JP2019143002A - Chloroprene polymer latex and manufacturing method therefor - Google Patents
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本発明はクロロプレン重合体ラテックスとその製造方法に関するものであり、さらに詳しくは、浸漬成型により優れた柔軟性と力学物性を有する加硫ゴム製品を得ることのできるクロロプレン重合体ラテックスとその製造方法に関するものである。 The present invention relates to a chloroprene polymer latex and a method for producing the same, and more particularly to a chloroprene polymer latex capable of obtaining a vulcanized rubber product having excellent flexibility and mechanical properties by immersion molding and a method for producing the same. Is.
クロロプレン重合体ラテックスは、機械的強度、耐候性、耐油性、耐熱性、難燃性、接着性などのバランスが良好であるため、手袋や被膜等の浸漬成型体、糸ゴム、接着剤、表面処理剤などの用途として幅広く用いられている。特に手袋用途においては従来天然ゴムラテックスが用いられてきたが、天然ゴムに含まれるタンパク質等による医療従事者や患者のアレルギーが問題となるため、合成ゴム手袋が勧められてきた（特許文献１）。中でもクロロプレンゴムは柔軟性や風合い等各種物性が天然ゴムに近いため、天然ゴム手袋からの代替が進められている。 Chloroprene polymer latex has a good balance of mechanical strength, weather resistance, oil resistance, heat resistance, flame retardancy, adhesion, etc., so it can be used for immersion molding such as gloves and coatings, thread rubber, adhesives, surface Widely used as a treatment agent. In particular, natural rubber latex has been conventionally used for gloves, but synthetic rubber gloves have been recommended because allergies of medical workers and patients due to proteins contained in natural rubber become a problem (Patent Document 1). . Among them, chloroprene rubber is being replaced with natural rubber gloves because various physical properties such as flexibility and texture are close to those of natural rubber.
しかしながらクロロプレン重合体ラテックスを用いた手袋は天然ゴムやイソプレンゴムと比べて柔軟性などの物性が劣るため、更なる物性の向上が望まれてきた。手袋等浸漬用途に用いられるクロロプレン重合体ラテックスは、液中の重合体固形分を高く保つため、また優れた作業性（成型時の未加硫状態での変形防止、型からの離型性など）を得るために重合転化率を高く設定し、単離した重合体を１重量％トルエン溶液にした際に溶け残る超高分子重合体（ゲルと呼称する）を含ませる必要がある。ゲルはラテックス粒子内で高度に架橋しており、これを含むクロロプレン重合体ラテックスを手袋用途に使用することにより高い破断強度や耐摩耗性などの物性や優れた作業性を得ることができる（特許文献２）。 However, gloves using chloroprene polymer latex are inferior in physical properties such as flexibility as compared with natural rubber and isoprene rubber, and therefore further improvement in physical properties has been desired. Chloroprene polymer latex used for gloves and other dipping applications keeps the polymer solids in the liquid high, and has excellent workability (preventing deformation in the unvulcanized state during molding, releasability from the mold, etc.) In order to obtain the above, it is necessary to set the polymerization conversion rate high and to include an ultra-high molecular weight polymer (referred to as a gel) that remains undissolved when the isolated polymer is made into a 1% by weight toluene solution. Gel is highly cross-linked in latex particles, and by using chloroprene polymer latex containing this for glove applications, physical properties such as high breaking strength and wear resistance and excellent workability can be obtained (patent) Reference 2).
一方で手袋に必要な物性として柔軟性が挙げられ（特許文献３）、ゴム物性としては低伸び時の引張応力（モジュラス）が相当する。しかし前述のゲルを含んだクロロプレンゴムを用いた手袋では低伸び時の引張応力が高くなり柔軟性が劣るため、高い破断強度を有したまま天然ゴムやイソプレンゴムに匹敵する柔軟性を有し、かつ良好な作業性を持つクロロプレン重合体ラテックスが望まれてきた。 On the other hand, flexibility is mentioned as a physical property necessary for gloves (Patent Document 3), and a tensile stress (modulus) at low elongation corresponds to a rubber physical property. However, in the glove using chloroprene rubber containing the gel described above, the tensile stress at the time of low elongation is high and the flexibility is inferior, so it has flexibility comparable to natural rubber and isoprene rubber while having high breaking strength, A chloroprene polymer latex having good workability has been desired.
本発明は、上記の課題に鑑みてなされたものであり、その目的は、浸漬成型により加硫ゴム製品を与え得るクロロプレン重合体ラテックスであり、破断強度等の力学特性を維持し、優れた柔軟性すなわち低伸長時の低モジュラスの両立を可能とした加硫ゴムを与えうるクロロプレン重合体ラテックスを提供することである。 The present invention has been made in view of the above problems, and its purpose is a chloroprene polymer latex capable of giving a vulcanized rubber product by immersion molding, maintaining mechanical properties such as breaking strength and excellent flexibility. It is to provide a chloroprene polymer latex capable of providing a vulcanized rubber capable of coexisting with a low modulus at a low elongation.
