JP6459564B2 - Synthetic isoprene polymer latex for dip molding, dip molding composition and dip molded body - Google Patents
Synthetic isoprene polymer latex for dip molding, dip molding composition and dip molded body Download PDFInfo
- Publication number
- JP6459564B2 JP6459564B2 JP2015015130A JP2015015130A JP6459564B2 JP 6459564 B2 JP6459564 B2 JP 6459564B2 JP 2015015130 A JP2015015130 A JP 2015015130A JP 2015015130 A JP2015015130 A JP 2015015130A JP 6459564 B2 JP6459564 B2 JP 6459564B2
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- JP
- Japan
- Prior art keywords
- dip
- synthetic isoprene
- isoprene polymer
- dip molding
- polymer latex
- 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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- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 title claims description 205
- 229920000642 polymer Polymers 0.000 title claims description 96
- 238000000465 moulding Methods 0.000 title claims description 71
- 229920000126 latex Polymers 0.000 title claims description 58
- 239000004816 latex Substances 0.000 title claims description 58
- 239000000203 mixture Substances 0.000 title claims description 49
- 229930004725 sesquiterpene Natural products 0.000 claims description 35
- 150000004354 sesquiterpene derivatives Chemical class 0.000 claims description 35
- 238000004073 vulcanization Methods 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 19
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 19
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 12
- 238000004945 emulsification Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 description 33
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- -1 bisabolen Chemical compound 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
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- 239000007787 solid Substances 0.000 description 11
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 6
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- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- CXENHBSYCFFKJS-UHFFFAOYSA-N (3E,6E)-3,7,11-Trimethyl-1,3,6,10-dodecatetraene Natural products CC(C)=CCCC(C)=CCC=C(C)C=C CXENHBSYCFFKJS-UHFFFAOYSA-N 0.000 description 2
- JSNRRGGBADWTMC-QINSGFPZSA-N (E)-beta-Farnesene Natural products CC(C)=CCC\C(C)=C/CCC(=C)C=C JSNRRGGBADWTMC-QINSGFPZSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 2
- GIUBHMDTOCBOPA-UHFFFAOYSA-N 3h-1,3-benzothiazole-2-thione;zinc Chemical compound [Zn].C1=CC=C2SC(S)=NC2=C1 GIUBHMDTOCBOPA-UHFFFAOYSA-N 0.000 description 2
- NVEQFIOZRFFVFW-UHFFFAOYSA-N 9-epi-beta-caryophyllene oxide Natural products C=C1CCC2OC2(C)CCC2C(C)(C)CC21 NVEQFIOZRFFVFW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PDSNLYSELAIEBU-UHFFFAOYSA-N Longifolene Chemical compound C1CCC(C)(C)C2C3CCC2C1(C)C3=C PDSNLYSELAIEBU-UHFFFAOYSA-N 0.000 description 2
- ZPUKHRHPJKNORC-UHFFFAOYSA-N Longifolene Natural products CC1(C)CCCC2(C)C3CCC1(C3)C2=C ZPUKHRHPJKNORC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
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- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 2
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- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- FAMPSKZZVDUYOS-UHFFFAOYSA-N alpha-Caryophyllene Natural products CC1=CCC(C)(C)C=CCC(C)=CCC1 FAMPSKZZVDUYOS-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 2
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- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Moulding By Coating Moulds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ディップ成形用合成イソプレン重合体ラテックス、ディップ成形用組成物およびディップ成形体に関する。さらに詳しくは、所定の条件において発生するセスキテルペン量が所定量以下である界面活性剤を使用したディップ成形用合成イソプレン重合体ラテックス、このラテックスを含むディップ成形用組成物、およびこの組成物をディップ成形して得られるディップ成形体に関する。 The present invention relates to a synthetic isoprene polymer latex for dip molding, a dip molding composition, and a dip molded body. More specifically, a synthetic isoprene polymer latex for dip molding using a surfactant having an amount of sesquiterpene generated under a predetermined condition below a predetermined amount, a dip molding composition containing the latex, and the dip molding composition. The present invention relates to a dip-molded body obtained by molding.
従来、天然ゴムのラテックスを含有するディップ成形用組成物をディップ成形して、乳首、風船、手袋、バルーン、サック等の人体と接触して使用されるディップ成形体が得られることが知られている。しかしながら、天然ゴムのラテックスは、人体にアレルギー症状を引き起こすような蛋白質を含有するため、生体粘膜又は臓器と直接接触するディップ成形体としては問題がある場合があった。そのため、天然ゴムのラテックスの代わりに合成イソプレン重合体のラテックスを用いる検討がされてきている。 Conventionally, it is known that a dip molding composition containing a latex of natural rubber is dip-molded to obtain a dip-molded body used in contact with a human body such as a nipple, a balloon, a glove, a balloon, and a sack. Yes. However, since natural rubber latex contains a protein that causes allergic symptoms in the human body, there are cases in which there is a problem as a dip-molded product that is in direct contact with a living mucous membrane or an organ. Therefore, studies have been made to use synthetic isoprene polymer latex instead of natural rubber latex.
合成イソプレン重合体ラテックスは、合成イソプレン重合体を溶剤に溶解し、それを界面活性剤と一緒に乳化し、更に脱溶媒する方法で製造されることが知られている。この方法において、界面活性剤としてロジン酸塩が一般的に使用されるが、精製されていない天然由来(ガムロジン)のロジン酸の塩を使用している場合は、ディップ後の加硫工程においてセスキテルペンが揮発していた。 It is known that a synthetic isoprene polymer latex is produced by a method in which a synthetic isoprene polymer is dissolved in a solvent, emulsified with a surfactant, and further desolvated. In this method, rosinate is generally used as a surfactant. However, when a non-purified salt of rosin acid of natural origin (gum rosin) is used, sesquiskies are used in the vulcanization step after dipping. The terpene was volatilized.
セスキテルペンは、3つのイソプレンから構成されC15H24の分子式を持つものである。セスキテルペンは非常に種類が多く3000以上存在すると言われており、ファルネセン、ロンギホレン、ビサボレン、カリオフィレン、セリネンなどは精油として使用されている場合がある。このように、リラックス効果のある物質も含まれているが、加硫工程において、加硫剤である硫黄由来の臭気にこのセスキテルペン系の臭気が混合した臭気は不快であり異臭を訴える作業員が増える傾向があった。このため、排気設備の拡充や強化が必要になる等、設備投資が大きくなる場合があった。 A sesquiterpene is composed of three isoprenes and has a molecular formula of C 15 H 24 . It is said that sesquiterpenes are very various and exist in 3000 or more, and farnesene, longifolene, bisabolen, caryophyllene, serinen, etc. may be used as essential oils. In this way, substances that have a relaxing effect are also included, but in the vulcanization process, the odor resulting from mixing this sesquiterpene odor with the sulfur-derived odor, which is the vulcanizing agent, is unpleasant and complains of a strange odor. There was a tendency to increase. For this reason, there has been a case where capital investment becomes large, for example, expansion and strengthening of exhaust facilities are required.
例えば特許文献1および特許文献2には、合成イソプレン重合体ラテックスの製造に用いる界面活性剤として、ロジン酸塩を用いることが開示されている。しかし、ロジン酸塩を得るためのロジンについては、特に説明も限定もなく、加硫時のセスキテルペンの発生については何ら言及されていなかった。 For example, Patent Document 1 and Patent Document 2 disclose the use of a rosinate as a surfactant used in the production of a synthetic isoprene polymer latex. However, the rosin for obtaining the rosinate is not particularly explained or limited, and no mention is made of generation of sesquiterpene during vulcanization.
本発明は、加硫時における不快な臭いの発生を抑制することができるディップ成形用合成イソプレン重合体ラテックス、このラテックスを含むディップ成形用組成物、およびこの組成物をディップ成形して得られるディップ成形体を提供することを目的とする。 The present invention relates to a synthetic isoprene polymer latex for dip molding capable of suppressing generation of an unpleasant odor during vulcanization, a dip molding composition containing the latex, and a dip obtained by dip molding the composition. It aims at providing a molded object.
本発明者らは、上記課題を解決すべく鋭意研究した結果、界面活性剤として特定のロジン系物質を使用することにより製造したディップ成形用合成イソプレン重合体ラテックスが、上記目的を達成できることを見出し、本発明を完成させるに至った。 As a result of diligent research to solve the above problems, the present inventors have found that a synthetic isoprene polymer latex for dip molding produced by using a specific rosin-based substance as a surfactant can achieve the above object. The present invention has been completed.
即ち、本発明によれば、
(1) 160℃加熱時に発生するセスキテルペン量が500ppm以下のロジン系物質の存在下で乳化することにより得られるディップ成形用合成イソプレン重合体ラテックス、
(2) (1)に記載のディップ成形用合成イソプレン重合体ラテックス、硫黄系加硫剤、および加硫促進剤を含有してなるディップ成形用組成物、
(3) (2)に記載のディップ成形用組成物をディップ成形してなるディップ成形体
が提供される。
That is, according to the present invention,
(1) A synthetic isoprene polymer latex for dip molding obtained by emulsifying in the presence of a rosin-based substance having a sesquiterpene amount of 500 ppm or less generated when heated at 160 ° C.,
(2) A composition for dip molding comprising the synthetic isoprene polymer latex for dip molding according to (1), a sulfur vulcanizing agent, and a vulcanization accelerator,
(3) A dip-molded product obtained by dip-molding the dip-molding composition described in (2) is provided.
