JP6479510B2 - Mold release agent for vulcanized rubber hose molding - Google Patents
Mold release agent for vulcanized rubber hose molding Download PDFInfo
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- JP6479510B2 JP6479510B2 JP2015047321A JP2015047321A JP6479510B2 JP 6479510 B2 JP6479510 B2 JP 6479510B2 JP 2015047321 A JP2015047321 A JP 2015047321A JP 2015047321 A JP2015047321 A JP 2015047321A JP 6479510 B2 JP6479510 B2 JP 6479510B2
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- 239000004636 vulcanized rubber Substances 0.000 title claims description 32
- 238000000465 moulding Methods 0.000 title claims description 17
- 239000006082 mold release agent Substances 0.000 title description 18
- 229920001971 elastomer Polymers 0.000 claims description 37
- 239000005060 rubber Substances 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 150000002009 diols Chemical class 0.000 claims description 25
- 125000006353 oxyethylene group Chemical group 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 8
- -1 oxypropylene group Chemical group 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 16
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 14
- 238000004073 vulcanization Methods 0.000 description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000004800 polyvinyl chloride Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920000915 polyvinyl chloride Polymers 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
Landscapes
- Moulds For Moulding Plastics Or The Like (AREA)
Description
本発明は、加硫ゴムホース成形用離型剤に関するものである。 The present invention relates to a release agent for forming a vulcanized rubber hose.
加硫ゴムホースは、例として自動車部品、鉄道部品、建設機械などに使用されている。これらの加硫ゴムホースは、マンドレルなどの芯材で加硫成形し、これを脱着することにより得られるが、脱着を容易に行うために、芯材やゴムホースには離型剤が塗布されている。 Vulcanized rubber hoses are used, for example, in automobile parts, railway parts, construction machines and the like. These vulcanized rubber hoses are obtained by vulcanizing and forming a core material such as a mandrel and removing the same, but in order to facilitate desorption, the core material and the rubber hose are coated with a release agent .
このような離型剤としては、シリコーンが使用されているが、加硫後のゴムホースに付着した離型剤を除去するためには洗剤などを用いる必要があり、その改善が求められている。そこで、容易に除去可能な離型剤として、特許文献１では、グリセリン脂肪酸エステルのアルキレンオキサイド付加物が開示されている。また、特許文献２では、オキシエチレン基の含有量が２０％以上４０％未満であるポリオキシエチレン・ポリオキシプロピレンブロックコポリマーが開示されている。 Although silicone is used as such a mold release agent, in order to remove the mold release agent adhering to the rubber hose after vulcanization, it is necessary to use a detergent etc., and the improvement is calculated | required. Thus, as an easily removable release agent, Patent Document 1 discloses an alkylene oxide adduct of a glycerin fatty acid ester. Patent Document 2 discloses a polyoxyethylene / polyoxypropylene block copolymer in which the content of oxyethylene groups is 20% or more and less than 40%.
しかしながら、特許文献１および２に記載の離型剤においては、使用するゴムの種類によって新たな問題が生じることが判明した。例えば、自動車用途や航空機用途などの耐摩耗性が要求される用途では、加硫ゴムホースのゴム材料として、アクリロニトリル−ブタジエン共重合ゴム（ＮＢＲ）とポリ塩化ビニル（ＰＶＣ）とをブレンドしたゴムが使用される。このようなＮＢＲとＰＶＣをブレンドしたゴムに上記離型剤を使用した場合、作業時の応力によりゴムホースにクラックが発生することがわかった。 However, in the mold release agents described in Patent Documents 1 and 2, it has been found that a new problem arises depending on the type of rubber used. For example, in applications where wear resistance is required, such as automotive applications and aircraft applications, rubber blended with acrylonitrile-butadiene copolymer rubber (NBR) and polyvinyl chloride (PVC) is used as a rubber material of a vulcanized rubber hose. Be done. It has been found that when the above-mentioned mold release agent is used for a rubber obtained by blending such NBR and PVC, a crack is generated in the rubber hose due to the stress at the time of operation.
本発明は、作業時の応力によるクラックの発生を抑制するとともに、製造後に離型剤を容易に除去できる加硫ゴムホース成形用離型剤を提供することを目的とする。 An object of the present invention is to provide a release agent for molding a vulcanized rubber hose, which can suppress generation of a crack due to stress during operation and can easily remove the release agent after production.
本発明に係る加硫ゴムホース成形用離型剤は、下記一般式（１）で表されるポリオキシアルキレンジオールであって、オキシエチレン基の含有量が８０〜９５質量％であるポリオキシアルキレンジオールを含有するものである。 The release agent for molding a vulcanized rubber hose according to the present invention is a polyoxyalkylene diol represented by the following general formula (1), wherein the content of the oxyethylene group is 80 to 95 mass%. Containing
ＨＯ−（ＥＯ）a−（ＰＯ）b−Ｘ−Ｏ−（ＰＯ）c−（ＥＯ）d−Ｈ （１）
ただし、式中、ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基を表し、ａ、ｂ、ｃおよびｄはそれぞれ平均付加モル数であって、ａ＋ｄが２０〜４５０の数、ｂ＋ｃが１〜１４０の数であり、Ｘは炭素数２〜１０のアルキレン基である。
HO- (EO) a- (PO) b- X-O- (PO) c- (EO) d- H (1)
However, in the formula, EO represents an oxyethylene group, PO represents an oxypropylene group, a, b, c and d represent the average addition mole number, and a + d is the number of 20 to 450 and b + c is 1 to 140 It is a number and X is a C2-C10 alkylene group.