本発明者は、上記課題を解決するために鋭意検討した結果、本発明を完成するに至ったものである。すなわち本発明は、１重量％トルエン不溶分量が１５〜８５重量％であり、トルエン可溶なゾル部分の重量平均分子量が２０万〜５０万であるクロロプレン重合体を含むクロロプレン重合体ラテックスであって、（８，１５−イソピマル酸の含有量）÷（ジヒドロピマル酸の含有量）の値が１より小さいロジン酸のアルカリ金属塩からなる乳化剤をラテックス１００重量％に対して１．５〜８．０重量％含有することを特徴とするクロロプレン重合体ラテックスである。 As a result of intensive studies to solve the above-described problems, the present inventor has completed the present invention. That is, the present invention is a chloroprene polymer latex containing a chloroprene polymer having a 1% by weight toluene-insoluble content of 15 to 85% by weight and a toluene-soluble sol portion having a weight average molecular weight of 200,000 to 500,000. An emulsifier comprising an alkali metal salt of rosin acid having a value of (8,15-isopimalic acid content) ÷ (dihydropimalic acid content) smaller than 1 is 1.5 to 8.0 with respect to 100% by weight of latex. It is a chloroprene polymer latex characterized by containing by weight.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のクロロプレン重合体ラテックスは、重合体中の１重量％トルエン不溶分量が１５〜８５重量％であり、トルエン可溶なゾル部分の重量平均分子量が２０万〜５０万であるクロロプレン重合体を含むクロロプレン重合体ラテックスである。クロロプレン重合体の１重量％トルエン不溶分量が１５％未満では加硫物の耐摩耗性や離型性に劣り、１重量％トルエン不溶分量が８５％より多いと加硫物の破断強度や柔軟性に劣る。クロロプレン重合体のトルエン可溶なゾル部分の重量平均分子量が２０万未満では加硫物の耐摩耗性や離形性に劣り、５０万を超えると加硫物の柔軟性に劣る。 The chloroprene polymer latex of the present invention is a chloroprene polymer having a 1% by weight toluene insoluble content in the polymer of 15 to 85% by weight and a toluene-soluble sol portion having a weight average molecular weight of 200,000 to 500,000. A chloroprene polymer latex containing. If the 1% by weight toluene insoluble content of the chloroprene polymer is less than 15%, the abrasion resistance and releasability of the vulcanized product is inferior. If the 1% by weight toluene insoluble content is more than 85%, the rupture strength and flexibility of the vulcanized product are poor. Inferior to When the weight-average molecular weight of the sol-soluble sol part of the chloroprene polymer is less than 200,000, the abrasion resistance and releasability of the vulcanizate is poor, and when it exceeds 500,000, the flexibility of the vulcanizate is poor.
本発明のクロロプレン重合体ラテックスは（８，１５−イソピマル酸の含有量）÷（ジヒドロピマル酸の含有量）の値が１より小さいロジン酸のアルカリ金属塩からなる乳化剤を、ラテックス中１．５〜８．０重量％含有する。含有するロジン酸のアルカリ金属塩からなる乳化剤の（８，１５−イソピマル酸の含有量）÷（ジヒドロピマル酸の含有量）の値が１以上の場合は、浸漬成型により得られた加硫ゴムを浸漬成型用の型から剥がすことが困難となり、離型性に劣る。また、ラテックス１００重量％に対してロジン酸のアルカリ金属塩からなる乳化剤の含有量が１．５重量％より少ない場合はラテックスの貯蔵安定性に劣り、８．０重量％より多い場合は浸漬成型時に形成される被膜が形成されにくく、生産性に劣る。 The chloroprene polymer latex of the present invention contains an emulsifier composed of an alkali metal salt of rosin acid having a value of (8,15-isopimalic acid content) ÷ (dihydropimalic acid content) smaller than 1 in the latex. Contains 8.0% by weight. When the value of (8,15-isopimalic acid content) ÷ (dihydropimalic acid content) of the emulsifier comprising an alkali metal salt of rosin acid contained is 1 or more, the vulcanized rubber obtained by immersion molding is used. It becomes difficult to peel off from the mold for immersion molding, and the releasability is poor. Further, when the content of an emulsifier composed of an alkali metal salt of rosin acid is less than 1.5% by weight with respect to 100% by weight of latex, the storage stability of the latex is inferior, and when more than 8.0% by weight, immersion molding is performed. The film formed sometimes is difficult to be formed and the productivity is poor.
本発明のクロロプレン重合体ラテックスの製造方法について以下に説明する。 The method for producing the chloroprene polymer latex of the present invention will be described below.
