JP4426394B2 - Bonding method - Google Patents
Bonding method Download PDFInfo
- Publication number
- JP4426394B2 JP4426394B2 JP2004211154A JP2004211154A JP4426394B2 JP 4426394 B2 JP4426394 B2 JP 4426394B2 JP 2004211154 A JP2004211154 A JP 2004211154A JP 2004211154 A JP2004211154 A JP 2004211154A JP 4426394 B2 JP4426394 B2 JP 4426394B2
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- JP
- Japan
- Prior art keywords
- weight
- paste
- component
- block
- isobutylene
- Prior art date
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Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、特にポリウレタンとの接着性に優れ、かつ柔軟性・絶縁性に優れるペーストを用いた接着方法に関する。 The present invention relates to an adhesion method using a paste that is particularly excellent in adhesiveness to polyurethane and is excellent in flexibility and insulation.
従来、ポリ塩化ビニル／フタル酸可塑剤系やポリウレタン／有機溶剤系のペーストの熱処理から得られる成形品のひとつに手袋があるが、これらの成形品は、耐油性や耐摩耗性には優れているものの、体積抵抗率が１０12〜１０13［Ω・ｃｍ］であるため、絶縁特性に劣り、２００Ｖ以下で使用せざるを得ない状況であった。 Conventionally, gloves are one of the molded products obtained by heat treatment of polyvinyl chloride / phthalic acid plasticizer system and polyurethane / organic solvent system pastes, but these molded products have excellent oil resistance and wear resistance. However, since the volume resistivity was 10 12 to 10 13 [Ω · cm], the insulating properties were inferior, and it was inevitable to use at 200 V or less.
また、天然ゴムラテックスから得られる手袋は絶縁特性には優れるものの、皮膚へのアレルギー問題や、ゴム臭気、ゴワゴワ感があり、細かい作業や長時間の作業には耐えられず、原因となると考えられる天然ゴムに含まれる蛋白質量を減らすために、−ＯＨ基を有する微粒子をゴムラテックスに含有させたり（例えば、特許文献１参照。）、プロテアーゼを添加させたり（例えば、特許文献２参照。）しているが、未だ満足な結果が得られず、追加の工程を必要とするという問題を有するという状況にある。
このように従来は絶縁特性、耐油性、耐摩耗性、柔軟性全てにわたり充分な特性を持ちディッピング成形に適する素材がなかった。
また、多層構造を実現するためには特にディッピング成形を行った場合の各層間の接着性が必要であったが、上記の特性を全て満たす組み合わせは見いだされていなかった。
In addition, although gloves obtained from natural rubber latex have excellent insulation properties, they have skin allergy problems, rubber odors, and tingling sensations, and they cannot withstand fine work or long work, which may be the cause. In order to reduce the amount of protein contained in natural rubber, fine particles having —OH groups are contained in rubber latex (for example, see Patent Document 1) or protease is added (for example, see Patent Document 2). However, it still has a problem that a satisfactory result cannot be obtained and an additional process is required.
As described above, there has been no material suitable for dipping molding having sufficient characteristics in all of insulating properties, oil resistance, wear resistance, and flexibility.
Further, in order to realize a multilayer structure, adhesion between the respective layers was particularly required when dipping molding was performed, but no combination satisfying all of the above characteristics was found.
本発明の目的は、特に、ポリウレタンとの接着性に優れ、かつ柔軟性・絶縁性・ディッピング成形性に優れるペーストを用いた接着方法を提供することにある。 An object of the present invention is to provide an adhesion method using a paste that is particularly excellent in adhesion to polyurethane and that is excellent in flexibility, insulation, and dipping formability.
請求項１に記載の発明は、型上に、下記（１）のペーストおよび下記（２）のペーストを任意の順番でディッピング成形することを特徴とする、イソブチレン系化合物ブロック及び芳香族ビニル系化合物ブロックから構成されるイソブチレン系ブロック共重合体とポリウレタンとの接着方法である。
（１）（ａ）イソブチレン系化合物ブロック及び芳香族ビニル系化合物ブロックから構成されるイソブチレン系ブロック共重合体を含有するペースト
（２）ポリウレタンペースト
請求項２に記載の発明は、前記（１）のペーストが、前記（ａ）イソブチレン系ブロック共重合体１００重量部に対し、（ｂ）水添及び／または部分水添共重合体１〜８０重量部を含むことを特徴とする請求項１に記載の接着方法である。
請求項３に記載の発明は、前記（１）のペーストが、前記（ａ）イソブチレン系ブロック共重合体１００重量部に対し、（ｃ）非芳香族系ゴム用軟化剤１〜１００重量部を含むことを特徴とする請求項１又は２に記載の接着方法である。
請求項４に記載の発明は、前記（１）のペーストが、前記（ａ）イソブチレン系ブロック共重合体１００重量部に対し、（ｄ）石油樹脂１〜５０重量部を含むことを特徴とする請求項１〜３いずれか１項に記載の接着方法である。 The invention according to claim 1 is characterized in that the paste of the following (1) and the paste of the following (2) are dip-molded on the mold in an arbitrary order, and the isobutylene compound block and the aromatic vinyl compound This is an adhesion method between an isobutylene block copolymer composed of blocks and polyurethane.