本発明はまた、該離型剤を用いた加硫ゴムホースの製造方法を提供するものであり、同製造方法は、マンドレル（即ち、ゴムホース芯材）と未加硫のゴムホースの少なくとも一方に該加硫ゴムホース成形用離型剤を塗布する工程と、前記未加硫ゴムホースにマンドレルを挿入しゴムホースを加硫成形する工程、とを含むものである。 The present invention also provides a method for producing a vulcanized rubber hose using the mold release agent, which comprises adding at least one of a mandrel (i.e., a rubber hose core) and an unvulcanized rubber hose. And a step of applying a release agent for forming a vulcanized rubber hose, and a step of inserting a mandrel into the unvulcanized rubber hose and vulcanizing and forming the rubber hose.
上記加硫ゴムホース成形用離型剤であると、離型剤が付着したゴムホースにおいて作業時の応力によるクラックの発生を抑制することができるとともに、製造後に離型剤を容易に除去することができる。 While being able to suppress generation | occurrence | production of the crack by the stress at the time of working in the rubber hose to which the mold release agent adhered that it is a mold release agent for said vulcanized rubber hose, a mold release agent can be easily removed after manufacture. .
＜ポリオキシアルキレンジオール＞
本実施形態に係る加硫ゴムホース成形用離型剤は、下記一般式（１）で表されるポリオキシアルキレンジオールを含有する。
<Polyoxyalkylene diol>
The vulcanized rubber hose molding release agent according to this embodiment contains a polyoxyalkylene diol represented by the following general formula (1).
ＨＯ−（ＥＯ）a−（ＰＯ）b−Ｘ−Ｏ−（ＰＯ）c−（ＥＯ）d−Ｈ （１）
式（１）中、ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基を表す。ａおよびｄは、オキシエチレン基の平均付加モル数を示し、ｂおよびｃは、オキシプロピレン基の平均付加モル数を示す。ＥＯおよびＰＯの付加形態はブロック付加であり、−Ｘ−Ｏ−で表される基の両末端にＰＯがブロック付加され、その両末端にＥＯがブロック付加された構造を有する。
HO- (EO) a- (PO) b- X-O- (PO) c- (EO) d- H (1)
In Formula (1), EO represents an oxyethylene group, and PO represents an oxypropylene group. a and d show the average added mole number of the oxyethylene group, and b and c show the average added mole number of the oxypropylene group. The addition form of EO and PO is block addition, and PO has a block addition to the both ends of the group represented by -X-O- and EO has a block addition to the both ends.
ａ＋ｄで表されるＥＯの平均付加モル数の合計は、２０〜４５０の数である。ａ＋ｄの下限は４０以上であることが好ましく、より好ましくは６０以上である。ａ＋ｄの下限は３００以下であることが好ましく、より好ましくは２００以下である。なお、ａおよびｄのそれぞれの数は、ａ＋ｄが上記の範囲内である限り特に限定されず、０より大きい数でもよく、１以上でもよく、１０以上でもよく、２０以上でもよい。 The sum of the average addition mole number of EO represented by a + d is a number of 20 to 450. The lower limit of a + d is preferably 40 or more, more preferably 60 or more. The lower limit of a + d is preferably 300 or less, more preferably 200 or less. The number of each of a and d is not particularly limited as long as a + d is in the above range, and may be a number larger than 0, 1 or more, 10 or more, or 20 or more.
ｂ＋ｃで表されるＰＯの平均付加モル数の合計は、１〜１４０の数である。ｂ＋ｃの下限は２以上であることが好ましく、より好ましくは４以上であり、更に好ましくは８以上であり、１０以上でもよい。ｂ＋ｃの上限は１００以下であることが好ましく、より好ましくは７０以下であり、更に好ましくは５０以下であり、４０以下でもよい。なお、ｂおよびｃのそれぞれの数は、ｂ＋ｃが上記の範囲内である限り特に限定されず、０より大きい数でもよく、１以上でもよく、２以上でもよく、４以上でもよい。 The sum of the average addition mole number of PO represented by b + c is a number of 1 to 140. The lower limit of b + c is preferably 2 or more, more preferably 4 or more, and still more preferably 8 or more, and may be 10 or more. The upper limit of b + c is preferably 100 or less, more preferably 70 or less, still more preferably 50 or less, and 40 or less. The number of b and c is not particularly limited as long as b + c is in the above range, and may be a number greater than 0, 1 or more, 2 or more, or 4 or more.
Ｘは、炭素数２〜１０のアルキレン基（即ち、アルカンジイル基）であり、直鎖でも分岐鎖を持つものでもよい。アルキレン基の炭素数は２〜５であることが好ましく、より好ましくは３又は４である。Ｘの具体例としては、エチレン基、プロピレン基、トリメチレン基、ブチレン基、イソブチレン基、テトラメチレン基、ペンタメチレン基、が挙げられる。 X is a C2-C10 alkylene group (namely, alkanediyl group), which may be linear or branched. The carbon number of the alkylene group is preferably 2 to 5, and more preferably 3 or 4. Specific examples of X include ethylene group, propylene group, trimethylene group, butylene group, isobutylene group, tetramethylene group and pentamethylene group.