本発明のクロロプレン重合体ラテックスは、１重量％トルエン不溶分量が７０重量％以上であるクロロプレン重合体Ａを含むラテックスと、１重量％トルエン不溶分量が１０重量％以下であるクロロプレン重合体Ｂを含むラテックスとを混合することで得られる。ＡとＢとの混合比は重量比で２：８〜８：２であることが好ましい。Ａの１重量％トルエン不溶分量が７０重量％未満の場合はラテックス粒子中の重合体架橋密度が低く、浸漬成型により得られる加硫ゴムの架橋密度が十分に高くならず破断強度等の加硫物性に劣る。Ｂの１重量％トルエン不溶分量が１０重量％より大きいとラテックス粒子中の重合体架橋密度の低い成分が少なく、浸漬成型により得られる加硫ゴムの低伸長時のモジュラスが高くなるため柔軟性に劣る。ＡとＢの混合比が２：８〜８：２の範囲であれば、高破断強度と柔軟性のバランスに優れた加硫物が得られるため好ましい。 The chloroprene polymer latex of the present invention contains a latex containing chloroprene polymer A having a 1 wt% toluene insoluble content of 70 wt% or more and a chloroprene polymer B having a 1 wt% toluene insoluble content of 10 wt% or less. It is obtained by mixing with latex. The mixing ratio of A and B is preferably 2: 8 to 8: 2 by weight. When the amount of 1% by weight of toluene insoluble in A is less than 70% by weight, the crosslink density of the polymer in the latex particles is low, and the crosslink density of the vulcanized rubber obtained by dip molding is not sufficiently high. Inferior in physical properties. When the 1% by weight toluene insoluble content of B is greater than 10% by weight, there are few components with a low polymer crosslinking density in the latex particles, and the modulus at the time of low elongation of the vulcanized rubber obtained by immersion molding becomes high, so that flexibility is achieved. Inferior. If the mixing ratio of A and B is in the range of 2: 8 to 8: 2, it is preferable because a vulcanizate having an excellent balance between high breaking strength and flexibility can be obtained.
クロロプレン重合体ラテックスが含有するクロロプレン重合体の原料としては、クロロプレン単独、又はクロロプレン及びこれと共重合可能な単量体との混合物が用いられる。共重合可能な単量体としては、例えば、２，３−ジクロロ−１，３−ブタジエン、２−シアノ−１，３−ブタジエン、１−クロロ−１，３−ブタジエン、１，３−ブタジエン、スチレン、アクリロニトリル、メチルメタクリレート、メタクリル酸、アクリル酸等が挙げられ、このうち単独でまたは２種類以上を併用することができる。これら単量体を含む量は特に限定するものではないが、浸漬成型により得られる加硫ゴムの性質を損なわない程度で、０〜２０重量％が好ましい。 As a raw material of the chloroprene polymer contained in the chloroprene polymer latex, chloroprene alone or a mixture of chloroprene and a monomer copolymerizable therewith is used. Examples of the copolymerizable monomer include 2,3-dichloro-1,3-butadiene, 2-cyano-1,3-butadiene, 1-chloro-1,3-butadiene, 1,3-butadiene, Styrene, acrylonitrile, methyl methacrylate, methacrylic acid, acrylic acid and the like can be mentioned, and among these, alone or in combination of two or more. The amount containing these monomers is not particularly limited, but is preferably 0 to 20% by weight as long as the properties of the vulcanized rubber obtained by immersion molding are not impaired.
本発明のクロロプレン重合体ラテックスの製造方法では、連鎖移動剤を用いてもよい。連鎖移動剤としては、例えば、アルキルメルカプタン、ハロゲン炭化水素、アルキルキサントゲンジスルフィド、アルキルキサントゲンポリスルフィド、硫黄等の分子量調節剤等があげられ、これらのうち、作業性の面からｎ−ドデシルメルカプタン、アルキルキサントゲンジスルフィドが好ましい。連鎖移動剤の量としては、分子量調整のため一般のラジカル重合で使用される量であれば特に限定するものではないが、得られる重合体の分子量を目的通りにし、さらに、浸漬成型により得られる加硫ゴムの柔軟性と良好な力学物性のため、連鎖移動剤以外の単量体混合物１００重量％に対して０．０１〜１．０重量％であることが好ましい。特に、重合体中の１重量％トルエン不溶分量が７０％以上である高分子量クロロプレン重合体ラテックスＡを製造する際の連鎖移動剤の量としては、連鎖移動剤以外の単量体混合物１００重量％に対して０．０１〜０．１０重量％であることが好ましく、重合体中の１重量％トルエン不溶分量が１０％以下である低分子量クロロプレン重合体ラテックスＢを製造する際の連鎖移動剤の量としては、連鎖移動剤以外の単量体混合物１００重量％に対して０．１２〜１．０重量％であることが好ましく、０．１４〜０．６０重量％がさらに好ましい。 In the method for producing a chloroprene polymer latex of the present invention, a chain transfer agent may be used. Examples of the chain transfer agent include molecular weight regulators such as alkyl mercaptans, halogen hydrocarbons, alkyl xanthogen disulfides, alkyl xanthogen polysulfides, sulfur, etc. Among these, n-dodecyl mercaptan, alkyl xanthogens are preferred from the viewpoint of workability. Disulfide is preferred. The amount of the chain transfer agent is not particularly limited as long as it is an amount used in general radical polymerization for adjusting the molecular weight, but the molecular weight of the obtained polymer is set as intended, and further obtained by immersion molding. In view of the flexibility and good mechanical properties of the vulcanized rubber, the content is preferably 0.01 to 1.0% by weight with respect to 100% by weight of the monomer mixture other than the chain transfer agent. In particular, the amount of the chain transfer agent in producing the high molecular weight chloroprene polymer latex A having a 1% by weight toluene insoluble content in the polymer of 70% or more is 100% by weight of a monomer mixture other than the chain transfer agent. The chain transfer agent used in the production of the low molecular weight chloroprene polymer latex B having a 1% by weight toluene insoluble content in the polymer of preferably 10% or less is preferably 0.01 to 0.10% by weight based on the weight of the polymer. The amount is preferably 0.12 to 1.0% by weight, more preferably 0.14 to 0.60% by weight, based on 100% by weight of the monomer mixture other than the chain transfer agent.