(1) (a) Paste containing an isobutylene block copolymer composed of an isobutylene compound block and an aromatic vinyl compound block
(2) Polyurethane paste
The invention according to claim 2 is characterized in that the paste of (1) is (b) hydrogenated and / or partially hydrogenated copolymers 1 to 80 with respect to 100 parts by weight of the (a) isobutylene block copolymer. The bonding method according to claim 1, further comprising a weight part.
The invention according to claim 3 is characterized in that the paste of (1) comprises (c) 1 to 100 parts by weight of a non-aromatic rubber softener for 100 parts by weight of the isobutylene block copolymer. The adhesion method according to claim 1, wherein the adhesion method is included.
The invention according to claim 4 is characterized in that the paste of (1) contains (d) 1 to 50 parts by weight of a petroleum resin with respect to 100 parts by weight of the (a) isobutylene block copolymer. It is the adhesion | attachment method of any one of Claims 1-3.
本発明は、特にポリウレタンとの接着性に優れ、かつ柔軟性・絶縁性に優れるペーストを用いた接着方法に関する。 The present invention relates to an adhesion method using a paste that is particularly excellent in adhesiveness to polyurethane and is excellent in flexibility and insulation.
まず前記（１）のペースト（以下、組成物または樹脂組成物ともいう）の構成成分のうち、（ａ）イソブチレン系化合物ブロック及び芳香族ビニル系化合物ブロックから構成されるイソブチレン系ブロック共重合体について説明する。 Or not a (1) of paste of constituents (hereinafter compositions or also referred to as resin composition), (a) isobutylene-based compound block and aromatic vinyl isobutylene block copolymer comprising a Compound blocks Will be described.
本発明で使用されるイソブチレン系ブロック共重合体は、イソブチレンを主体とするユニットと芳香族ビニル化合物を主体とするユニットを有しているものであれば、いずれの構造を有するものも使用可能であるが、物性のバランスと合成の簡便さから、（芳香族ビニル化合物を主体とするユニットとイソブチレンを主体とするユニットと芳香族ビニル化合物を主体とするユニット）の構造を有するトリブロック体、（イソブチレンを主体とするユニットと芳香族ビニル化合物を主体とするユニット）の構造を有するジブロック体、またはこれらの混合物を用いることができる。ブロック共重合体のイソブチレンを主体とするユニットと芳香族ビニル化合物を主体とするユニットの割合は、物性のバランスから、イソブチレンを主体とする単量体９５〜２０重量％と芳香族ビニル化合物を主体とする単量体５〜８０重量％が好ましく、さらにイソブチレンを主体とする単量体９０〜６０重量％と芳香族ビニル化合物を主体とする単量体１０〜４０重量％が好ましい。 The isobutylene block copolymer used in the present invention may be any having any structure as long as it has a unit mainly composed of isobutylene and a unit mainly composed of an aromatic vinyl compound. However, a triblock body having a structure of (a unit mainly composed of an aromatic vinyl compound, a unit mainly composed of isobutylene, and a unit mainly composed of an aromatic vinyl compound) from the balance of physical properties and ease of synthesis, A diblock body having a structure of a unit mainly composed of isobutylene and a unit mainly composed of an aromatic vinyl compound), or a mixture thereof can be used. The ratio of the unit mainly composed of isobutylene and the unit mainly composed of aromatic vinyl compound in the block copolymer is mainly composed of 95 to 20% by weight of monomer mainly composed of isobutylene and aromatic vinyl compound from the balance of physical properties. The monomer is preferably 5 to 80% by weight, more preferably 90 to 60% by weight of the monomer mainly composed of isobutylene and 10 to 40% by weight of the monomer mainly composed of the aromatic vinyl compound.