本実施形態で用いるポリオキシアルキレンジオールは、オキシエチレン基を８０〜９５質量％含有するものである。このようにオキシエチレン基の含有量が高いポリオキシアルキレンジオールを用いることにより、加硫成形後の洗浄性を向上することができる。また、この含有量が８０〜９５質量％であることにより、離型剤が付着したゴムホースに対して作業時にある程度の応力が加わった場合でも、クラックの発生を抑制することができる。オキシエチレン基の含有量は８０〜９０質量％であることが好ましく、クラックの発生をより効果的に抑制することができる。 The polyoxyalkylene diol used in the present embodiment contains 80 to 95% by mass of an oxyethylene group. By using a polyoxyalkylene diol having a high content of oxyethylene groups as described above, the washability after vulcanization molding can be improved. In addition, when the content is 80 to 95% by mass, the occurrence of cracks can be suppressed even when a certain amount of stress is applied to the rubber hose to which the release agent is attached at the time of operation. The content of the oxyethylene group is preferably 80 to 90% by mass, and the generation of cracks can be suppressed more effectively.
本実施形態で用いるポリオキシアルキレンジオールは、数平均分子量（Ｍｎ）が２０００〜２００００であることが好ましい。このような数平均分子量のものを用いることにより、離型剤の粘度がより低くなり、作業性を向上することができる。ポリオキシアルキレンジオールの数平均分子量は、３０００〜１００００であることがより好ましい。 The polyoxyalkylene diol used in the present embodiment preferably has a number average molecular weight (Mn) of 2,000 to 20,000. By using the thing of such a number average molecular weight, the viscosity of a mold release agent becomes lower, and workability can be improved. The number average molecular weight of the polyoxyalkylene diol is more preferably 3000 to 10000.
該ポリオキシアルキレンジオールの製造方法は特に限定されず、公知のポリオキシアルキレンジオールの合成方法を利用して製造することができる。例えば、アルキレンオキシド付加重合により製造する場合、炭素数２〜１０のアルカンジオールに、アルカリ触媒または酸触媒を加えて８０〜１５０℃でプロピレンオキサイドを反応させ、続いて、８０〜１５０℃でエチレンオキサイドを反応させることにより得られる。この場合、式（１）中のＸは、出発原料であるアルカンジオールの残基である。なお、出発原料がプロピレングリコールである場合、Ｘ−Ｏは、その両側に付加するＰＯとの区別ができないが、そのような態様でもよい。 The method for producing the polyoxyalkylene diol is not particularly limited, and the polyoxyalkylene diol can be produced using a known synthetic method for polyoxyalkylene diol. For example, in the case of production by alkylene oxide addition polymerization, an alkali catalyst or an acid catalyst is added to an alkanediol having 2 to 10 carbon atoms, and propylene oxide is reacted at 80 to 150 ° C., followed by ethylene oxide at 80 to 150 ° C. Can be obtained by reacting In this case, X in the formula (1) is a residue of alkanediol which is a starting material. In addition, when a starting material is propylene glycol, although XO can not be distinguished from PO added to the both sides, such an aspect may be sufficient.
＜加硫ゴムホース成形用離型剤＞
本実施形態に係る加硫ゴムホース成形用離型剤は、上記ポリオキシアルキレンジオールのみで構成されてもよいが、水などの溶媒で希釈されたものであってもよい。例えば、上記ポリオキシアルキレンジオールの濃度が１０〜６０質量％（より好ましくは２０〜４０質量％）となるように水で希釈したものが挙げられる。
<Release agent for vulcanized rubber hose molding>
The release agent for molding a vulcanized rubber hose according to the present embodiment may be composed only of the above polyoxyalkylene diol, but may be diluted with a solvent such as water. For example, what diluted with water so that the density | concentration of the said polyoxyalkylene diol may be 10-60 mass% (preferably 20-40 mass%) is mentioned.
本実施形態に係る加硫ゴムホース成形用離型剤は、その効果を損なわない範囲で、ノニオン系又はアニオン系の界面活性剤やシリコーン類などの公知の離型剤成分を含有してもよい。 The vulcanized rubber hose molding release agent according to the present embodiment may contain a known release agent component such as a nonionic or anionic surfactant or silicones, as long as the effect is not impaired.
＜加硫ゴムホースの製造方法＞
本実施形態に係る加硫ゴムホースの製造方法では、マンドレルと未加硫のゴムホースの少なくとも一方に上記加硫ゴムホース成形用離型剤を塗布し、その後、前記未加硫ゴムホースにマンドレルを挿入しゴムホースを加硫成形する。
<Method of manufacturing vulcanized rubber hose>
In the method of manufacturing a vulcanized rubber hose according to the present embodiment, the above-mentioned release agent for molding a vulcanized rubber hose is applied to at least one of a mandrel and an unvulcanized rubber hose, and then the mandrel is inserted into the unvulcanized rubber hose Is vulcanized and molded.
マンドレルに離型剤を塗布する方法としては、例えば、未加硫ゴムホースを装着する前に、マンドレルにおける未加硫ゴムホースと接触する部分に、離型剤をハケやスプレーなどで塗布する方法が挙げられる。また、未加硫ゴムホースに離型剤を塗布する方法としては、例えば、未加硫ゴムホースの先端を離型剤に浸漬する方法が挙げられる。 As a method of applying the mold release agent to the mandrel, for example, a method of applying the mold release agent to the portion of the mandrel in contact with the unvulcanized rubber hose by brushing or spraying before mounting the unvulcanized rubber hose is mentioned. Be Moreover, as a method of apply | coating a mold release agent to an unvulcanized rubber hose, the method of immersing the front-end | tip of an unvulcanized rubber hose in a mold release agent is mentioned, for example.