本発明のクロロプレン重合体ラテックスを得るための乳化剤としては、（８，１５−イソピマル酸の含有量）÷（ジヒドロピマル酸の含有量）の値が１より小さいロジン酸のアルカリ金属塩からなる乳化剤を使用する。アルカリ金属塩としてはリチウム、ナトリウム、カリウム、セシウム等が挙げられる。これらは、１種類でも良く、２種類以上を含んでいても良い。このようロジン酸のアルカリ金属塩としては、荒川化学（株）製、ロンヂスＫ−２５（（８，１５−イソピマル酸の含有量）÷（ジヒドロピマル酸の含有量）＝０．５）等の市販品を使用することができる。 As an emulsifier for obtaining the chloroprene polymer latex of the present invention, an emulsifier comprising an alkali metal salt of rosin acid having a value of (8,15-isopimalic acid content) ÷ (dihydropimalic acid content) smaller than 1. use. Examples of the alkali metal salt include lithium, sodium, potassium, cesium and the like. These may be one type or may include two or more types. As such an alkali metal salt of rosin acid, commercially available from Arakawa Chemical Co., Ltd., Longis K-25 ((8,15-isopimalic acid content) ÷ (dihydropimalic acid content) = 0.5), etc. Goods can be used.
重合は、混合攪拌しながら１０〜５０℃の温度で、重合系のｐＨ７〜１３において触媒液を添加して行われることが望ましい。ｐＨ調節剤としては、例えば、水酸化ナトリウム、水酸化カリウム、燐酸ナトリウム、燐酸カリウム、トリエチルアミン、ジエチルアミン、トリエタノールアミン、ジエタノールアミン、エタノールアミン、アンモニア等の塩基性化合物のうち、いずれか１種類以上を単独または併用して用いる。 The polymerization is desirably performed at a temperature of 10 to 50 ° C. with mixing and stirring at a pH of 7 to 13 in the polymerization system and adding a catalyst solution. Examples of the pH adjuster include at least one of basic compounds such as sodium hydroxide, potassium hydroxide, sodium phosphate, potassium phosphate, triethylamine, diethylamine, triethanolamine, diethanolamine, ethanolamine, and ammonia. Use alone or in combination.
重合を開始させるための触媒（重合開始剤）としては、例えば、過硫酸カリウム、過硫酸アンモニウム、過酸化水素、ｔ−ブチルハイドロパーオキサイド等が用いられる。 As a catalyst (polymerization initiator) for initiating polymerization, for example, potassium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, or the like is used.
重合は、重合転化率４０〜９９％程度まで行なわれ、次いで重合禁止剤を少量添加して停止させる。 The polymerization is carried out to a polymerization conversion rate of about 40 to 99%, and then stopped by adding a small amount of a polymerization inhibitor.
重合禁止剤としては、例えば、チオジフェニルアミン、４−ｔ−ブチルカテコール、２，６−ジ−ｔ−ブチル−４−メチルフェノール、２，２’−メチレンビス（４−エチル−６−ｔ−ブチルフェノール）、４，４’−チオビス（３−メチル−６−ｔ−ブチルフェノール）、２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、ハイドロキノン、Ｎ，Ｎ−ジエチルヒドロキシルアミンなどが挙げられ、このうち１種類以上を単独又は併用して用いる。 Examples of the polymerization inhibitor include thiodiphenylamine, 4-t-butylcatechol, 2,6-di-t-butyl-4-methylphenol, and 2,2′-methylenebis (4-ethyl-6-t-butylphenol). 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), hydroquinone, N, N-diethylhydroxylamine and the like. Of these, one or more of them are used alone or in combination.