本発明のディップ成形用合成イソプレン重合体ラテックスによれば、加硫時における不快な臭いの発生を抑制することができる。また、本発明によればこのラテックスを含むディップ成形用組成物、およびこの組成物をディップ成形して得られるディップ成形体が提供される。 According to the synthetic isoprene polymer latex for dip molding of the present invention, generation of unpleasant odor during vulcanization can be suppressed. In addition, according to the present invention, there are provided a dip-molding composition containing this latex, and a dip-molded body obtained by dip-molding this composition.
以下、本発明のディップ成形用合成イソプレン重合体ラテックスについて説明する。本発明のディップ成形用合成イソプレン重合体ラテックスは、160℃加熱時に発生するセスキテルペン量が500ppm以下のロジン系物質の存在下で乳化することにより得られる。ロジン系物質中のセキステルペン量は好ましくは400ppm以下である。
前記ロジン系物質中のセキステルペン量は、ロジン系物質を160℃で加熱することにより発生した成分を吸着管(TenaxGR+Carboxen569)へ捕集し、特定条件で測定した場合の発生量であり、詳細は後述の実施例における方法により測定された量である。
Hereinafter, the synthetic isoprene polymer latex for dip molding of the present invention will be described. The synthetic isoprene polymer latex for dip molding of the present invention can be obtained by emulsification in the presence of a rosin-based substance whose amount of sesquiterpene generated when heated at 160 ° C. is 500 ppm or less. The amount of sexterpene in the rosin-based material is preferably 400 ppm or less.
The amount of sexeterpene in the rosin-based material is the amount generated when the components generated by heating the rosin-based material at 160 ° C. are collected in an adsorption tube (TenaxGR + Carboxen569) and measured under specific conditions. It is the quantity measured by the method in the examples.
(ディップ成形用合成イソプレン重合体ラテックス)
本発明のディップ成形用合成イソプレン重合体ラテックスは、イソプレンを重合して得られる合成イソプレン重合体のラテックスである。
(Synthetic isoprene polymer latex for dip molding)
The synthetic isoprene polymer latex for dip molding of the present invention is a latex of a synthetic isoprene polymer obtained by polymerizing isoprene.
(合成イソプレン重合体)
合成イソプレン重合体は、イソプレンと共重合可能な他のエチレン性不飽和単量体を共重合したものであってもよい。合成イソプレン重合体のイソプレン単位の含有量は、柔軟で、引張強さに優れるディップ成形体が得られ易いことから、全単量体単位に対して、好ましくは70重量%以上、より好ましくは90重量%以上、さらに好ましくは95重量%以上、特に好ましくは100重量%(イソプレンの単独重合体)である。
(Synthetic isoprene polymer)
The synthetic isoprene polymer may be a copolymer of another ethylenically unsaturated monomer copolymerizable with isoprene. The content of isoprene units in the synthetic isoprene polymer is flexible, and it is easy to obtain a dip-molded product excellent in tensile strength. Therefore, it is preferably 70% by weight or more, more preferably 90%, based on all monomer units. % By weight or more, more preferably 95% by weight or more, particularly preferably 100% by weight (homopolymer of isoprene).
イソプレンと共重合可能な他のエチレン性不飽和単量体としては、例えば、ブタジエン、クロロプレン、1,3−ペンタジエン等のイソプレン以外の共役ジエン単量体;アクリロニトリル、メタクリロニトリル、フマロニトリル、α−クロロアクリロニトリル等のエチレン性不飽和ニトリル単量体;スチレン、アルキルスチレンなどのビニル芳香族単量体;(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル、(メタ)アクリル酸−2−エチルヘキシルなどのエチレン性不飽和カルボン酸エステル単量体;ジビニルベンゼン、ジエチレングリコールジ(メタ)アクリレート、ペンタエリスリトール(メタ)アクリレート等の架橋性単量体;が挙げられる。なお、これらのイソプレンと共重合可能な他のエチレン性不飽和単量体は、1種を単独で用いてもよいし、複数種を併用してもよい。 Examples of other ethylenically unsaturated monomers copolymerizable with isoprene include conjugated diene monomers other than isoprene such as butadiene, chloroprene and 1,3-pentadiene; acrylonitrile, methacrylonitrile, fumaronitrile, α- Ethylenically unsaturated nitrile monomers such as chloroacrylonitrile; vinyl aromatic monomers such as styrene and alkylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) And ethylenically unsaturated carboxylic acid ester monomers such as acrylic acid-2-ethylhexyl; and crosslinkable monomers such as divinylbenzene, diethylene glycol di (meth) acrylate, and pentaerythritol (meth) acrylate. In addition, the other ethylenically unsaturated monomer copolymerizable with these isoprenes may be used individually by 1 type, and may use multiple types together.
合成イソプレン重合体中のイソプレン単位としては、イソプレンの結合状態により、シス結合単位、トランス結合単位、1,2−ビニル結合単位、3,4−ビニル結合単位の4種類が存在する。 There are four types of isoprene units in the synthetic isoprene polymer, cis bond units, trans bond units, 1,2-vinyl bond units, and 3,4-vinyl bond units, depending on the bond state of isoprene.
そして、ディップ成形体の引張強さ向上の観点から、合成イソプレン重合体に含まれるイソプレン単位中のシス結合単位の含有割合は、全イソプレン単位に対して、好ましくは70重量%以上、より好ましくは80重量%以上である。 From the viewpoint of improving the tensile strength of the dip-molded product, the content of cis-bond units in the isoprene units contained in the synthetic isoprene polymer is preferably 70% by weight or more, more preferably, based on the total isoprene units. 80% by weight or more.
合成イソプレン重合体の重量平均分子量は、ゲル・パーミエーション・クロマトグラフィー分析による標準ポリスチレン換算で、10,000〜5,000,000、好ましくは500,000〜5,000,000、特に好ましくは800,000〜3,000,000である。合成イソプレン重合体の重量平均分子量が小さ過ぎると、ディップ成形体の引張強さが低下する傾向があり、逆に大き過ぎると、合成イソプレン重合体のラテックスが製造し難くなる傾向がある。 The weight average molecular weight of the synthetic isoprene polymer is 10,000 to 5,000,000, preferably 500,000 to 5,000,000, particularly preferably 800 in terms of standard polystyrene by gel permeation chromatography analysis. , 3,000 to 3,000,000. If the weight average molecular weight of the synthetic isoprene polymer is too small, the tensile strength of the dip-molded product tends to decrease, and conversely if too large, the synthetic isoprene polymer latex tends to be difficult to produce.
また、合成イソプレン重合体のポリマームーニー粘度〔ML1+4、100℃〕は、50〜80、好ましくは60〜80、特に好ましくは70〜80である。 Moreover, the polymer Mooney viscosity [ML1 + 4 , 100 degreeC] of a synthetic isoprene polymer is 50-80, Preferably it is 60-80, Most preferably, it is 70-80.
また、合成イソプレン重合体ラテックス中のラテックス粒子(合成イソプレン重合体粒子)の体積平均粒子径は、好ましくは0.5〜10μm、より好ましくは0.5〜3μm、特に好ましくは0.5〜2μmである。この体積平均粒子径が小さすぎると、ラテックス粘度が高くなりすぎて取り扱い難くなる場合があり、逆に大きすぎると、合成イソプレン重合体ラテックスを貯蔵した際に、ラテックス表面に皮膜が生成する場合がある。 The volume average particle diameter of latex particles (synthetic isoprene polymer particles) in the synthetic isoprene polymer latex is preferably 0.5 to 10 μm, more preferably 0.5 to 3 μm, and particularly preferably 0.5 to 2 μm. It is. If the volume average particle size is too small, the latex viscosity may become too high and difficult to handle. Conversely, if the volume average particle size is too large, a film may be formed on the latex surface when the synthetic isoprene polymer latex is stored. is there.
合成イソプレン重合体ラテックスの電導度は、1.0mS/cm〜2.0mS/cmであることが好ましい。電導度が1.0mS/cm未満の場合は乳化時や濃縮時に凝集物が多量に発生する場合がある。また、電導度が2.0mS/cmを超える場合には、脱溶剤時に発泡が激しくなったり、ディップ成形用組成物を移送する際や配合時に泡立ちが激しく、手袋にピンホールなどの欠陥を残す場合がある。 The electrical conductivity of the synthetic isoprene polymer latex is preferably 1.0 mS / cm to 2.0 mS / cm. When the conductivity is less than 1.0 mS / cm, a large amount of aggregates may be generated during emulsification or concentration. Further, when the electrical conductivity exceeds 2.0 mS / cm, foaming becomes severe at the time of solvent removal, foaming is severe at the time of transferring the composition for dip molding or at the time of blending, and defects such as pinholes are left in the glove. There is a case.
なお、電導度は、METTLER TOLEDO社製導電率計(商品名:SG78−FK2)を使用し、測定温度25℃で測定した値である。 The conductivity is a value measured at a measurement temperature of 25 ° C. using a conductivity meter (trade name: SG78-FK2) manufactured by METLER TOLEDO.
本発明のディップ成形用合成イソプレン重合体ラテックスの製造方法としては、例えば、有機溶媒に溶解または微分散した合成イソプレン重合体の溶液または微細懸濁液を、界面活性剤の存在下に、水中で乳化し、必要により有機溶媒を除去して、ディップ成形用合成イソプレン重合体ラテックスを製造する方法が挙げられる。 As a method for producing a synthetic isoprene polymer latex for dip molding according to the present invention, for example, a solution or fine suspension of a synthetic isoprene polymer dissolved or finely dispersed in an organic solvent is dissolved in water in the presence of a surfactant. A method of emulsifying and removing an organic solvent as necessary to produce a synthetic isoprene polymer latex for dip molding is mentioned.