ゴムホースの加硫成形は、常法に従い行うことができ、マンドレルに未加硫ゴムホースを装着した後、加熱すればよく、これにより、未加硫ゴムホースとマンドレルとの界面に離型剤を介在させた状態で加硫成形がなされる。その後、マンドレルからゴムホースを引き抜き、ゴムホースの表面に付着した離型剤を温水洗浄などで洗浄することにより、加硫ゴムホースが得られる。 Vulcanization molding of the rubber hose can be carried out according to a conventional method, and after mounting the unvulcanized rubber hose on the mandrel, it may be heated, thereby interposing a release agent at the interface between the unvulcanized rubber hose and the mandrel Vulcanization molding is performed in a state of Thereafter, the rubber hose is pulled out from the mandrel, and the release agent adhering to the surface of the rubber hose is washed with warm water or the like to obtain a vulcanized rubber hose.
加硫ゴムホースを構成する加硫ゴムの種類は、特に制限されるものではないが、具体例としては、アクリロニトリル−ブタジエン共重合ゴム（ＮＢＲ）、エチレン・プロピレン・ジエン共重合ゴム（ＥＰＤＭ）、ＮＢＲとポリ塩化ビニル（ＰＶＣ）とをブレンドしたゴム（ＮＢＲ／ＰＶＣ）、アクリルゴム（ＡＣＭ）、フッ素ゴム（ＦＫＭ）などが挙げられる。これらの中でも、ＮＢＲとＰＶＣとをブレンドしたゴムを使用したゴムホースに用いることが好ましい。 The type of vulcanized rubber constituting the vulcanized rubber hose is not particularly limited. Specific examples thereof include acrylonitrile-butadiene copolymer rubber (NBR), ethylene / propylene / diene copolymer rubber (EPDM), and NBR. And rubber blended with polyvinyl chloride (PVC) (NBR / PVC), acrylic rubber (ACM), fluororubber (FKM) and the like. Among these, it is preferable to use for the rubber hose using the rubber which blended NBR and PVC.
それら加硫ゴムは、例えば、次のように製造することができる。ポリマーに、加硫剤、加硫助剤、加工助剤、可塑剤、プロセスオイル、カーボンブラック、白色充填材、老化防止剤等を適宜に混合し、ロール、ニーダー、バンバリーミキサー等の混練機を用いて混練することにより、目的とする加硫ゴム組成物を調製する。 These vulcanized rubbers can be produced, for example, as follows. Polymers are appropriately mixed with vulcanizing agents, vulcanizing aids, processing aids, plasticizers, process oils, carbon black, white fillers, anti-aging agents, etc., and kneaders such as rolls, kneaders and Banbury mixers are used. The target vulcanized rubber composition is prepared by using and kneading.
以下、実施例により本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
数平均分子量、オキシエチレン基含有量、ａ＋ｄおよびｂ＋ｃの各測定方法は、以下の通りである。 Each measuring method of a number average molecular weight, oxyethylene group content, a + d and b + c is as follows.
（数平均分子量の測定方法）
数平均分子量は、ＧＰＣ法により求めた。ＧＰＣ装置及び分析条件は以下の通りであり、標準サンプルとして分子量３２７、２０００、８２５０、１９７００のポリエチレングリコールで校正したものを用いた。
(Method of measuring number average molecular weight)
The number average molecular weight was determined by GPC method. The GPC apparatus and analysis conditions were as follows, and those calibrated with polyethylene glycols of molecular weights 327, 2000, 8250, and 19700 were used as standard samples.
ＧＰＣ装置：システムコントローラー：ＳＣＬ−１０Ａ（島津製作所社製）
検出器：ＲＩＤ−１０Ａ（島津製作所社製）
カラム：Ｓｈｏｄｅｘ ＧＰＣ ＫＦ−Ｇ、ＫＦ−８０３、ＫＦ８０２．５、ＫＦ−８０２、ＫＦ−８０１を連結したもの（いずれも昭和電工社製）
溶離液：テトラヒドロフラン
サンプル注入：０．５重量％溶液、８０μＬ
流速：０．８ｍＬ／ｍｉｎ
温度：２５℃
GPC apparatus: System controller: SCL-10A (manufactured by Shimadzu Corporation)
Detector: RID-10A (manufactured by Shimadzu Corporation)
Column: A combination of Shodex GPC KF-G, KF-803, KF 802.5, KF-802 and KF-801 (all manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran Sample injection: 0.5 wt% solution, 80 μL
Flow rate: 0.8 mL / min
Temperature: 25 ° C
（オキシエチレン基含有量、ａ＋ｄおよびｂ＋ｃの測定方法）
1Ｈ−ＮＭＲ（溶媒：ＣＤＣｌ3）により算出した。
(Measurement method of oxyethylene group content, a + d and b + c)