次いで得られたクロロプレン重合体ラテックスは、未反応単量体を減圧スチームストリッピング法などにより除去、回収し、クロロプレン重合体ラテックスを得る。得られた重合体中の１重量％トルエン不溶分量が７０％以上であるクロロプレン重合体ラテックスＡと、重合体中の１重量％トルエン不溶分量が１０％以下であるクロロプレン重合体ラテックスＢを重合体の重量比でＡ：Ｂ＝２：８〜８：２の範囲で混合することで、目的とするクロロプレン重合体ラテックスを得る。 Next, from the obtained chloroprene polymer latex, unreacted monomers are removed and recovered by a reduced pressure steam stripping method or the like to obtain a chloroprene polymer latex. A chloroprene polymer latex A having a 1% by weight toluene insoluble content in the obtained polymer of 70% or more and a chloroprene polymer latex B having a 1% by weight toluene insoluble content in the polymer of 10% or less. The target chloroprene polymer latex is obtained by mixing in a weight ratio of A: B = 2: 8 to 8: 2.
本発明のクロロプレン重合体ラテックスは浸漬成形用に用いられる。浸漬成型にて加硫ゴム製品を製造するためには、通常の浸漬成型の手法が利用できる。例えば、本発明のクロロプレン重合体ラテックスに必要に応じて受酸剤、充填剤、補強剤、老化防止剤、可塑剤、滑剤、酸化亜鉛、加硫促進剤、硫黄等、またはそれらを水に分散させた分散液、さらに必要により乳化剤、粘度調節剤、ｐＨ調節剤を添加したラテックス組成物を作製し、その中へ硝酸カルシウム等の凝固剤を含浸させた目的とする加硫ゴム成型物の型を浸漬することで、型上にゴム膜を形成させる。さらにゴム膜を型とともに水に浸け、余分な乳化剤などを水洗除去した後、型とともにオーブン等で加熱し、乾燥および加硫するという手法等が挙げられる。 The chloroprene polymer latex of the present invention is used for immersion molding. In order to produce a vulcanized rubber product by immersion molding, a normal immersion molding technique can be used. For example, the chloroprene polymer latex of the present invention may be acid acceptor, filler, reinforcing agent, anti-aging agent, plasticizer, lubricant, zinc oxide, vulcanization accelerator, sulfur, etc. A dispersion composition, and a latex composition to which an emulsifier, a viscosity modifier, and a pH modifier are added if necessary, and a mold of a desired vulcanized rubber molded product impregnated with a coagulant such as calcium nitrate therein Is immersed to form a rubber film on the mold. Furthermore, after the rubber film is soaked in water together with the mold, excess emulsifier and the like are washed away and then heated in an oven together with the mold, dried and vulcanized.
本発明のクロロプレン重合体ラテックスは、ラテックス粒子内のポリマー架橋密度が調整されており、容易に浸漬成型が可能でかつ浸漬加硫フィルムの高い破断強度と優れた柔軟性と力学物性を有する加硫ゴムを製造することができるため、これらの物性が要求される用途、例えば試験検査用手袋、医療用手袋などとして使用することができる。 The chloroprene polymer latex of the present invention has a polymer crosslink density adjusted in the latex particles, can be easily dip-molded, and has a high breaking strength, excellent flexibility and mechanical properties of the dip vulcanized film. Since rubber can be produced, it can be used for applications that require these physical properties, such as test gloves and medical gloves.
本発明のクロロプレン重合体ラテックスは、高分子量重合体と低分子量重合体を含むことにより、浸漬成型により作製された加硫ゴムにおいて優れた柔軟性と力学物性を両立することができる。 By including the high molecular weight polymer and the low molecular weight polymer, the chloroprene polymer latex of the present invention can achieve both excellent flexibility and mechanical properties in the vulcanized rubber produced by immersion molding.
本発明を以下の実施例により具体的に説明する。但し、本発明はこれらに限定されるものではない。 The present invention will be specifically described by the following examples. However, the present invention is not limited to these.
＜１重量％トルエン不溶分量＞
重合体中の１重量％トルエン不溶分量は、クロロプレン重合体ラテックスに酢酸を加えｐＨ＝６．０に調整したのちシャーレ上に広げて凍結させ、真空乾燥機による凍結乾燥により得た重合体を１％の濃度でトルエンに溶解し、２０時間攪拌したのちに２００メッシュの金網にて濾別される不溶分量として求めた。
<1% by weight toluene insoluble content>
The amount of 1% by weight toluene insoluble in the polymer was adjusted to pH = 6.0 by adding acetic acid to the chloroprene polymer latex, then spread on a petri dish and frozen, and the polymer obtained by freeze-drying with a vacuum dryer was 1 It was calculated | required as the amount of insoluble matter which is melt | dissolved in toluene by the density | concentration of%, and after stirring for 20 hours, it is filtered by a 200 mesh wire net.