イソブチレン系ブロック共重合体の重量平均分子量は、特に制限はないが、４０，０００〜５００，０００が好ましく、６０，０００〜４００，０００が特に好ましい。重量平均分子量が４０，０００未満の場合、機械特性が低下、また、５００，０００を超える場合、成形性が悪化する。 The weight average molecular weight of the isobutylene block copolymer is not particularly limited, but is preferably 40,000 to 500,000, particularly preferably 60,000 to 400,000. When the weight average molecular weight is less than 40,000, the mechanical properties are deteriorated, and when it exceeds 500,000, the moldability is deteriorated.
上記芳香族ビニル系重合体ブロックで用いられる芳香族ビニル化合物としては、スチレン、α−メチルスチレン、β−メチルスチレン、ｐ−メチルスチレン、ｔ−ブチルスチレン、モノクロロスチレン、ジクロロスチレン、メトキシスチレン等が挙げられる。上記化合物の中でもコストと物性及び生産性のバランスからスチレン、α−メチルスチレン、ｐ−メチルスチレンが好ましく、その中から２種以上選んでもよい。 Examples of the aromatic vinyl compound used in the aromatic vinyl polymer block include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, t-butylstyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, and the like. Can be mentioned. Among the above compounds, styrene, α-methylstyrene, and p-methylstyrene are preferable from the balance of cost, physical properties, and productivity, and two or more of them may be selected.
イソブチレン系ブロック共重合体の具体例としては、鐘淵化学（株）製の１０３Ｔ（数平均分子量＝９２，０００、重量平均分子量＝１００，０００）又は０７３Ｔ（数平均分子量＝６０，０００、重量平均分子量＝６５，０００）等を挙げることができる。 Specific examples of the isobutylene block copolymer include 103T (number average molecular weight = 92,000, weight average molecular weight = 100,000) or 073T (number average molecular weight = 60,000, weight) manufactured by Kaneka Chemical Co., Ltd. Average molecular weight = 65,000).
必要に応じて添加する成分（ｂ）水添及び／または部分水添共重合体は、増粘剤（粘度調整剤）として機能する。成分（ｂ）としては、芳香族ビニル化合物−共役ジエン化合物系ブロック共重合体の水添物及び／または部分水添物、共役ジエン化合物系ブロック共重合体の水添物及び／または部分水添物、芳香族ビニル化合物−共役ジエン化合物系ランダム共重合体の水添物及び／または部分水添物等を挙げることができる。これらの中では、芳香族ビニル化合物−共役ジエン化合物系ブロック共重合体の水添物及び／または部分水添物、共役ジエン化合物系ブロック共重合体の水添物及び／または部分水添物が好ましい。 The component (b) hydrogenated and / or partially hydrogenated copolymer added as necessary functions as a thickener (viscosity modifier). As component (b), hydrogenated and / or partially hydrogenated aromatic vinyl compound-conjugated diene compound block copolymer, hydrogenated and / or partially hydrogenated conjugated diene compound block copolymer And hydrogenated and / or partially hydrogenated products of aromatic vinyl compound-conjugated diene compound-based random copolymers. Among these, hydrogenated products and / or partially hydrogenated aromatic vinyl compound-conjugated diene compound block copolymers, hydrogenated products and / or partially hydrogenated conjugated diene compound block copolymers are included. preferable.
上記芳香族ビニル化合物−共役ジエン化合物系ブロック共重合体の水添物及び／または部分水添物としては、芳香族ビニル化合物を主体とする少なくとも１個の重合体ブロックＡと、共役ジエン化合物を主体とする少なくとも１個の重合体ブロックＢとからなるブロック共重合体を水素添加物及び／又は部分水素添加物を挙げることができる。
芳香族ビニル化合物を主体とする少なくとも１個の重合体ブロックＡと、共役ジエン化合物を主体とする少なくとも１個の重合体ブロックＢとからなるブロック共重合体の水素添加物及び／又は部分水素添加物成分は、芳香族ビニル化合物を主体とする重合体ブロックＡの少なくとも１個と、共役ジエン化合物を主体とする重合体ブロックＢの少なくとも１個とからなるブロック共重合体を水素添加して得られる重合体である。例えば、Ａ−Ｂ、Ａ−Ｂ−Ａ、Ｂ−Ａ−Ｂ−Ａ、Ａ−Ｂ−Ａ−Ｂ−Ａ等の構造を有する芳香族ビニル化合物−共役ジエン化合物のブロック共重合体を水素添加して得られるものである。
As the hydrogenated product and / or partially hydrogenated product of the aromatic vinyl compound-conjugated diene compound block copolymer, at least one polymer block A mainly composed of an aromatic vinyl compound and a conjugated diene compound are used. Examples of the block copolymer comprising at least one polymer block B as a main component include a hydrogenated product and / or a partially hydrogenated product.
