートを重ね合わせ、卓上型テストプレス機にセットし、金型温度１８０℃、圧力２０ｋｇ／ｃｍ２で２０分間加圧し、加硫した。その後、加硫済みの前記ゴムシートを引き剥がした。剥離性（離型性）は、密着無く容易に剥離（離型）できたものを５級、剥離（離型）できたものを４級、剥離抗力が大きいが離型できたものと３級、一部密着し剥離（離型）しがたいものを２級、全面密着し剥離（離型）不可能なものを１級と評価した。
(Releasability)
The release agent water dispersion for the inner surface of each tire was spray-coated on a 4 cm × 7 cm × 0.2 cm unvulcanized inner liner rubber sheet so that the amount applied after drying was 10 g / m 2 . Next, a bladder rubber sheet of the same size was superposed on this unvulcanized rubber sheet, set in a tabletop test press machine, pressed at a mold temperature of 180 ° C. and a pressure of 20 kg / cm 2 for 20 minutes, and vulcanized. .. Then, the vulcanized rubber sheet was peeled off. The peelability (release property) is 5th grade for those that can be easily peeled (released) without adhesion, 4th grade for those that can be peeled (released), and 3rd grade for those that have a large peeling drag but can be released. Those that were partially in close contact and difficult to peel off (release) were evaluated as grade 2, and those that were in close contact with the entire surface and could not be peeled (released) were evaluated as grade 1.
（滑性）
前記各タイヤ内面用離型剤水分散液を、４ｃｍ×７ｃｍ×０．２ｃｍの未加硫インナーライナーゴムシートに、乾燥後塗布量が１０ｇ／ｍ２となるようにスプレー塗布した。つぎに、この未加硫ゴムシートに加硫ブラダーゴムシート（３ｃｍ×３ｃｍ×０．１ｃｍ）を重ね合わせ、１ｋｇの重量をかけて２０ｃｍ引っ張った際の滑り状態を評価した。滑性は、引っ掛かり回数が多いほど悪いと判断し、３回以下を合格とした。
(Slippery)
The release agent water dispersion for the inner surface of each tire was spray-coated on a 4 cm × 7 cm × 0.2 cm unvulcanized inner liner rubber sheet so that the amount applied after drying was 10 g / m 2 . Next, a vulcanized bladder rubber sheet (3 cm × 3 cm × 0.1 cm) was superposed on this unvulcanized rubber sheet, and the slip state when pulled by 20 cm with a weight of 1 kg was evaluated. It was judged that the slipperiness was worse as the number of times of catching was increased, and 3 times or less was judged as passing.
上記評価結果を、前記表２および３に示した。表２に示したとおり、実施例１～１０は、塗布面外観、離型性および滑性の評価のいずれも良好であった。これに対し、表３に示したとおり、成分（Ｄ）に代えて、Ｌ＊値が９０である白雲母を用いた比較例１は、塗布面外観が不良となった。また、成分（Ｄ）を用いなかった比較例２は、離型性および滑性が悪かった。 The evaluation results are shown in Tables 2 and 3 above. As shown in Table 2, Examples 1 to 10 were all good in the evaluation of the appearance of the coated surface, the releasability and the slipperiness. On the other hand, as shown in Table 3, in Comparative Example 1 in which muscovite having an L * value of 90 was used instead of the component (D), the appearance of the coated surface was poor. In addition, Comparative Example 2 in which the component (D) was not used had poor releasability and slipperiness.
Claims (7)
下記成分（Ａ）の含有率が、タイヤ内面用離型剤の質量全体に対して１０～９０質量％であり、
下記成分（Ｂ）の含有率が、タイヤ内面用離型剤の質量全体に対して１～３０質量％であり、
下記成分（Ｃ）の含有率が、タイヤ内面用離型剤の質量全体に対して１～２０質量％であり、
下記成分（Ｄ）の含有率が、タイヤ内面用離型剤の質量全体に対して１～７５質量％である
ことを特徴とする粉末状のタイヤ内面用離型剤。
（Ａ）下記成分（Ｄ）、硼ケイ酸ガラス製ガラスビーズ、および焼成カオリン以外の無機成分
（Ｂ）２５℃において、１０００～１０万ｍＰａ・ｓであるシリコーン成分
（Ｃ）ポリオキシエチレンノニルフェニルエーテル、ドデシルベンゼンスルホン酸ナトリウム以外の界面活性剤
（Ｄ）Ｌ＊値が１５以上、７０以下であるマイカ Contains the following components (A) to (D)
The content of the following component (A) is 10 to 90% by mass with respect to the total mass of the mold release agent for the inner surface of the tire.