1 H-NMR (solvent: CDCl 3) was calculated by.
（合成例１）
ステンレス製オートクレーブに、プロピレングリコール７６ｇ（１モル）、水酸化カリウム３ｇを仕込み、反応器内を窒素置換した。１００℃に昇温し、プロピレンオキシド７５４ｇ（１３モル）を内圧０．３ＭＰａ以下に保ちながら導入した。プロピレンオキシドの導入終了後、１００℃で２時間保持し、圧力低下が見られなくなるまで反応させた。続いて、エチレンオキシド３２１２ｇ（７３モル）を内圧０．３ＭＰａ以下に保ちながら導入した。エチレンオキシドの導入終了後、１００℃で２時間保持し、圧力低下が見られなくなるまで反応させることにより、一般式（１）で表されるポリオキシアルキレンジオール（数平均分子量Ｍｎ＝４０００、オキシエチレン基含有量＝８０質量％、ａ＋ｄ＝７３、ｂ＋ｃ＝１３）を得た。
Synthesis Example 1
Into a stainless steel autoclave, 76 g (1 mol) of propylene glycol and 3 g of potassium hydroxide were charged, and the inside of the reactor was purged with nitrogen. The temperature was raised to 100 ° C., and 754 g (13 moles) of propylene oxide was introduced while maintaining the internal pressure at 0.3 MPa or less. After completing the introduction of propylene oxide, it was kept at 100 ° C. for 2 hours, and was reacted until no pressure drop was observed. Subsequently, 3212 g (73 moles) of ethylene oxide was introduced while maintaining the internal pressure at 0.3 MPa or less. After completion of the introduction of ethylene oxide, the polyoxyalkylene diol represented by the general formula (1) (number average molecular weight Mn = 4000, oxyethylene group) is maintained by maintaining at 100 ° C. for 2 hours until no pressure drop is observed. Content = 80 mass%, a + d = 73, b + c = 13) were obtained.
（合成例２）
プロピレンオキシドの使用量を１２７６ｇ（２２モル）に、エチレンオキシド５２３６ｇ（１１９モル）に変更した以外は合成例１と同様の操作を行い、一般式（１）で表されるポリオキシアルキレンジオール（数平均分子量Ｍｎ＝６５００、オキシエチレン基含有量＝８０質量％、ａ＋ｄ＝１１９、ｂ＋ｃ＝２２）を得た。
(Composition example 2)
The same operation as in Synthesis Example 1 is carried out except that the amount of propylene oxide used is changed to 1276 g (22 mol) and ethylene oxide 5236 g (119 mol), and the polyoxyalkylene diol represented by the general formula (1) (number average Molecular weight Mn = 6500, oxyethylene group content = 80% by mass, a + d = 119, b + c = 22) were obtained.
（合成例３）
プロピレンオキシドの使用量を１９７２ｇ（３４モル）に、エチレンオキシド８００８ｇ（１８２モル）に変更した以外は合成例１と同様の操作を行い、一般式（１）で表されるポリオキシアルキレンジオール（数平均分子量Ｍｎ＝１００００、オキシエチレン基含有量＝８０質量％、ａ＋ｄ＝１８２、ｂ＋ｃ＝３４）を得た。
(Composition example 3)
The same operation as in Synthesis Example 1 is carried out except that the amount of propylene oxide used is changed to 1972 g (34 moles) and ethylene oxide 8008 g (182 moles), and the polyoxyalkylene diol represented by the general formula (1) (number average Molecular weight Mn = 10000, oxyethylene group content = 80% by mass, a + d = 182, b + c = 34).
（合成例４）
プロピレンオキシドの使用量を９２８ｇ（１６モル）に、エチレンオキシド５５４ｇ（１２６モル）に変更した以外は合成例１と同様の操作を行い、一般式（１）で表されるポリオキシアルキレンジオール（数平均分子量Ｍｎ＝６５００、オキシエチレン基含有量＝８５質量％、ａ＋ｃ＝１２６、ｂ＝１６）を得た。
(Composition example 4)
The same operation as in Synthesis Example 1 is carried out except that the amount of propylene oxide used is changed to 928 g (16 mol) and ethylene oxide 554 g (126 mol), and the polyoxyalkylene diol represented by the general formula (1) (number average Molecular weight Mn = 6500, oxyethylene group content = 85% by mass, a + c = 126, b = 16) were obtained.
（合成例５）
プロピレンオキシドの使用量を６３８ｇ（１１モル）に、エチレンオキシド５８５２ｇ（１３３モル）に変更した以外は合成例１と同様の操作を行い、一般式（１）で表されるポリオキシアルキレンジオール（数平均分子量Ｍｎ＝６５００、オキシエチレン基含有量＝９０質量％、ａ＋ｄ＝１３３、ｂ＋ｃ＝１１）を得た。
(Composition example 5)
The same operation as in Synthesis Example 1 is carried out except that the amount of propylene oxide used is changed to 638 g (11 mol) and ethylene oxide 5852 g (133 mol), and the polyoxyalkylene diol represented by the general formula (1) (number average Molecular weight Mn = 6500, oxyethylene group content = 90% by mass, a + d = 133, b + c = 11) were obtained.
（合成例６）
プロピレンオキシドの使用量を３１９０ｇ（５５モル）に、エチレンオキシド３２５６ｇ（７４モル）に変更した以外は合成例１と同様の操作を行い、一般式（１）で表されるポリオキシアルキレンジオール（数平均分子量Ｍｎ＝６５００、オキシエチレン基含有量＝５０質量％）を得た。
Synthesis Example 6
The same operation as in Synthesis Example 1 is carried out except that the amount of propylene oxide used is changed to 3190 g (55 mol) and ethylene oxide 3256 g (74 mol), and the polyoxyalkylene diol represented by the general formula (1) (number average Molecular weight Mn = 6500, oxyethylene group content = 50% by mass) was obtained.