合成イソプレン重合体は、従来公知の方法、例えばトリアルキルアルミニウム−四塩化チタンからなるチーグラー系重合触媒やn−ブチルリチウム、sec−ブチルリチウムなどのアルキルリチウム重合触媒を用いて、不活性重合溶媒中で、イソプレンを溶液重合して得ることができる。そして、得られた合成イソプレン重合体の重合体溶液を、そのまま用いても良いが、該重合体溶液から固形の合成イソプレン重合体を取り出した後、その固形の合成イソプレン重合体を有機溶媒に溶解して用いることもできる。 Synthetic isoprene polymer is obtained by using a conventionally known method such as a Ziegler polymerization catalyst composed of trialkylaluminum-titanium tetrachloride or an alkyllithium polymerization catalyst such as n-butyllithium or sec-butyllithium in an inert polymerization solvent. And isoprene can be obtained by solution polymerization. The polymer solution of the obtained synthetic isoprene polymer may be used as it is, but after removing the solid synthetic isoprene polymer from the polymer solution, the solid synthetic isoprene polymer is dissolved in an organic solvent. It can also be used.
この際、イソプレン重合体を合成した後に、重合体溶液中に残った重合触媒の残渣などの不純物を取り除いてもよい。また、重合中または重合後の溶液に、後述する老化防止剤を添加してもよい。
また、市販の固形の合成イソプレン重合体を用いてもよい。
At this time, after synthesizing the isoprene polymer, impurities such as a residue of the polymerization catalyst remaining in the polymer solution may be removed. Moreover, you may add the anti-aging agent mentioned later to the solution during superposition | polymerization or after superposition | polymerization.
A commercially available solid synthetic isoprene polymer may also be used.
本発明のディップ成形用合成イソプレン重合体ラテックスを製造する際に用いる有機溶媒としては、例えば、ベンゼン、トルエン、キシレン等の芳香族炭化水素溶媒;シクロペンタン、シクロペンテン、シクロヘキサン、シクロヘキセン等の脂環族炭化水素溶媒;ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素溶媒;塩化メチレン、クロロホルム、二塩化エチレン等のハロゲン化炭化水素溶媒;等を挙げることができる。これらのうち、芳香族炭化水素溶媒および脂環族炭化水素溶媒が好ましく、シクロヘキサンおよびトルエンが特に好ましい。
なお、有機溶媒の使用量は、合成イソプレン重合体100重量部に対して、好ましくは2,000重量部以下、より好ましくは20〜1,500重量部である。
Examples of the organic solvent used in producing the synthetic isoprene polymer latex for dip molding of the present invention include, for example, aromatic hydrocarbon solvents such as benzene, toluene, and xylene; and alicyclic groups such as cyclopentane, cyclopentene, cyclohexane, and cyclohexene. Hydrocarbon solvents; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; halogenated hydrocarbon solvents such as methylene chloride, chloroform and ethylene dichloride; Of these, aromatic hydrocarbon solvents and alicyclic hydrocarbon solvents are preferred, with cyclohexane and toluene being particularly preferred.
In addition, the usage-amount of an organic solvent becomes like this. Preferably it is 2,000 weight part or less with respect to 100 weight part of synthetic isoprene polymers, More preferably, it is 20-1,500 weight part.
合成イソプレン重合体ラテックスの脂環族炭化水素溶媒および芳香族炭化水素溶媒の合計含有量は500重量ppm以下であることが好ましい。また、脂環族炭化水素溶媒としてはシクロヘキサンが好ましく、芳香族炭化水素溶媒としてはトルエンが好ましい。脂環族炭化水素溶媒および芳香族炭化水素溶媒の合計含有量、特にシクロヘキサンおよびトルエンの合計含有量が多すぎると、ディップ成形用組成物の臭気がきつくなる傾向がある。 The total content of the alicyclic hydrocarbon solvent and the aromatic hydrocarbon solvent in the synthetic isoprene polymer latex is preferably 500 ppm by weight or less. The alicyclic hydrocarbon solvent is preferably cyclohexane, and the aromatic hydrocarbon solvent is preferably toluene. If the total content of the alicyclic hydrocarbon solvent and the aromatic hydrocarbon solvent, particularly the total content of cyclohexane and toluene, is too large, the odor of the dip-forming composition tends to be tight.
なお、脂環族炭化水素溶媒および芳香族炭化水素溶媒の合計含有量の測定は、ガスクロマトグラフィー法など、一般的に使用可能な測定方法で測定することができる。 The total content of the alicyclic hydrocarbon solvent and the aromatic hydrocarbon solvent can be measured by a generally usable measurement method such as a gas chromatography method.
本発明のディップ成形用合成イソプレン重合体ラテックスを製造する際に、界面活性剤として、160℃で加熱したときのセスキテルペン発生量が500ppm以下、好ましくは400ppm以下であるロジン系物質を用いる。 When producing the synthetic isoprene polymer latex for dip molding according to the present invention, a rosin-based material having a sesquiterpene generation amount of 500 ppm or less, preferably 400 ppm or less when heated at 160 ° C. is used as a surfactant.
ここで、ロジン系物質とは、ロジン由来の物質であり、トールロジンなどのロジン、ロジン酸ナトリウムやロジン酸カリウムなどのロジン酸塩などが挙げられる。これらのなかでも、トールロジン、精製ロジンのロジン酸塩が好ましい。 Here, the rosin-based substance is a substance derived from rosin, and examples thereof include rosin such as tall rosin, and rosinate such as sodium rosinate and potassium rosinate. Among these, tall rosin and rosin salt of purified rosin are preferable.
160℃で加熱したときのセスキテルペン量が上記範囲であるロジン系物質を用いることにより乳化時の乳化安定性が良好となる。また、得られるディップ成形体を強度に優れたものにすることができる。 By using a rosin-based material having a sesquiterpene amount within the above range when heated at 160 ° C., the emulsification stability during emulsification is improved. Moreover, the dip-molded body obtained can be made excellent in strength.
ここで、セスキテルペンとは、3つのイソプレンから構成されC15H24の分子式を持つものである。セスキテルペンとしては、例えばファルネセン、ロンギホレン、ビサボレン、カリオフィレン、およびセリネンなどが挙げられる。 Here, the sesquiterpene is composed of three isoprenes and has a molecular formula of C 15 H 24 . Examples of sesquiterpenes include farnesene, longifolene, bisabolen, caryophyllene, and selenium.
界面活性剤の使用量は、合成イソプレン重合体100重量部に対して、好ましくは0.5〜50重量部、より好ましくは0.5〜30重量部である。この量が少なすぎると、ラテックスの安定性が劣る傾向にあり、逆に多すぎると、発泡しやすくなり、ディップ成形時に問題が起きる可能性がある。 The amount of the surfactant used is preferably 0.5 to 50 parts by weight, more preferably 0.5 to 30 parts by weight with respect to 100 parts by weight of the synthetic isoprene polymer. If the amount is too small, the stability of the latex tends to be inferior. On the other hand, if the amount is too large, foaming tends to occur and problems may occur during dip molding.
本発明のディップ成形用合成イソプレン重合体ラテックスを製造する際に使用する水の量は、合成イソプレン重合体100重量部に対して、好ましくは50〜5,000重量部、より好ましくは100〜3,000重量部である。 The amount of water used in producing the synthetic isoprene polymer latex for dip molding of the present invention is preferably 50 to 5,000 parts by weight, more preferably 100 to 3 parts per 100 parts by weight of the synthetic isoprene polymer. 1,000 parts by weight.
使用する水の種類としては、硬水、軟水、イオン交換水、蒸留水、ゼオライトウォーターなどが挙げられる。また、メタノールなどのアルコールに代表される極性溶媒を水と併用してもよい。 Examples of the water used include hard water, soft water, ion exchange water, distilled water, and zeolite water. Moreover, you may use together the polar solvent represented by alcohol, such as methanol, with water.
合成イソプレン重合体の有機溶媒溶液または微細懸濁液を、界面活性剤の存在下、水中で乳化する装置は、一般に乳化機又は分散機として市販されているものであれば特に限定されず使用できる。そして、界面活性剤の添加方法は、特に限定されず、予め水および/または合成イソプレン重合体の有機溶媒溶液または微細懸濁液に添加しても、乳化操作を行っている最中に、乳化液に添加してもよく、一括添加しても、分割添加してもよい。 An apparatus for emulsifying an organic solvent solution or fine suspension of a synthetic isoprene polymer in water in the presence of a surfactant is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser. . The addition method of the surfactant is not particularly limited. Even if the surfactant is added in advance to an organic solvent solution or fine suspension of water and / or synthetic isoprene polymer, emulsification is performed during the emulsification operation. It may be added to the liquid, or may be added all at once or dividedly.