＜（８，１５−イソピマル酸の含有量）÷（ジヒドロピマル酸の含有量）の値＞
使用するロジン酸のアルカリ金属塩からなる乳化剤をメチル化後、ガスクロマトグラフによる測定を実施し、各成分のピーク面積から８，１５−イソピマル酸およびジヒドロピマル酸の比率［（８，１５−イソピマル酸の含有量）÷（ジヒドロピマル酸の含有量）の値］を算出した。既製品ラテックスの乳化剤分析においては、ラテックスを乾燥後、クロロホルムに溶解し、塩酸−メタノールにて再沈精製した後、ろ液を濃縮、メチル化し、ガスクロマトグラフによる測定を実施し、上記と同様に各成分のピーク面積から８，１５−イソピマル酸およびジヒドロピマル酸の比率を算出した。
<(8,15-Isopimaric acid content) / (dihydropimalic acid content)>
After methylation of an emulsifier composed of an alkali metal salt of rosin acid to be used, measurement by gas chromatography was carried out. From the peak area of each component, the ratio of 8,15-isopimalic acid and dihydropimalic acid [(8,15-isopimalic acid (Content) ÷ (content of dihydropimaric acid)] was calculated. In the analysis of emulsifiers for ready-made latexes, the latex was dried, dissolved in chloroform, purified by reprecipitation with hydrochloric acid-methanol, the filtrate was concentrated, methylated, and measured by gas chromatography. The ratio of 8,15-isopimalic acid and dihydropimalic acid was calculated from the peak area of each component.
使用カラム：ＤＢ−５ ０．２５ｍｍφ×３０ｍ（膜厚１μｍ）
カラム温度：１５０℃→３００℃（３０ｍｉｎ保持）
昇温速度：５℃／ｍｉｎ
注入口温度：２５０℃
検出器温度：２５０℃
注入量：１μｌ
＜常態物性＞
加硫物の常態物性は、得られた浸漬成型体から、ＡＳＴＭ Ｄ−４１２に準じてダンベル形状Ｃ型の試験片を用い、引張り速度５００ｍｍ／分、２３℃の条件により破断時の引張強度および破断時の伸び、１００％伸長応力（モジュラス）、３００％伸長応力、５００％伸長応力を測定した。
Column used: DB-5 0.25 mmφ × 30 m (film thickness 1 μm)
Column temperature: 150 ° C. → 300 ° C. (30 min hold)
Temperature increase rate: 5 ° C / min
Inlet temperature: 250 ° C
Detector temperature: 250 ° C
Injection volume: 1 μl
<Normal physical properties>
The normal physical properties of the vulcanizate were determined by using a dumbbell-shaped C-type test piece according to ASTM D-412 from the obtained dip-molded product, and a tensile strength at breakage under the conditions of a pulling speed of 500 mm / min and 23 ° C. The elongation at break, 100% elongation stress (modulus), 300% elongation stress, and 500% elongation stress were measured.
実施例１
表１で示した割合のクロロプレン単量体、ｎ−ドデシルメルカプタン、ロジン酸カリウム（荒川化学（株）製、商品名ロンヂスＫ−２５、（８，１５−イソピマル酸の含有量）÷（ジヒドロピマル酸の含有量）＝０．５）、ナフタレンスルホン酸ナトリウムとホルムアルデヒドの縮合物、水酸化ナトリウム、ハイドロサルファイトナトリウム、及び純水を攪拌機付き１０Ｌオートクレーブ中４０℃で重合を行った。重合は窒素雰囲気下で０．３５重量％の過硫酸カリウム水溶液を連続的に滴下して行い、重合転化率９０％で、重合停止剤として２，６−ターシャリーブチル−４−メチルフェノール０．０５重量％を添加し重合を停止した。その後、減圧下で未反応単量体の除去を行ない、ラテックスＡとＢを得た。得られたラテックスＡとＢを表１に示す比率で混合し、目的のクロロプレン重合体ラテックスを得た。
Example 1
Chloroprene monomer, n-dodecyl mercaptan, potassium rosinate (trade name Longus K-25, manufactured by Arakawa Chemical Co., Ltd., (content of 8,15-isopimalic acid) / (dihydropimalic acid) in the proportions shown in Table 1 Content) = 0.5), a condensate of sodium naphthalenesulfonate and formaldehyde, sodium hydroxide, sodium hydrosulfite and pure water were polymerized at 40 ° C. in a 10 L autoclave equipped with a stirrer. Polymerization was carried out by continuously dropping 0.35% by weight aqueous potassium persulfate in a nitrogen atmosphere, with a polymerization conversion rate of 90% and 2,6-tertiarybutyl-4-methylphenol as a polymerization terminator. The polymerization was stopped by adding 05% by weight. Thereafter, unreacted monomers were removed under reduced pressure to obtain latexes A and B. The obtained latexes A and B were mixed at the ratio shown in Table 1 to obtain the desired chloroprene polymer latex.