（合成例７）
プロピレンオキシドの使用量を４５２４ｇ（７８モル）に、エチレンオキシド１９８０ｇ（４５モル）に変更した以外は合成例１と同様の操作を行い、一般式（１）で表されるポリオキシアルキレンジオール（数平均分子量Ｍｎ＝６５００、オキシエチレン基含有量＝３０質量％）を得た。
Synthesis Example 7
The same operation as in Synthesis Example 1 is carried out except that the amount of propylene oxide used is changed to 4524 g (78 mol) and ethylene oxide 1980 g (45 mol), and the polyoxyalkylene diol represented by the general formula (1) (number average Molecular weight Mn = 6500, oxyethylene group content = 30% by mass) was obtained.
（合成例８）
ステンレス製オートクレーブに、１−ブタノール７４ｇ（１モル）、水酸化カリウム３ｇを仕込み、反応器内を窒素置換した。１００℃に昇温し、エチレンオキシド２５９６ｇ（５９モル）を内圧０．３ＭＰａ以下に保ちながら導入した。エチレンオキシドの導入終了後、１００℃で２時間保持し、圧力低下が見られなくなるまで反応させた。続いて、プロピレンオキシド１２７６ｇ（２２モル）を内圧０．３ＭＰａ以下に保ちながら導入した。プロピレンオキシドの導入終了後、１００℃で２時間保持し、圧力低下が見られなくなるまで反応させた。さらに、エチレンオキシド２５９６ｇ（５９モル）を内圧０．３ＭＰａ以下に保ちながら導入した。エチレンオキシドの導入終了後、１００℃で２時間保持し、圧力低下が見られなくなるまで反応させることにより、ポリオキシアルキレンモノブチルエーテル（数平均分子量Ｍｎ＝６５００、オキシエチレン基含有量＝８０質量％）を得た。
Synthesis Example 8
In a stainless steel autoclave, 74 g (1 mol) of 1-butanol and 3 g of potassium hydroxide were charged, and the inside of the reactor was purged with nitrogen. The temperature was raised to 100 ° C., and 2596 g (59 moles) of ethylene oxide was introduced while maintaining the internal pressure at 0.3 MPa or less. After completion of the introduction of ethylene oxide, the reaction solution was maintained at 100 ° C. for 2 hours, until no pressure drop was observed. Subsequently, 1276 g (22 moles) of propylene oxide was introduced while maintaining the internal pressure at 0.3 MPa or less. After completing the introduction of propylene oxide, it was kept at 100 ° C. for 2 hours, and was reacted until no pressure drop was observed. Furthermore, 2596 g (59 moles) of ethylene oxide was introduced while maintaining the internal pressure at 0.3 MPa or less. After completion of the introduction of ethylene oxide, the reaction mixture is maintained at 100 ° C. for 2 hours and reacted until no pressure drop is observed, thereby obtaining polyoxyalkylene monobutyl ether (number average molecular weight Mn = 6500, oxyethylene group content = 80 mass%). Obtained.
（ＮＢＲ／ＰＶＣ）
ＰＶＣポリブレンドのアクリロニトリルブタジエンポリマー（ＪＳＲ製：ＪＳＲ ＮＶ７２）１００質量部に対し、ステアリン酸１質量部、亜鉛化５質量部、ＦＥＦカーボンブラック５５質量部、可塑剤ＤＯＰ１５質量部、老化防止剤１質量部、硫黄１．５質量部、加硫促進剤ＴＥＴ１質量部、加硫促進剤ＣＺ１質量部を配合してなる組成物を用いた。
(NBR / PVC)
1 part by mass of stearic acid, 5 parts by mass of zincation, 55 parts by mass of FEF carbon black, 15 parts by mass of plasticizer DOP, 1 part by mass of an antioxidant butadiene polymer (JSR product: JSR NV72) of PVC polyblend A composition obtained by blending 1 part by mass, 1.5 parts by mass of sulfur, 1 part by mass of the vulcanization accelerator TET, and 1 part by mass of the vulcanization accelerator CZ was used.
（ＮＢＲ）
アクリロニトリルブタジエンポリマー１００質量部（ＪＳＲ社製：ＪＳＲ ２３０Ｓ）に対し、ステアリン酸１質量部、亜鉛化５質量部、ＦＥＦカーボンブラック５５質量部、可塑剤ＤＯＰ１５質量部、老化防止剤１質量部、硫黄１．５質量部、加硫促進剤ＴＥＴ１質量部、加硫促進剤ＣＺ１質量部を配合してなる組成物を用いた。
(NBR)
1 part by mass of stearic acid, 5 parts by mass of zincation, 55 parts by mass of FEF carbon black, 15 parts by mass of plasticizer DOP, 1 part by mass of an antioxidant, sulfur relative to 100 parts by mass of acrylonitrile butadiene polymer (manufactured by JSR: JSR 230S) A composition obtained by blending 1.5 parts by mass, 1 part by mass of the vulcanization accelerator TET, and 1 part by mass of the vulcanization accelerator CZ was used.