乳化装置としては、例えば、商品名:ホモジナイザー(IKA社製)、商品名:ポリトロン(キネマティカ社製)、商品名:TKオートホモミキサー(特殊機化工業社製)等のバッチ式乳化機;商品名:TKパイプラインホモミキサー(特殊機化工業社製)、商品名:コロイドミル(神鋼パンテック社製)、商品名:スラッシャー(日本コークス工業社製)、商品名:トリゴナル湿式微粉砕機(三井三池化工機社製)、商品名:キャビトロン(ユーロテック社製)、商品名:マイルダー(大平洋機工社製)、商品名:ファインフローミル(大平洋機工社製)等の連続式乳化機;商品名:マイクロフルイダイザー(みずほ工業社製)、商品名:ナノマイザー(ナノマイザー社製)、商品名:APVガウリン(ガウリン社製)等の高圧乳化機;膜乳化機(冷化工業社製)等の膜乳化機;商品名:バイブロミキサー(冷化工業社製)等の振動式乳化機;商品名:超音波ホモジナイザー(ブランソン社製)等の超音波乳化機;等が挙げられる。なお、乳化装置による乳化操作の条件は、特に限定されず、所望の分散状態になるように、処理温度、処理時間などを適宜選定すれば良い。 Examples of the emulsifier include a batch type emulsifier such as trade name: homogenizer (manufactured by IKA), trade name: polytron (manufactured by Kinematica), trade name: TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), etc. Name: TK Pipeline Homomixer (manufactured by Koki Kogyo Kogyo Co., Ltd.), Product Name: Colloid Mill (made by Shinko Pantech Co., Ltd.), Product Name: Thrasher (manufactured by Nihon Coke Kogyo Co., Ltd.), Product Name: Trigonal Wet Fine Crusher ( Continuous emulsifiers such as Mitsui Miike Kako Co., Ltd., trade name: Cavitron (Eurotech Co., Ltd.), trade name: Milder (Daiyo Kiko Co., Ltd.), trade name: Fine Flow Mill (Daiyo Kiko Co., Ltd.) Product name: Microfluidizer (manufactured by Mizuho Industry Co., Ltd.), Product name: Nanomizer (manufactured by Nanomizer), Product name: APV Gaurin (manufactured by Gaurin), etc .; Membrane emulsifiers such as chemical generators (manufactured by Chilling Industries Co., Ltd.); Product name: Vibratory emulsifiers such as Vibro mixers (manufactured by Chilling Industries Co., Ltd.); Product names: Ultrasonic emulsification such as ultrasonic homogenizers (manufactured by Branson) Machine; and the like. In addition, the conditions of the emulsification operation by the emulsification apparatus are not particularly limited, and the treatment temperature, the treatment time, and the like may be appropriately selected so as to obtain a desired dispersion state.
本発明のディップ成形用合成イソプレン重合体ラテックスを製造する際には、乳化操作を経て得られた乳化物から、有機溶媒を除去して、合成イソプレン重合体ラテックスを得ることが好ましい。乳化物から有機溶媒を除去する方法は、特に限定されず、減圧蒸留、常圧蒸留、水蒸気蒸留、遠心分離等の方法を採用することができる。 When the synthetic isoprene polymer latex for dip molding of the present invention is produced, it is preferable to obtain a synthetic isoprene polymer latex by removing the organic solvent from the emulsion obtained through the emulsification operation. The method for removing the organic solvent from the emulsion is not particularly limited, and methods such as vacuum distillation, atmospheric distillation, steam distillation, and centrifugation can be employed.
また、有機溶媒を除去した後、必要に応じ、合成イソプレン重合体ラテックスの固形分濃度を上げるために、減圧蒸留、常圧蒸留、遠心分離、膜濃縮等の方法で濃縮操作を施してもよい。 Further, after removing the organic solvent, if necessary, in order to increase the solid content concentration of the synthetic isoprene polymer latex, a concentration operation may be performed by a method such as vacuum distillation, atmospheric distillation, centrifugation, membrane concentration, etc. .
合成イソプレン重合体ラテックスの固形分濃度は、好ましくは30〜70重量%、より好ましくは40〜70重量%である。固形分濃度が低すぎると、合成イソプレン重合体ラテックスを貯蔵した際に、合成イソプレン重合体粒子が分離する懸念があり、逆に高すぎると、合成イソプレン重合体粒子同士が凝集して粗大凝集物が発生する場合がある。 The solid content concentration of the synthetic isoprene polymer latex is preferably 30 to 70% by weight, more preferably 40 to 70% by weight. If the solid content concentration is too low, there is a concern that the synthetic isoprene polymer particles may be separated when the synthetic isoprene polymer latex is stored. Conversely, if the solid content concentration is too high, the synthetic isoprene polymer particles are aggregated to form coarse aggregates. May occur.
また、合成イソプレン重合体ラテックスには、ラテックスの分野で通常配合される、pH調整剤、消泡剤、防腐剤、架橋剤、キレート化剤、酸素捕捉剤、分散剤、老化防止剤等の添加剤を配合しても良い。 In addition, the synthetic isoprene polymer latex usually contains a pH adjuster, an antifoaming agent, a preservative, a crosslinking agent, a chelating agent, an oxygen scavenger, a dispersant, an anti-aging agent, etc. An agent may be blended.
pH調整剤としては、例えば、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属の水酸化物;炭酸ナトリウム、炭酸カリウムなどのアルカリ金属の炭酸塩;炭酸水素ナトリウムなどのアルカリ金属の炭酸水素塩;アンモニア;トリメチルアミン、トリエタノールアミンなどの有機アミン化合物;等が挙げられるが、アルカリ金属の水酸化物またはアンモニアが好ましい。 Examples of the pH adjuster include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium bicarbonate; ammonia An organic amine compound such as trimethylamine or triethanolamine; an alkali metal hydroxide or ammonia is preferred.
(ディップ成形用組成物)
本発明のディップ成形用組成物は、ディップ成形用合成イソプレン重合体ラテックス、硫黄系加硫剤、および加硫促進剤を含有してなる。
(Dip molding composition)
The dip molding composition of the present invention comprises a synthetic isoprene polymer latex for dip molding, a sulfur vulcanizing agent, and a vulcanization accelerator.
(加硫剤)
加硫剤としては、例えば、粉末硫黄、硫黄華、沈降硫黄、コロイド硫黄、表面処理硫黄、不溶性硫黄等の硫黄;塩化硫黄、二塩化硫黄、モルホリン・ジスルフィド、アルキルフェノール・ジスルフィド、N,N'−ジチオ−ビス(ヘキサヒドロ−2H−アゼピノン−2)、含りんポリスルフィド、高分子多硫化物、2−(4'−モルホリノジチオ)ベンゾチアゾール等の硫黄系加硫剤を用いることができる。なかでも、硫黄が好ましく使用できる。これらの加硫剤は、1種を単独で用いてもよいし、2種以上を併用してもよい。
(Vulcanizing agent)
Examples of the vulcanizing agent include sulfur such as powdered sulfur, sulfur white, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur, etc .; sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, N, N′— Sulfur-based vulcanizing agents such as dithio-bis (hexahydro-2H-azepinone-2), phosphorus-containing polysulfides, polymer polysulfides, and 2- (4′-morpholinodithio) benzothiazole can be used. Of these, sulfur is preferably used. These vulcanizing agents may be used alone or in combination of two or more.
加硫剤の使用量は、特に限定されないが、合成イソプレン重合体100重量部に対して、好ましくは0.1〜10重量部、より好ましくは0.2〜3重量部である。この量が少なすぎても、多すぎても、ディップ成形体の引張強さが低下する傾向がある。 Although the usage-amount of a vulcanizing agent is not specifically limited, Preferably it is 0.1-10 weight part with respect to 100 weight part of synthetic isoprene polymers, More preferably, it is 0.2-3 weight part. If the amount is too small or too large, the tensile strength of the dip-molded product tends to decrease.
(加硫促進剤)
加硫促進剤としては、ディップ成形において通常用いられるものが使用でき、例えば、ジエチルジチオカルバミン酸、ジブチルジチオカルバミン酸、ジ−2−エチルヘキシルジチオカルバミン酸、ジシクロヘキシルジチオカルバミン酸、ジフェニルジチオカルバミン酸、ジベンジルジチオカルバミン酸などのジチオカルバミン酸類およびそれらの亜鉛塩;2−メルカプトベンゾチアゾール、2−メルカプトベンゾチアゾール亜鉛、2−メルカプトチアゾリン、ジベンゾチアジル・ジスルフィド、2−(2,4−ジニトロフェニルチオ)ベンゾチアゾール、2−(N,N−ジエチルチオ・カルバイルチオ)ベンゾチアゾール、2−(2,6−ジメチル−4−モルホリノチオ)ベンゾチアゾール、2−(4′−モルホリノ・ジチオ)ベンゾチアゾール、4−モルホニリル−2−ベンゾチアジル・ジスルフィド、1,3−ビス(2−ベンゾチアジル・メルカプトメチル)ユリアなどが挙げられるが、ジエチルジチオカルバミン酸亜鉛、2−メルカプトベンゾチアゾール、2−メルカプトベンゾチアゾール亜鉛が好ましい。これらの加硫促進剤は、1種を単独で用いてもよいし、2種以上を併用してもよい。
(Vulcanization accelerator)
As the vulcanization accelerator, those usually used in dip molding can be used, for example, diethyldithiocarbamic acid, dibutyldithiocarbamic acid, di-2-ethylhexyldithiocarbamic acid, dicyclohexyldithiocarbamic acid, diphenyldithiocarbamic acid, dibenzyldithiocarbamic acid and the like. Dithiocarbamic acids and their zinc salts; 2-mercaptobenzothiazole, 2-mercaptobenzothiazole zinc, 2-mercaptothiazoline, dibenzothiazyl disulfide, 2- (2,4-dinitrophenylthio) benzothiazole, 2- (N , N-diethylthio-carbylthio) benzothiazole, 2- (2,6-dimethyl-4-morpholinothio) benzothiazole, 2- (4'-morpholino-dithio) benzothiazo And 4-morpholinyl-2-benzothiazyl disulfide, 1,3-bis (2-benzothiazyl mercaptomethyl) urea, etc., but zinc diethyldithiocarbamate, 2-mercaptobenzothiazole, and 2-mercaptobenzothiazole zinc preferable. These vulcanization accelerators may be used alone or in combination of two or more.