一方、酸化亜鉛、硫黄、加硫促進剤ＤＰＴＵ（Ｎ，Ｎ‘−ジフェニルチオウレア）、加硫促進剤ＤＰＧ（１，３−ジフェニルグアニジン）それぞれを１００重量％として、アンモニウムガゼイン３重量％、ナフタレンスルホン酸ナトリウムのホルマリン縮合物３重量％、蒸留水１００重量％をそれぞれ混合し、ボールミルにて１日撹拌することにより、各配合剤の安定な懸濁液を作製した。 On the other hand, zinc oxide, sulfur, vulcanization accelerator DPTU (N, N'-diphenylthiourea), vulcanization accelerator DPG (1,3-diphenylguanidine) is 100% by weight, ammonium gazein 3% by weight, naphthalene sulfone 3% by weight of a formalin condensate of sodium acid and 100% by weight of distilled water were mixed and stirred in a ball mill for 1 day to prepare a stable suspension of each compounding agent.
クロロプレン重合体ラテックス中の固形分量を１００重量部として、酸化亜鉛５重量部、硫黄１重量部、加硫促進剤ＤＰＴＵを３重量部、加硫促進剤ＤＰＧを２重量部％となるように各配合剤の懸濁液をクロロプレン重合体ラテックスへ添加し、２４時間撹拌することによりラテックス組成物を作製した。 The solid content in the chloroprene polymer latex is 100 parts by weight, each of the zinc oxide 5 parts by weight, sulfur 1 part by weight, vulcanization accelerator DPTU 3 parts by weight, and vulcanization accelerator DPG 2 parts by weight. The suspension of the compounding agent was added to the chloroprene polymer latex and stirred for 24 hours to prepare a latex composition.
２５％硝酸カルシウム水溶液に浸漬し、乾燥させた平板状の型をクロロプレン重合体ラテックス組成物に浸漬することで、平板上にゴムフィルムを凝集形成させた。次いで型とともに６０℃温水に浸し、水溶性の不純物を溶出させた後、１２０℃の熱風乾燥機にて３０分間加熱し乾燥および加硫を行なった。型からゴムを剥がし、厚さ０．２５ｍｍ程度の加硫ゴムシートを得た。 A rubber plate was agglomerated and formed on the flat plate by immersing the dried flat plate mold in a 25% calcium nitrate aqueous solution in the chloroprene polymer latex composition. Next, the mold was immersed in 60 ° C. warm water together with the mold to elute out water-soluble impurities, and then heated and dried for 30 minutes in a 120 ° C. hot air dryer. The rubber was removed from the mold to obtain a vulcanized rubber sheet having a thickness of about 0.25 mm.
次に得られた加硫ゴムシートの常態特性を測定した。加硫物特性を表１に示す。高破断強度と低モジュラスを有した、強度と柔軟性に優れる加硫ゴムが得られた。 Next, normal characteristics of the obtained vulcanized rubber sheet were measured. The vulcanizate properties are shown in Table 1. A vulcanized rubber having high breaking strength and low modulus and excellent strength and flexibility was obtained.
実施例２〜１２
実施例１と同様に、それぞれ表１に示した組成で重合を行ない、目的のクロロプレンラテックス重合体を得た。次いで実施例１と同様にラテックス組成物を作製し、浸漬操作を行なうことでそれぞれ加硫ゴムシートを得た。いずれも高破断強度と低モジュラスを有した、強度と柔軟性に優れる加硫ゴムが得られた。
Examples 2-12
In the same manner as in Example 1, polymerization was carried out with the compositions shown in Table 1 to obtain the intended chloroprene latex polymer. Next, a latex composition was prepared in the same manner as in Example 1, and a vulcanized rubber sheet was obtained by performing an immersion operation. In all cases, a vulcanized rubber having high strength at break and low modulus and excellent in strength and flexibility was obtained.
比較例１，２，５
実施例１と同様に、表２に示した組成で重合を行ない、目的のクロロプレンラテックス重合体を得た。次いで実施例１と同様にラテックス組成物を作製し、浸漬操作を行なうことでそれぞれ加硫ゴムシートを得た。破断強度に劣った。
Comparative Examples 1, 2, 5
In the same manner as in Example 1, polymerization was carried out with the composition shown in Table 2 to obtain the desired chloroprene latex polymer. Next, a latex composition was prepared in the same manner as in Example 1, and a vulcanized rubber sheet was obtained by performing an immersion operation. It was inferior in breaking strength.
比較例３，４
実施例１と同様に、表１に示した組成で重合を行ない、目的のクロロプレンラテックス重合体を得た。次いで実施例１と同様にラテックス組成物を作製し、浸漬操作を行なうことでそれぞれ加硫ゴムシートを得た。破断強度と柔軟性に劣った。
Comparative Examples 3 and 4
In the same manner as in Example 1, polymerization was carried out with the composition shown in Table 1 to obtain the intended chloroprene latex polymer. Next, a latex composition was prepared in the same manner as in Example 1, and a vulcanized rubber sheet was obtained by performing an immersion operation. Inferior in breaking strength and flexibility.