The content of the following component (B) is 1 to 30% by mass with respect to the total mass of the mold release agent for the inner surface of the tire.
The content of the following component (C) is 1 to 20% by mass with respect to the total mass of the mold release agent for the inner surface of the tire.
The content of the following component (D) is 1 to 75% by mass with respect to the total mass of the mold release agent for the inner surface of the tire.
A powdery tire release agent for the inner surface of a tire.
(A) The following component (D) , glass beads made of borosilicate glass, and an inorganic component (B) other than calcined kaolin . Silicone component (C) polyoxyethylene nonylphenyl which is 1,000 to 100,000 mPa · s at 25 ° C. Surfactants other than ether and sodium dodecylbenzene sulfonate (D) L * Mica with a value of 15 or more and 70 or less
前記離型用前処理工程後、成形型内で前記生タイヤに収容された前記ブラダーを膨張させることにより、前記成形型内面に前記生タイヤ外面を押し当て、その状態で前記生タイヤを加熱して加硫する加硫工程と、
を含むことを特徴とするタイヤの製造方法。 The release pretreatment step of adhering the release agent water dispersion for the inner surface of the tire according to claim 5 to at least one of the inner surface of the unvulcanized rubber raw tire and the outer surface of the bladder and further volatilizing the water.
After the mold release pretreatment step, the bladder housed in the raw tire is expanded in the mold to press the outer surface of the raw tire against the inner surface of the mold, and the raw tire is heated in that state. Vulcanization process and vulcanization process
A method of manufacturing a tire, which comprises.
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| WO2021167025A1 (en) * | 2020-02-21 | 2021-08-26 | ライオン・スペシャリティ・ケミカルズ株式会社 | Rubber-inner-surface release agent, rubber-inner-surface release-agent manufacturing method, rubber-inner-surface release-agent water dispersion liquid, rubber-product manufacturing method, tire manufacturing method, rubber product, and tire |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005193448A (en) | 2004-01-05 | 2005-07-21 | Sumitomo Rubber Ind Ltd | Mold release agent for vulcanization molding of tire |
| JP2010260258A (en) | 2009-05-07 | 2010-11-18 | Yokohama Rubber Co Ltd:The | Method for manufacturing pneumatic tire |
| JP2016040080A (en) | 2014-08-12 | 2016-03-24 | 松本油脂製薬株式会社 | Mold release agent for tire inner surface |
| JP2017019231A (en) | 2015-07-14 | 2017-01-26 | 松本油脂製薬株式会社 | Mold release agent for tire inner face and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0839575A (en) * | 1994-07-26 | 1996-02-13 | Toray Dow Corning Silicone Co Ltd | Tire mold release agent composition |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005193448A (en) | 2004-01-05 | 2005-07-21 | Sumitomo Rubber Ind Ltd | Mold release agent for vulcanization molding of tire |
| JP2010260258A (en) | 2009-05-07 | 2010-11-18 | Yokohama Rubber Co Ltd:The | Method for manufacturing pneumatic tire |
| JP2016040080A (en) | 2014-08-12 | 2016-03-24 | 松本油脂製薬株式会社 | Mold release agent for tire inner surface |
| JP2017019231A (en) | 2015-07-14 | 2017-01-26 | 松本油脂製薬株式会社 | Mold release agent for tire inner face and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| 太田俊一，合成マイカとその応用，粘土科学，日本，一般社団法人 日本粘土学会，2004年05月26日，第４４巻、第１号，３１－３６頁 |
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