加硫促進剤の使用量は、合成イソプレン重合体100重量部に対して、好ましくは0.05〜5重量部であり、更に好ましくは0.1〜2重量部である。この量が少ないとディップ成形体の引張強さが低下する場合がある。また、この量が過大であると、ディップ成形体の伸び、および引張強さが低下する場合がある。 The amount of the vulcanization accelerator used is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the synthetic isoprene polymer. If this amount is small, the tensile strength of the dip-molded product may decrease. On the other hand, if this amount is excessive, the elongation and tensile strength of the dip-formed product may be lowered.
(その他の成分)
(酸化亜鉛)
本発明のディップ成形用組成物は、さらに酸化亜鉛を含有することが好ましい。酸化亜鉛の含有量は、特に限定されないが、合成イソプレン重合体100重量部に対して、好ましくは0.1〜5重量部、より好ましくは0.2〜2重量部である。この量が少なすぎるとディップ成形体の引張強さが低下する傾向があり、逆に多すぎると、ディップ成形用組成物中の合成イソプレン重合体粒子の安定性が低下して粗大な凝集物が発生する場合がある。
(Other ingredients)
(Zinc oxide)
The dip molding composition of the present invention preferably further contains zinc oxide. The content of zinc oxide is not particularly limited, but is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 2 parts by weight with respect to 100 parts by weight of the synthetic isoprene polymer. If this amount is too small, the tensile strength of the dip-molded product tends to decrease. Conversely, if it is too large, the stability of the synthetic isoprene polymer particles in the dip-molding composition decreases, resulting in coarse aggregates. May occur.
(分散剤)
本発明のディップ成形用組成物は、分散剤を必要に応じて含有してもよく、分散剤としては、例えば、ラウリン酸、ミリスチン酸、パルミチン酸、オレイン酸、リノレン酸及びロジン酸などの脂肪酸のナトリウムまたはカリウム塩、ドデシルベンゼンスルホン酸ナトリウムなどのアルキルベンゼンスルホン酸塩、高級アルコール硫酸エステル塩、アルキルスルホコハク酸塩等のアニオン性界面活性剤等が挙げられるが、ドデシルベンゼンスルホン酸ナトリウムが特に好ましい。なお、これらの界面活性剤は、1種を単独で用いてもよいし、2種以上を併用してもよい。
(Dispersant)
The dip molding composition of the present invention may contain a dispersant as necessary. Examples of the dispersant include fatty acids such as lauric acid, myristic acid, palmitic acid, oleic acid, linolenic acid, and rosin acid. And anionic surfactants such as alkyl alcohol sulfonates such as sodium dodecylbenzene sulfonate, higher alcohol sulfates and alkyl sulfosuccinates, sodium dodecyl benzene sulfonate is particularly preferable. In addition, these surfactants may be used individually by 1 type, and may use 2 or more types together.
分散剤の使用量は、合成イソプレン重合体100重量部に対して、好ましくは0.01〜5重量部であり、更に好ましくは0.05〜3重量部である。この量が少ないとディップ成形用組成物の配合安定性が低下したり、前加硫時に凝集物が多くなる場合がある。また、この量が過大であると、ディップ成形用組成物が泡立ち易くなり、ピンホールが発生し易くなる場合がある。 The amount of the dispersant used is preferably 0.01 to 5 parts by weight and more preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the synthetic isoprene polymer. If this amount is small, the blending stability of the dip-forming composition may be reduced, or aggregates may increase during pre-vulcanization. On the other hand, if this amount is excessive, the dip-forming composition tends to foam and pinholes are likely to occur.
(配合剤)
本発明のディップ成形用組成物には、さらに、老化防止剤;カーボンブラック、シリカ、タルク等の補強剤;炭酸カルシウム、クレー等の充填剤;紫外線吸収剤;可塑剤;等の配合剤を必要に応じて配合することができる。
(Combination agent)
The dip molding composition of the present invention further requires a compounding agent such as an anti-aging agent; a reinforcing agent such as carbon black, silica and talc; a filler such as calcium carbonate and clay; an ultraviolet absorber; a plasticizer; It can be blended according to.
老化防止剤としては、2,6−ジ−4−メチルフェノール、2,6−ジ−t−ブチルフェノール、ブチルヒドロキシアニソール、2,6−ジ−t−ブチル−α−ジメチルアミノ−p−クレゾール、オクタデシル−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート、スチレン化フェノール、2,2'−メチレン−ビス(6−α−メチル−ベンジル−p−クレゾール)、4,4'−メチレンビス(2,6−ジ−t−ブチルフノール)、2,2'−メチレン−ビス(4−メチル−6−t−ブチルフェノール)、アルキル化ビスフェノール、p−クレゾールとジシクロペンタジエンのブチル化反応生成物、などの硫黄原子を含有しないフェノール系老化防止剤;2,2'−チオビス−(4−メチル−6−t−ブチルフェノール)、4,4'−チオビス−(6−t−ブチル−o−クレゾール)、2,6−ジ−t−ブチル−4−(4,6−ビス(オクチルチオ)−1,3,5−トリアジン−2−イルアミノ)フェノールなどのチオビスフェノール系老化防止剤;トリス(ノニルフェニル)ホスファイト、ジフェニルイソデシルホスファイト、テトラフェニルジプロピレングリコール・ジホスファイトなどの亜燐酸エステル系老化防止剤;チオジプロピオン酸ジラウリルなどの硫黄エステル系老化防止剤;フェニル−α−ナフチルアミン、フェニル−β−ナフチルアミン、p−(p−トルエンスルホニルアミド)−ジフェニルアミン、4,4'―(α,α−ジメチルベンジル)ジフェニルアミン、N,N−ジフェニル−p−フェニレンジアミン、N−イソプロピル−N'−フェニル−p−フェニレンジアミン、ブチルアルデヒド−アニリン縮合物などのアミン系老化防止剤;6−エトキシ−2,2,4−トリメチル−1,2−ジヒドロキノリンなどのキノリン系老化防止剤;2,5−ジ−(t−アミル)ハイドロキノンなどのハイドロキノン系老化防止剤;などが挙げられる。これらの老化防止剤は、1種を単独で用いてもよいし、または2種以上を併用してもよい。 Anti-aging agents include 2,6-di-4-methylphenol, 2,6-di-t-butylphenol, butylhydroxyanisole, 2,6-di-t-butyl-α-dimethylamino-p-cresol, Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, styrenated phenol, 2,2′-methylene-bis (6-α-methyl-benzyl-p-cresol), 4, Butylation of 4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), alkylated bisphenol, p-cresol and dicyclopentadiene Phenol-based antioxidants containing no sulfur atom, such as reaction products; 2,2′-thiobis- (4-methyl-6-tert-butylphenol), , 4′-thiobis- (6-tert-butyl-o-cresol), 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine-2- Thiobisphenol-based antioxidants such as ylamino) phenol; phosphite-based antioxidants such as tris (nonylphenyl) phosphite, diphenylisodecyl phosphite, tetraphenyldipropylene glycol diphosphite; and dilauryl thiodipropionate Sulfur ester type anti-aging agent: phenyl-α-naphthylamine, phenyl-β-naphthylamine, p- (p-toluenesulfonylamido) -diphenylamine, 4,4 ′-(α, α-dimethylbenzyl) diphenylamine, N, N— Diphenyl-p-phenylenediamine, N-isopropyl-N′-phenyl-p Amine-based antioxidants such as phenylenediamine and butyraldehyde-aniline condensate; quinoline-based antioxidants such as 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline; 2,5-di- ( hydroquinone anti-aging agents such as t-amyl) hydroquinone; and the like. These anti-aging agents may be used alone or in combination of two or more.
老化防止剤の使用量は、合成イソプレン重合体100重量部に対して、好ましくは0.05〜10重量部、より好ましくは0.1〜5重量部である。この量が少なすぎると、合成イソプレン重合体が劣化する場合がある。また、この量が多すぎると、ディップ成形体の引張強さが低下する場合がある。 The amount of the anti-aging agent used is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the synthetic isoprene polymer. If this amount is too small, the synthetic isoprene polymer may deteriorate. Moreover, when there is too much this quantity, the tensile strength of a dip molded object may fall.
ディップ成形用組成物の調製方法は、特に限定されない。当該調整方法としては、ボールミル、ニーダー、ディスパー等の分散機を用いて、合成イソプレン重合体のラテックスに、加硫剤、加硫促進剤、酸化亜鉛、上記の分散剤および必要に応じて配合される老化防止剤などのその他の配合剤を混合する方法や、予め上記の分散機を用いて、合成イソプレン重合体のラテックス以外の所望の配合成分の水性分散液を調製した後、該水性分散液を合成イソプレン重合体のラテックスに混合する方法などが挙げられる。また、合成イソプレン重合体のラテックスに前記の分散剤を予め混合した後、加硫剤、加硫促進剤、および老化防止剤などのその他の配合剤、を添加することもできる。
ディップ成形用組成物のpHは、7以上であることが好ましく、pH8〜12の範囲であることがより好ましい。
The method for preparing the dip molding composition is not particularly limited. As the adjustment method, using a disperser such as a ball mill, a kneader, a disper, etc., the latex of the synthetic isoprene polymer is blended with a vulcanizing agent, a vulcanization accelerator, zinc oxide, the above-mentioned dispersing agent and, if necessary. After preparing an aqueous dispersion of a desired compounding component other than a latex of a synthetic isoprene polymer using a method of mixing other compounding agents such as an anti-aging agent or the above-mentioned disperser in advance, the aqueous dispersion And the like are mixed with latex of synthetic isoprene polymer. In addition, after the above-mentioned dispersant is mixed in advance with the latex of the synthetic isoprene polymer, other compounding agents such as a vulcanizing agent, a vulcanization accelerator, and an anti-aging agent can be added.