比較例６
実施例１と同様に、表１に示した組成で重合を行ない、目的のクロロプレンラテックス重合体を得た。次いで実施例１と同様にラテックス組成物を作製し、浸漬操作を行なうことでそれぞれ加硫ゴムシートを得た。柔軟性に劣った。
Comparative Example 6
In the same manner as in Example 1, polymerization was carried out with the composition shown in Table 1 to obtain the intended chloroprene latex polymer. Next, a latex composition was prepared in the same manner as in Example 1, and a vulcanized rubber sheet was obtained by performing an immersion operation. Poor flexibility.
比較例７
実施例１と同様に、表２に示した組成で重合を行ない、目的のクロロプレンラテックス重合体を得た。重合には、（８，１５−イソピマル酸の含有量）÷（ジヒドロピマル酸の含有量）＝６．７であるロジン酸カリウム（ハリマ化成（株）製、商品名バンディスＴ−２５ＫＰ）を用いた。次いで実施例１と同様にラテックス組成物を作製し、浸漬操作を行なうことでそれぞれ加硫ゴムシートを得た。実施例と比較して平板と加硫シートの粘着が強く、離型性に劣った。
Comparative Example 7
In the same manner as in Example 1, polymerization was carried out with the composition shown in Table 2 to obtain the desired chloroprene latex polymer. For the polymerization, potassium rosinate (Harima Kasei Co., Ltd., trade name Bandis T-25KP) in which (content of 8,15-isopimalic acid) ÷ (content of dihydropimalic acid) = 6.7 was used. . Next, a latex composition was prepared in the same manner as in Example 1, and a vulcanized rubber sheet was obtained by performing an immersion operation. Compared with the Examples, the adhesion between the flat plate and the vulcanized sheet was strong, and the releasability was poor.
比較例８
実施例１と同様に、表２に示した組成で重合を行ない、目的のクロロプレンラテックス重合体を得た。重合には、（８，１５−イソピマル酸の含有量）÷（ジヒドロピマル酸の含有量）＝４．２であるロジン酸カリウム（ハリマ化成（株）製、商品名バンディスＴ−３４Ｋ）を用いた。次いで実施例１と同様にラテックス組成物を作製し、浸漬操作を行なうことでそれぞれ加硫ゴムシートを得た。実施例と比較して平板と加硫シートの粘着が強く、離型性に劣った。
Comparative Example 8
In the same manner as in Example 1, polymerization was carried out with the composition shown in Table 2 to obtain the desired chloroprene latex polymer. For the polymerization, potassium rosinate (trade name Bandis T-34K, manufactured by Harima Kasei Co., Ltd.) with (8,15-isopimalic acid content) ÷ (dihydropimalic acid content) = 4.2 was used. . Next, a latex composition was prepared in the same manner as in Example 1, and a vulcanized rubber sheet was obtained by performing an immersion operation. Compared with the Examples, the adhesion between the flat plate and the vulcanized sheet was strong, and the releasability was poor.
比較例９
実施例１と同様に、表２に示した組成で重合を行ない、目的のクロロプレンラテックス重合体を得た。次いで実施例１と同様にラテックス組成物を作製し、浸漬操作を行なうことでそれぞれ加硫ゴムシートを得た。実施例と比較しフィルムの形成性が劣ったため、ムラの多い加硫ゴムシートを得た。結果、破断強度に劣った。
Comparative Example 9
In the same manner as in Example 1, polymerization was carried out with the composition shown in Table 2 to obtain the desired chloroprene latex polymer. Next, a latex composition was prepared in the same manner as in Example 1, and a vulcanized rubber sheet was obtained by performing an immersion operation. Since the film formability was inferior to that of the example, a vulcanized rubber sheet with a lot of unevenness was obtained. As a result, the breaking strength was inferior.
比較例１０
実施例１と同様に、表２に示した組成で重合を行ない、目的のクロロプレンラテックス重合体を得た。次いで実施例１と同様にラテックス組成物を作製したが、２４時間撹拌後にゴムの析出が見られ、平板への均一がフィルム形成ができなかった。
Comparative Example 10
In the same manner as in Example 1, polymerization was carried out with the composition shown in Table 2 to obtain the desired chloroprene latex polymer. Next, a latex composition was produced in the same manner as in Example 1. However, after 24 hours of stirring, rubber deposition was observed, and the film could not be uniformly formed on a flat plate.
本発明のクロロプレン重合体ラテックスは、容易に浸漬成型が可能でかつ浸漬加硫フィルムの高い破断強度と優れた柔軟性と力学物性を要求される用途、例えば試験検査用手袋、医療用手袋などとして使用することができる。 The chloroprene polymer latex of the present invention can be easily dip-molded and used in applications requiring high rupture strength, excellent flexibility and mechanical properties of immersion vulcanized films, such as test inspection gloves and medical gloves. Can be used.
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