（ＥＰＤＭ）
エチレンプロピレンポリマー１００質量部（住友化学工業社製：エスプレン５３２）に対し、ステアリン酸１質量部、亜鉛化５質量部、ＦＥＦカーボンブラック１１５質量部、プロセスオイル６５質量部、硫黄１質量部、加硫促進剤ＴＥＴ１質量部、加硫促進剤ＣＺ１質量部を配合してなる組成物を用いた。
(EPDM)
1 part by mass of stearic acid, 5 parts by mass of zincation, 115 parts by mass of FEF carbon black, 65 parts by mass of process oil, 1 part by mass of sulfur, based on 100 parts by mass of ethylene propylene polymer (manufactured by Sumitomo Chemical Co., Ltd .: Esprene 532) A composition obtained by blending 1 part by mass of the vulcanization accelerator TET and 1 part by mass of the vulcanization accelerator CZ was used.
（実施例１〜７、比較例１〜５）
下記表１に記載の割合（質量比）で各原料を混合することにより、離型剤を得た。この離型剤を用いて、下記の評価を行った。なお、表中の「合成例１〜８」は上記の各合成例で得られたポリオキシアルキレンジオールまたはポリオキシアルキレンモノブチルエーテルであり、「ＰＥＧ」はポリエチレングリコール（数平均分子量Ｍｎ＝６５００）であり、「シリコーン」はジメチルポリシロキサン（商品名：ＫＦ−９６−２０ＣＳ、信越化学工業社製）である。
(Examples 1 to 7, Comparative Examples 1 to 5)
The release agent was obtained by mixing each raw material in the ratio (mass ratio) of following Table 1. The following evaluation was performed using this mold release agent. In the table, “Synthesis Examples 1 to 8” are polyoxyalkylene diol or polyoxyalkylene monobutyl ether obtained in each of the above synthesis examples, and “PEG” is polyethylene glycol (number average molecular weight Mn = 6500) Yes, “silicone” is dimethylpolysiloxane (trade name: KF-96-20CS, manufactured by Shin-Etsu Chemical Co., Ltd.).
（耐クラック性）
ＮＢＲ／ＰＶＣ製、ＮＢＲ製、ＥＰＤＭ製の未加硫ゴムホース(φ50mm,厚み2mm形状)を1cm幅で輪切りにしたものを切断して作製した短冊状の未加硫ゴム片を、ホース長手方向に伸張率が５０％となるように左右に引き伸ばして固定した。これに離型剤が伸長部全面に接触する量(0.15ml/cm2以上)を塗布した後、７０℃のオーブンに１時間静置し、その後、未加硫ゴムホース表面のクラック有無を目視で確認した。このとき、クラックの発生が認められないものを○、クラックの発生が認められるものを×とした。なお、クラックの発生が認められた離型剤については、挿入性、離型性および洗浄性の評価を実施しなかった（但し、比較例５は除く）。
(Crack resistance)
A strip-like unvulcanized rubber piece prepared by cutting a 1-cm-wide ring of an unvulcanized rubber hose (φ 50 mm, thickness 2 mm shape) made of NBR / PVC, NBR, and EPDM is cut in the longitudinal direction of the hose It was stretched and fixed to the left and right so that the expansion rate was 50%. After applying an amount (0.15 ml / cm 2 or more) with which the mold release agent contacts the entire surface of the extended portion, the sheet is allowed to stand in an oven at 70 ° C. for 1 hour. confirmed. At this time, those with no occurrence of cracks were evaluated as ○, and those with occurrence of cracks were ×. In addition, about the mold release agent in which generation | occurrence | production of the crack was recognized, evaluation of insertion property, mold release property, and washability was not implemented (however, except for Comparative Example 5).
（挿入性および離型性）
離型剤に浸漬したＮＢＲ／ＰＶＣ製、ＮＢＲ製、ＥＰＤＭ製の未加硫ゴムホースを、離型剤を塗布した成形ホース用マンドレルに挿入した。このときの作業性を挿入性とし、下記の基準で評価した。続いて、１５０℃で１時間加硫処理を行い、マンドレルから加硫ゴムホースを引き抜いた。このときの作業性を離型性とし、挿入性と同様に下記の基準で評価した。結果を表１に示す。
(Insertability and releasability)
A non-vulcanized rubber hose made of NBR / PVC, NBR, or EPDM dipped in a release agent was inserted into a mold hose mandrel coated with the release agent. The workability at this time was considered as insertability, and was evaluated according to the following criteria. Subsequently, a vulcanizing treatment was performed at 150 ° C. for 1 hour, and a vulcanized rubber hose was pulled out of the mandrel. The workability at this time was defined as releasability and was evaluated based on the following criteria in the same manner as the insertability. The results are shown in Table 1.
○：ジメチルポリシロキサンを用いた場合と作業性が同程度である
×：ジメチルポリシロキサンを用いた場合よりも作業性が悪い
○: Workability is comparable to when dimethylpolysiloxane is used ×: Workability is worse than when dimethylpolysiloxane is used
（洗浄性）
上記挿入性および離型性の評価で得られた加硫ゴムホースを、９０℃の水に１分間および３分間浸漬して取り出した。加硫ゴムホースの表面を目視で観察し、下記の基準で評価した。結果を表１に示す。
(Cleanability)
The vulcanized rubber hose obtained in the above evaluation of the insertability and releasability was taken out by being immersed in water at 90 ° C. for 1 minute and 3 minutes. The surface of the vulcanized rubber hose was visually observed and evaluated according to the following criteria. The results are shown in Table 1.