The pH of the dip molding composition is preferably 7 or more, more preferably in the range of pH 8-12.
ディップ成形用組成物の固形分濃度は、例えば、15〜70重量%の範囲である。本発明のディップ成形用組成物は、ディップ成形に供する前に、熟成(前加硫ともいう。)させることが好ましい。 The solid content concentration of the dip molding composition is, for example, in the range of 15 to 70% by weight. The dip molding composition of the present invention is preferably aged (also referred to as pre-vulcanization) before being subjected to dip molding.
前加硫する時間は、特に限定されず、前加硫温度にも依存するが、好適な引張強さを有するディップ成形体が得られる観点から、好ましくは1〜14日間であり、更に好ましくは1〜7日間である。
前加硫温度は、好ましくは20〜40℃である。
The time for pre-vulcanization is not particularly limited and depends on the pre-vulcanization temperature, but is preferably 1 to 14 days, more preferably from the viewpoint of obtaining a dip-molded body having suitable tensile strength. 1-7 days.
The pre-vulcanization temperature is preferably 20 to 40 ° C.
前加硫した後、ディップ成形に供されるまで、好適な引張強さを有するディップ成形体が得られる観点から、好ましくは10〜25℃で貯蔵することが好ましい。 From the viewpoint of obtaining a dip-molded body having a suitable tensile strength, it is preferably stored at 10 to 25 ° C. until it is subjected to dip molding after pre-vulcanization.
(ディップ成形体)
本発明のディップ成形体は、本発明のディップ成形用組成物をディップ成形して得られる。
(Dip molded body)
The dip-molded product of the present invention is obtained by dip-molding the dip-molding composition of the present invention.
ディップ成形は、ディップ成形用組成物に型を浸漬し、型の表面に当該組成物を沈着させ、次に型を当該組成物から引き上げ、型の表面に沈着した当該組成物を乾燥させる方法である。ディップ成形用組成物に浸漬される前の型を予熱させてもよい。型をディップ成形用組成物に浸漬する前又は型をディップ成形用組成物から引き上げた後、必要に応じて凝固剤を使用できる。凝固剤の使用方法の具体例は、ディップ成形用組成物に浸漬する前の型を凝固剤溶液に浸漬して型に凝固剤を付着させる方法(アノード凝着浸漬法)、ディップ成形用組成物を沈着させた型を凝固剤溶液に浸漬する方法(ティーグ凝着浸漬法)である。
厚みムラの少ないディップ成形体が得られる点で、アノード凝着浸漬法が好ましい。
Dip molding is a method in which a mold is immersed in a dip molding composition, the composition is deposited on the surface of the mold, the mold is then lifted from the composition, and the composition deposited on the mold surface is dried. is there. The mold before dipping in the dip molding composition may be preheated. A coagulant can be used as necessary before the mold is immersed in the dip molding composition or after the mold is pulled up from the dip molding composition. Specific examples of the method of using the coagulant include a method in which a mold before dipping in a dip molding composition is immersed in a coagulant solution to attach the coagulant to the mold (anode coagulation dipping method), a dip molding composition This is a method of immersing the mold in which the material is deposited in a coagulant solution (Teag adhesion dipping method).
An anode coagulation dipping method is preferred in that a dip-formed product with little thickness unevenness can be obtained.
凝固剤の具体例は、塩化バリウム、塩化カルシウム、塩化マグネシウム、塩化亜鉛、塩化アルミニウムなどのハロゲン化金属;硝酸バリウム、硝酸カルシウム、硝酸亜鉛などの硝酸塩;酢酸バリウム、酢酸カルシウム、酢酸亜鉛など酢酸塩;硫酸カルシウム、硫酸マグネシウム、硫酸アルミニウムなどの硫酸塩;などの水溶性多価金属塩である。なかでも、カルシウム塩が好ましく、硝酸カルシウムがより好ましい。これらの水溶性多価金属塩は、単独または2種以上組み合わせて用いることができ、好ましくは水溶液の状態で使用する。この水溶液は、さらにメチルアルコール、エチルアルコールなどの水溶性有機溶媒やノニオン性界面活性剤を含有し得る。凝固剤の濃度は、水溶性多価金属塩の種類によっても異なるが、好ましくは5〜50重量%、より好ましくは8〜30重量%である。
型をディップ成形用組成物から引き上げた後、例えば、加熱して型上に形成された沈着物を乾燥させる。乾燥条件は適宜選択する。
次いで、加熱して、型上に形成された沈着物を加硫する。
Specific examples of coagulants include metal halides such as barium chloride, calcium chloride, magnesium chloride, zinc chloride, and aluminum chloride; nitrates such as barium nitrate, calcium nitrate, and zinc nitrate; acetates such as barium acetate, calcium acetate, and zinc acetate Water-soluble polyvalent metal salts such as calcium sulfate, magnesium sulfate, and sulfates such as aluminum sulfate; Of these, calcium salts are preferable, and calcium nitrate is more preferable. These water-soluble polyvalent metal salts can be used alone or in combination of two or more, and are preferably used in the form of an aqueous solution. This aqueous solution may further contain a water-soluble organic solvent such as methyl alcohol and ethyl alcohol, and a nonionic surfactant. The concentration of the coagulant varies depending on the type of the water-soluble polyvalent metal salt, but is preferably 5 to 50% by weight, more preferably 8 to 30% by weight.
After the mold is lifted from the dip molding composition, for example, the deposit formed on the mold is dried by heating. Drying conditions are appropriately selected.
Subsequently, the deposit formed on the mold is vulcanized by heating.
加硫時の加熱条件は、特に限定されないが、好ましくは60〜150℃、より好ましくは100〜130℃の加熱温度で、好ましくは10〜120分の加熱時間である。
加熱の方法は、特に限定されないが、オーブンの中で温風で加熱する方法、赤外線を照射して加熱する方法などである。
The heating conditions at the time of vulcanization are not particularly limited, but are preferably 60 to 150 ° C, more preferably 100 to 130 ° C, and preferably 10 to 120 minutes.
The heating method is not particularly limited, and examples thereof include a method of heating with warm air in an oven and a method of heating by irradiating infrared rays.
ディップ成形用組成物を沈着させた型を加熱する前あるいは加熱した後に、水溶性不純物(例えば、余剰の界面活性剤、凝固剤)を除去するために、好ましくは型を水または温水で洗浄する。 Preferably, the mold is washed with water or warm water to remove water-soluble impurities (eg, excess surfactant, coagulant) before or after heating the mold on which the dip molding composition has been deposited. .
加硫後のディップ成形体は、型から脱着される。脱着方法の具体例は、手で型から剥がす方法、水圧又は圧縮空気圧力により剥がす方法である。形成途中のディップ成形体が脱着に対する十分な強度を有していれば、途中工程で脱着し、引き続き、その後の処理を継続してもよい。 The dip-formed body after vulcanization is desorbed from the mold. Specific examples of the desorption method include a method of peeling from a mold by hand, a method of peeling by water pressure or compressed air pressure. If the dip-molded product being formed has sufficient strength against desorption, it may be desorbed in the middle step and then the subsequent processing may be continued.
ディップ成形体が手袋である場合、ディップ成形体同士の接触面における密着を防止し、着脱の際の滑りをよくするために、タルク、炭酸カルシウムなどの無機微粒子又は澱粉粒子などの有機微粒子を手袋表面に散布したり、微粒子を含有するエラストマー層を手袋表面に形成したり、手袋の表面層を塩素化したりしてもよい。 When the dip-molded body is a glove, in order to prevent the dip-molded bodies from sticking to the contact surface and improve slipping during attachment and detachment, organic fine particles such as talc and calcium carbonate or starch particles are used as gloves. It may be dispersed on the surface, an elastomer layer containing fine particles may be formed on the surface of the glove, or the surface layer of the glove may be chlorinated.
以下、実施例により本発明が詳細に説明されるが、本発明はこれらの実施例に限定されない。なお、以下の「%」および「部」は、特に断りのない限り、重量基準である。なお、各種の物性は以下のように測定した。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. The following “%” and “part” are based on weight unless otherwise specified. Various physical properties were measured as follows.
(重量平均分子量)
実施例及び比較例で得られた合成イソプレン重合体ラテックスを固形分濃度で0.1重量%となるように、テトラヒドロフランに溶解した。この溶液をゲル・パーミエーション・クロマトグラフィー分析し、合成イソプレン重合体の標準ポリスチレン換算の重量平均分子量として算出した。
(Weight average molecular weight)
The synthetic isoprene polymer latex obtained in Examples and Comparative Examples was dissolved in tetrahydrofuran so that the solid content concentration was 0.1% by weight. This solution was subjected to gel permeation chromatography analysis and calculated as a weight average molecular weight in terms of standard polystyrene of the synthetic isoprene polymer.
(シス結合単位量)
実施例及び比較例で得られた合成イソプレン重合体ラテックスにメタノールを添加し、凝固した。得られた凝固物を乾燥した後、1H−NMR分析して、合成ポリイソプレン中の全イソプレン単位に対するシス結合単位の割合を示した。
(Cis bond unit amount)
Methanol was added to the synthetic isoprene polymer latex obtained in Examples and Comparative Examples to coagulate. The obtained solidified product was dried and analyzed by 1 H-NMR to show the ratio of cis-bond units to all isoprene units in the synthetic polyisoprene.
(界面活性剤における160℃加熱時に発生するセスキテルペン量測定)
(試料前処理)
不揮発分を15%に調整した界面活性剤20mgを清浄な容器に入れて加熱した。加熱により発生した成分を吸着管(TenaxGR+Carboxen569)へ捕集した。加熱条件および測定条件は以下に示した。なお、不揮発分とは、105℃に調整したオーブン内で2時間乾燥した場合の残渣であり、界面活性剤は、本発明に用いるロジン系物質を含む。
(Measurement of amount of sesquiterpene generated during heating at 160 ° C. in surfactant)
(Sample pretreatment)
20 mg of a surfactant having a non-volatile content adjusted to 15% was placed in a clean container and heated. Components generated by heating were collected in an adsorption tube (TenaxGR + Carboxen569). The heating conditions and measurement conditions are shown below. The non-volatile content is a residue when dried in an oven adjusted to 105 ° C. for 2 hours, and the surfactant contains the rosin-based material used in the present invention.
(加熱条件)
温度:160℃
捕集時間:20min
キャリアーガス:ボンベ空気(Air)(流量50ml/min、AirZERO−A:住友精化製)
(Heating conditions)
Temperature: 160 ° C
Collection time: 20 min
Carrier gas: cylinder air (Air) (flow rate 50 ml / min, AirZERO-A: manufactured by Sumitomo Seika)
(測定条件)
下記の機器および条件にて、セスキテルペン(C15H24)発生量を測定した。なお、検量線はトルエンを用いて作成した。検出下限は5ppmである。
・装置
熱脱離装置:TD−100(Markes製)
GC/MS:HP7890/5975C(Agilent製)
・熱脱離条件
1次脱離:260℃×15min(−30℃トラップ)
2次脱離:320℃×5min
・カラム
DB−5MS(30m×0.25mmID、膜厚1.0μm)J&W社製
・各温度
オーブン:40℃(4minHOLD)−>300℃(15minHOLD)
(10℃/min昇温)
注入口:225℃
トランスファーライン:280℃
イオン源:230℃
・キャリアーガス
He:流量1.5ml/min(スプリット比1:200)
・検出器
MS:電子イオン化(EI)、m/z 29〜600
(Measurement condition)
The amount of sesquiterpene (C 15 H 24 ) generated was measured with the following equipment and conditions. The calibration curve was prepared using toluene. The lower limit of detection is 5 ppm.
・ Device Thermal desorption device: TD-100 (manufactured by Markes)
GC / MS: HP7890 / 5975C (manufactured by Agilent)
・ Thermal desorption conditions Primary desorption: 260 ° C. × 15 min (−30 ° C. trap)
Secondary desorption: 320 ° C. × 5 min
Column DB-5MS (30 m × 0.25 mm ID, film thickness: 1.0 μm) manufactured by J & W ・ Each temperature oven: 40 ° C. (4 min HOLD)-> 300 ° C. (15 min HOLD)
(10 ° C / min temperature rise)
Inlet: 225 ° C
Transfer line: 280 ° C
Ion source: 230 ° C
Carrier gas He: flow rate 1.5 ml / min (split ratio 1: 200)
Detector MS: electron ionization (EI), m / z 29-600
(ディップ成形体における160℃加熱時に発生するセスキテルペン量測定)
(試料前処理)
加硫直前のディップ成形膜20mgをインピンジャーに入れて加熱した。加熱により発生した成分を吸着管(TenaxGR+Carboxen569)へ捕集した。加熱条件および測定条件は、界面活性剤における160℃加熱時に発生するセスキテルペン量測定と同一条件とした。
(Measurement of amount of sesquiterpene generated during heating at 160 ° C. in a dip-molded product)
(Sample pretreatment)
20 mg of a dip-formed film immediately before vulcanization was placed in an impinger and heated. Components generated by heating were collected in an adsorption tube (TenaxGR + Carboxen569). The heating conditions and measurement conditions were the same as those for measuring the amount of sesquiterpene generated during heating at 160 ° C. in the surfactant.
(加硫時の臭気の判定)
加硫時の臭気を下記基準により評価し、結果を表1に示した。
○:セスキテルペンの混じった臭いがしない
△:かすかにセスキテルペンの混じった臭いがするが、不快ではない
×:セスキテルペンの混じった不快な臭いがする
××:セスキテルペンの混じった不快な臭いが強い
(Determination of odor during vulcanization)
The odor during vulcanization was evaluated according to the following criteria, and the results are shown in Table 1.
○: No odor mixed with sesquiterpenes △: Slightly mixed sesquiterpenes but not unpleasant ×: Unpleasant odor mixed with sesquiterpenes XX: Unpleasant odor mixed with sesquiterpenes Is strong
(ディップ成形体の引張強度及び破断直前の伸び)
ディップ成形体の引張強度は、ASTM D412に基づいて測定した。具体的には、ディップ成形体のフィルムをダンベル(Die−C:ダンベル社製)で打ち抜き、引張強度測定用試験片を作製した。当該試験片をテンシロン万能試験機(商品名「RTC−1225A」、(株)オリエンテック製)で引張速度500mm/minで引っ張り、破断直前の引張強度(単位:MPa)、破断直前の伸び(単位:%)を測定した。ディップ成形体の引張強度は下記基準にて評価した。
A:引張強度が23MPa以上
B:引張強度が18MPa以上、23MPa未満
(Tensile strength of dip-formed body and elongation just before break)
The tensile strength of the dip-formed product was measured based on ASTM D412. Specifically, a film of a dip-molded product was punched out with a dumbbell (Die-C: manufactured by Dumbbell Co.) to prepare a test piece for measuring tensile strength. The test piece was pulled with a Tensilon universal testing machine (trade name “RTC-1225A”, manufactured by Orientec Co., Ltd.) at a tensile speed of 500 mm / min, tensile strength just before break (unit: MPa), elongation just before break (unit) :%). The tensile strength of the dip-formed product was evaluated according to the following criteria.
A: Tensile strength is 23 MPa or more B: Tensile strength is 18 MPa or more and less than 23 MPa
(実施例1)
アルキルリチウム系触媒を用いてシクロヘキサン中で溶液重合して得られる合成イソプレン重合体(重量平均分子量(MW)176万、Mw/Mn=1.24、シス結合単位量82%)を含む合成イソプレン重合体のシクロヘキサン溶液1250部(合成イソプレン重合体100部、シクロヘキサン1150部)を準備した。次に、界面活性剤(160℃加熱時に発生するセスキテルペン量が検出限界以下の「バンディスT−25K」(ハリマ化成(株)製))0.8重量%を含有してなる界面活性剤水溶液1245部を調整した。
Example 1
Synthetic isoprene polymer containing a synthetic isoprene polymer (weight average molecular weight (MW) 1,760,000, Mw / Mn = 1.24, cis bond unit amount 82%) obtained by solution polymerization in cyclohexane using an alkyllithium-based catalyst 1250 parts of a combined cyclohexane solution (100 parts of a synthetic isoprene polymer, 1150 parts of cyclohexane) were prepared. Next, a surfactant aqueous solution containing 0.8% by weight of a surfactant (“Bandis T-25K” (Harima Kasei Co., Ltd.) whose amount of sesquiterpene generated when heated at 160 ° C. is below the detection limit) 1245 parts were adjusted.
そして、上記の合成イソプレン重合体のシクロヘキサン溶液全量、および上記界面活性剤水溶液の全量を、SUS304製の溶液に入れて攪拌混合し、続いてホモジナイザー(商品名「マイルダーMDN−303V」、大平洋機工社製)により乳化分散処理を施し、乳化混合液を得た。 Then, the total amount of the above-mentioned synthetic isoprene polymer in cyclohexane solution and the total amount of the above surfactant aqueous solution were stirred and mixed in a solution made of SUS304, followed by a homogenizer (trade name “Milder MDN-303V”, Taiheiyo Kiko Co., Ltd.). Emulsified dispersion treatment was performed to obtain an emulsified mixed solution.
次に、消泡剤(商品名「SM5515」、東レ・ダウコーニング社製)を合成イソプレン重合体100部に対して400ppmになるように添加し、溶剤除去用タンク内で、上記乳化混合液からシクロヘキサンを留去して、合成イソプレン重合体ラテックスを得た。そして、200メッシュステンレス製金網を用い、合成イソプレン重合体ラテックス中の凝集物を除去した。 Next, an antifoaming agent (trade name “SM5515”, manufactured by Toray Dow Corning Co., Ltd.) was added so as to be 400 ppm with respect to 100 parts of the synthetic isoprene polymer, and the above emulsion mixture was used in the solvent removal tank. Cyclohexane was distilled off to obtain a synthetic isoprene polymer latex. And the aggregate in the synthetic isoprene polymer latex was removed using a 200 mesh stainless steel wire mesh.
次に、凝集物を除去後の合成イソプレン重合体ラテックスに対し、密閉ディスク型連続遠心分離機(アルファ・ラバル社製SGR509)により、9000G、通液流量1600L/hrで遠心分離した。その結果、固形分濃度66重量%の実施例1の合成イソプレン重合体ラテックスを得た。当該遠心分離機のボウルが開けられ、ディスクが解放されると、凝集物はほとんど見られなかった。 Next, the synthetic isoprene polymer latex from which the aggregates had been removed was centrifuged at 9000 G and a flow rate of 1600 L / hr using a closed disk type continuous centrifuge (SGR509 manufactured by Alfa Laval). As a result, a synthetic isoprene polymer latex of Example 1 having a solid content concentration of 66% by weight was obtained. When the centrifuge bowl was opened and the disc was released, there was little agglomeration.