◎：１分間浸漬後に加硫ゴムホースの表面に離型剤が残っていない
○：３分間浸漬後に加硫ゴムホースの表面に離型剤が残っていない
×：３分間浸漬後も加硫ゴムホースの表面に離型剤が残っている
: 1: No release agent remains on the surface of the vulcanized rubber hose after immersion for 1 minute ○: No release agent remains on the surface of the vulcanized rubber hose after immersion for 3 minutes ×: The surface of the vulcanized rubber hose after immersion for 3 minutes Mold release agent remains
表１に示すように、離型剤としてジメチルポリシロキサンを用いた比較例５では、耐クラック性と洗浄性に劣っていた。離型剤としてポリエチレングリコール（オキシエチレン基の含有量＝１００％）を用いた比較例４では、洗浄性には優れるものの、加硫成形時におけるマンドレルの挿入性および離型性に劣っていた。 As shown in Table 1, in Comparative Example 5 in which dimethylpolysiloxane was used as the release agent, the crack resistance and the washability were inferior. In Comparative Example 4 in which polyethylene glycol (content of oxyethylene group = 100%) was used as a release agent, although the cleaning property was excellent, the insertability and releasability of the mandrel during vulcanization molding were inferior.
式（１）で表されるポリオキシアルキレンジオールであるもののオキシエチレン基の含有量が５０質量％や３０質量％と低いものを離型剤として用いた比較例１および２では、応力を加えなければクラックは発生しなかったものの、比較的低い応力を加えた場合でもクラックが発生しており、耐クラック性に劣っていた。また、比較例３では、ポリオキシプロピレン基の両側にポリオキシエチレン基が付加した構造を持ち、かつオキシエチレン基の含有量が８０質量％と高いものであるが、モノブチルエーテルであるため、耐クラック性の改善効果は得られなかった。 In Comparative Examples 1 and 2 in which the polyoxyalkylene diol represented by the formula (1) and having a low content of 50% by mass or 30% by mass of the oxyethylene group is used as a release agent, no stress should be applied. For example, although the crack did not occur, the crack occurred even when a relatively low stress was applied, and the crack resistance was inferior. Further, Comparative Example 3 has a structure in which a polyoxyethylene group is added to both sides of a polyoxypropylene group, and the content of an oxyethylene group is as high as 80% by mass, but since it is monobutyl ether, The improvement effect of the crack property was not obtained.
これに対し、式（１）で表されかつ所定のオキシエチレン基含有量を持つポリオキシアルキレンジオールを離型剤として用いた実施例１〜５であると、ジメチルポリシロキサンを用いた比較例５に比べて、加硫成形時におけるマンドレルの挿入性および離型性を同程度に維持しつつ、洗浄性が顕著に改善されており、かつ耐クラック性が顕著に改善されていた。また、比較例１〜３に対しても耐クラック性が顕著に改善されていた。すなわち、作業時に想定される応力を十分に超える、伸張率５０％という高い応力が加わった場合でも、クラックの発生を抑制することができた。 On the other hand, Comparative Examples 5 using dimethylpolysiloxane as Examples 1 to 5 in which a polyoxyalkylene diol represented by the formula (1) and having a predetermined oxyethylene group content is used as a release agent Compared with the above, while maintaining the insertability and releasability of the mandrel at the time of vulcanization molding to the same extent, the washability was significantly improved and the crack resistance was significantly improved. Moreover, the crack resistance was significantly improved also to Comparative Examples 1 to 3. That is, even in the case where a high stress of 50% elongation rate was applied which sufficiently exceeds the stress assumed at the time of work, the generation of the crack could be suppressed.
使用するゴムを変更した場合でも、式（１）で表されかつ所定のオキシエチレン基含有量を持つポリオキシアルキレンジオールを離型剤として用いた実施例６および７であると、耐クラック性に優れるとともに、加硫成形時におけるマンドレルの挿入性および離型性に優れ、また加硫成形後の洗浄性にも優れていた。 Even when the rubber to be used is changed, in Examples 6 and 7 in which a polyoxyalkylene diol represented by the formula (1) and having a predetermined content of oxyethylene group is used as a releasing agent, crack resistance is obtained. While being excellent, it was excellent in the insertion property and mold release property of the mandrel at the time of vulcanization molding, and also excellent in the washability after vulcanization molding.
Claims (3)
ＨＯ−（ＥＯ）a−（ＰＯ）b−Ｘ−Ｏ−（ＰＯ）c−（ＥＯ）d−Ｈ （１）
ただし、式中、ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基を表し、ａ、ｂ、ｃおよびｄはそれぞれ平均付加モル数であって、ａ＋ｄが２０〜４５０の数、ｂ＋ｃが１〜１４０の数であり、Ｘは炭素数３のアルキレン基である。 A release agent for molding a vulcanized rubber hose, which is a polyoxyalkylene diol represented by the following general formula (1) and containing 80 to 95% by mass of an oxyethylene group.
HO- (EO) a- (PO) b- X-O- (PO) c- (EO) d- H (1)
However, in the formula, EO represents an oxyethylene group, PO represents an oxypropylene group, a, b, c and d represent the average addition mole number, and a + d is the number of 20 to 450 and b + c is 1 to 140 And X is an alkylene group having 3 carbon atoms.
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