(ディップ成形用組成物)
上記で得られた合成イソプレン重合体ラテックスを攪拌しながら、合成イソプレン重合体100部に対して、固形分換算で1部になるように濃度10%のドデシルベンゼンスルホン酸ソーダを添加した。そして、得られた混合物を攪拌しながら、混合物中の合成イソプレン重合体100部に対して、それぞれ固形分換算で、酸化亜鉛1.5部、硫黄1.5部、老化防止剤(商品名:Wingstay L、グッドイヤー社製)2部、ジエチルジチオカルバミン酸亜鉛0.3部、ジブチルジチオカルバミン酸亜鉛0.5部、メルカプトベンゾチアゾール亜鉛塩0.7部となるように、各配合剤の水分散液を添加した後、水酸化カリウム水溶液を添加して、pHを10.5に調整したディップ成形用組成物を得た。
その後、得られたディップ成形用組成物を、30℃に調整された恒温水槽で48時間熟成した。
(Dip molding composition)
While stirring the synthetic isoprene polymer latex obtained above, 10% concentration of sodium dodecylbenzenesulfonate was added to 100 parts of the synthetic isoprene polymer so as to be 1 part in terms of solid content. And stirring the obtained mixture, with respect to 100 parts of synthetic isoprene polymers in the mixture, 1.5 parts of zinc oxide, 1.5 parts of sulfur and anti-aging agent (trade name: trade name: Wingstay L (manufactured by Goodyear) 2 parts, zinc diethyldithiocarbamate 0.3 parts, zinc dibutyldithiocarbamate 0.5 parts, mercaptobenzothiazole zinc salt 0.7 parts After the addition, an aqueous potassium hydroxide solution was added to obtain a dip molding composition having a pH adjusted to 10.5.
Thereafter, the obtained dip molding composition was aged in a constant temperature water bath adjusted to 30 ° C. for 48 hours.
(ディップ成形体)
市販のセラミック製手型(株式会社シンコー製)を洗浄し、70℃のオーブン内で予備加熱した後、18重量%の硝酸カルシウムおよび0.05重量%のポリオキシエチレンラウリルエーテル(商品名:エマルゲン109P、花王(株)製)からなる凝固剤水溶液に5秒間浸漬し、取り出した。次いで、凝固剤で被覆された手型を70℃のオーブン内で30分以上乾燥した。
(Dip molded body)
After washing a commercially available ceramic hand mold (manufactured by Shinko Co., Ltd.) and preheating in an oven at 70 ° C., 18 wt% calcium nitrate and 0.05 wt% polyoxyethylene lauryl ether (trade name: Emulgen) 109P (manufactured by Kao Co., Ltd.) for 5 seconds. Next, the hand mold coated with the coagulant was dried in an oven at 70 ° C. for 30 minutes or more.
その後、凝固剤で被覆された手型をオーブンから取り出し、ディップ成形用組成物に10秒間浸漬した。その後、室温で10分間風乾してから、この手型を60℃の温水中に5分間浸漬した。この操作を繰り返し、フィルム状の合成イソプレン重合体で被覆された手型を2本作成した。 Thereafter, the hand mold coated with the coagulant was taken out of the oven and immersed in the dip molding composition for 10 seconds. Then, after air-drying for 10 minutes at room temperature, this hand mold was immersed in 60 degreeC warm water for 5 minutes. This operation was repeated to prepare two hand molds coated with a film-like synthetic isoprene polymer.
フィルム状の合成イソプレン重合体で被覆された手型の内、1本は130℃のオーブン内に置き、30分間加硫を行った後、オーブンのドアを開けて直ぐに臭気判定を行い、次いで、オーブンから取り出してディップ成形体の物性を測定した。また、残りの1本は、160℃加熱時に発生するセスキテルペン量測定用に使用した。 Of the hand molds coated with a film-like synthetic isoprene polymer, one is placed in an oven at 130 ° C., vulcanized for 30 minutes, then the oven door is opened, and odor determination is performed immediately. It was taken out from the oven and the physical properties of the dip-formed product were measured. The remaining one was used for measuring the amount of sesquiterpene generated when heated at 160 ° C.
加硫されたフィルムで被覆された手型を室温まで冷却し、タルクを散布した後、当該フィルムを手型から剥離した。得られたディップ成形体を用いて引張強度および破断時の伸びの評価を行った。結果を表1に示した。 The hand mold covered with the vulcanized film was cooled to room temperature and sprayed with talc, and then the film was peeled from the hand mold. The obtained dip-molded product was evaluated for tensile strength and elongation at break. The results are shown in Table 1.
(実施例2)
160℃加熱時に発生するセスキテルペン量が検出限界以下である「バンディスT−25K」(ハリマ化成(株)製)に、セスキテルペンの1種である(E)-β-ファルネセン(和光純薬社製)を添加し、160℃加熱時に発生するセスキテルペン量が400ppmになる界面活性剤を調整した。この界面活性剤を使用した以外は、実施例1と同様にして合成イソプレン重合体ラテックスを得た。これを用いて実施例1と同様に、ディップ成形用組成物およびディップ成形体の製造、160℃加熱時に発生するセスキテルペン量の測定、引張強度および破断時伸びの評価を行った。結果を表1に示した。
(Example 2)
“Bandis T-25K” (manufactured by Harima Kasei Co., Ltd.), whose amount of sesquiterpene generated when heated at 160 ° C. is below the detection limit, is a kind of sesquiterpene (E) -β-farnesene (Wako Pure Chemical Industries, Ltd.) Product) was added, and the surfactant was adjusted so that the amount of sesquiterpene generated when heated at 160 ° C. was 400 ppm. A synthetic isoprene polymer latex was obtained in the same manner as in Example 1 except that this surfactant was used. Using this, in the same manner as in Example 1, the production of a dip-molding composition and a dip-molded body, measurement of the amount of sesquiterpene generated when heated at 160 ° C., and evaluation of tensile strength and elongation at break were performed. The results are shown in Table 1.
(比較例1)
界面活性剤を、160℃加熱時に発生するセスキテルペン量が800ppmの「ロンジスN−18」(荒川化学(株)製)に変更した以外は、実施例1と同様に合成イソプレン重合体ラテックスを得た。また、これを用いて実施例1と同様にディップ成形用組成物およびディップ成形体の製造、160℃加熱時に発生するセスキテルペン量の測定、引張強度および破断時伸びの評価を行った。結果を表1に示した。
(Comparative Example 1)
A synthetic isoprene polymer latex was obtained in the same manner as in Example 1 except that the surfactant was changed to “Longis N-18” (manufactured by Arakawa Chemical Co., Ltd.) having an amount of sesquiterpene generated upon heating at 160 ° C. of 800 ppm. It was. In addition, using this, as in Example 1, the production of a dip-molding composition and a dip-molded body, measurement of the amount of sesquiterpene generated when heated at 160 ° C., and evaluation of tensile strength and elongation at break were performed. The results are shown in Table 1.
(比較例2)
160℃加熱時に発生するセスキテルペン量が検出限界以下である「バンディスT−25K」(ハリマ化成(株)製)に、セスキテルペンの1種である(E)-β-ファルネセン(和光純薬社製)を添加し、160℃加熱時に発生するセスキテルペン量が1000ppmになる界面活性剤を調整した。この界面活性剤を使用した以外は、実施例1と同様に合成イソプレン重合体ラテックスを得た。また、これを用いて実施例1と同様にディップ成形用組成物およびディップ成形体の製造、160℃加熱時に発生するセスキテルペン量の測定、引張強度および破断時伸びの評価を行った。結果を表1に示した。
(Comparative Example 2)
“Bandis T-25K” (manufactured by Harima Kasei Co., Ltd.), whose amount of sesquiterpene generated when heated at 160 ° C. is below the detection limit, is a kind of sesquiterpene (E) -β-farnesene (Wako Pure Chemical Industries, Ltd.) Product) was added, and the surfactant was adjusted so that the amount of sesquiterpene generated upon heating at 160 ° C. was 1000 ppm. A synthetic isoprene polymer latex was obtained in the same manner as in Example 1 except that this surfactant was used. In addition, using this, as in Example 1, the production of a dip-molding composition and a dip-molded body, measurement of the amount of sesquiterpene generated when heated at 160 ° C., and evaluation of tensile strength and elongation at break were performed. The results are shown in Table 1.
実施例1は、加硫時の不快な臭いがしなかった。さらに、ディップ成形体の引張強度と破断時伸びが高いものが得られた。 Example 1 did not have an unpleasant odor during vulcanization. Further, a dip-molded product having high tensile strength and high elongation at break was obtained.
実施例2は、加硫時にかすかにセスキテルペンの混じった臭いが発生したが、不快な臭いではなかった。さらに、ディップ成形体の引張強度と破断時伸びが高いものが得られた。 In Example 2, a odor with a slight sesquiterpene was generated during vulcanization, but it was not an unpleasant odor. Further, a dip-molded product having high tensile strength and high elongation at break was obtained.
一方、セスキテルペン発生量が多い界面活性剤を使用した比較例1においては、加硫時に不快な臭いが発生した。また、ディップ成形体の引張強度が低いものであった。 On the other hand, in Comparative Example 1 using a surfactant having a large amount of sesquiterpene, an unpleasant odor was generated during vulcanization. Moreover, the tensile strength of the dip-molded product was low.
また、セスキテルペンを多く添加した比較例2においては、加硫時に発生した不快な臭いが強いものであった。また、ディップ成形体の引張強度が低いものであり、破断時伸びも劣ったものであった。 Further, in Comparative Example 2 in which a large amount of sesquiterpene was added, the unpleasant odor generated during vulcanization was strong. Moreover, the tensile strength of the dip-formed product was low, and the elongation at break was also inferior.
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