Hydrogenated and / or partially hydrogenated block copolymer comprising at least one polymer block A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound The product component is obtained by hydrogenating a block copolymer comprising at least one polymer block A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound. Polymer. For example, a hydrogenated block copolymer of an aromatic vinyl compound-conjugated diene compound having a structure such as A-B, A-B-A, B-A-B-A, or A-B-A-B-A Is obtained.
芳香族ビニル化合物を主体とする重合体ブロックＡは、芳香族ビニル化合物のみからなる重合体か、芳香族ビニル化合物と５０重量％未満の共役ジエン化合物との共重合体であってもよい。また、共役ジエン化合物を主体とする重合体ブロックＢは、共役ジエン化合物のみからなる重合体か、共役ジエン化合物と５０重量％未満の芳香族ビニル化合物の共重合体であってもよい。 The polymer block A mainly composed of an aromatic vinyl compound may be a polymer composed only of an aromatic vinyl compound or a copolymer of an aromatic vinyl compound and less than 50% by weight of a conjugated diene compound. The polymer block B mainly composed of a conjugated diene compound may be a polymer composed solely of a conjugated diene compound or a copolymer of a conjugated diene compound and less than 50% by weight of an aromatic vinyl compound.
芳香族ビニル化合物−共役ジエン化合物系ブロック共重合体を構成する芳香族ビニル化合物としては、例えば、スチレン、α−メチルスチレン、ビニルトルエン、ｐ−第３ブチルスチレン等のうちから１種又は２種以上を選択でき、なかでもスチレンが好ましい。また共役ジエン化合物としては、例えば、ブタジエン、イソプレン、１，３−ペンタジエン、２，３−ジメチル−１，３−ブタジエン等のうちから１種又は２種以上が選ばれ、なかでもブタジエン、イソプレン及びこれらの組合せが好ましい。 Examples of the aromatic vinyl compound constituting the aromatic vinyl compound-conjugated diene compound block copolymer include one or two of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, and the like. From the above, styrene is preferable. In addition, as the conjugated diene compound, for example, one or two or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene and These combinations are preferred.
芳香族ビニル化合物を主体とする少なくとも１個の重合体ブロックＡと、共役ジエン化合物を主体とする少なくとも１個の重合体ブロックＢとからなるブロック共重合体の水素添加物及び／又は部分水素添加物成分は、共役ジエン化合物を主体とする重合体ブロックＢにおいて、その水素添加率は任意であるが、好ましくは５０％以上、より好ましくは５５％以上、更に好ましくは６０％以上である。また、そのミクロ構造は、任意であり、例えば、ブロックＢがブタジエン単独で構成される場合、ポリブタジエンブロックにおいては、１，２−ミクロ構造が好ましくは２０〜５０重量％、特に好ましくは２５〜４５重量％である。また、１，２−ミクロ構造を選択的に水素添加した物であっても良い。ブロックＢがイソプレンとブタジエンの混合物から構成される場合、１，２−ミクロ構造が好ましくは５０％未満、より好ましくは２５％未満、より更に好ましくは１５％未満である。 Hydrogenated and / or partially hydrogenated block copolymer comprising at least one polymer block A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound In the polymer block B mainly composed of a conjugated diene compound, the hydrogenation rate of the physical component is arbitrary, but it is preferably 50% or more, more preferably 55% or more, and still more preferably 60% or more. Further, the microstructure is arbitrary. For example, when the block B is composed of butadiene alone, the polybutadiene block preferably has a 1,2-microstructure of 20 to 50% by weight, particularly preferably 25 to 45%. % By weight. Moreover, the thing which selectively hydrogenated 1,2-microstructure may be sufficient. When block B is composed of a mixture of isoprene and butadiene, the 1,2-microstructure is preferably less than 50%, more preferably less than 25%, and even more preferably less than 15%.
ブロックＢがイソプレン単独で構成される場合、ポリイソプレンブロックにおいてはイソプレンの好ましくは７０〜１００重量％が１，４−ミクロ構造を有し、かつイソプレンに由来する脂肪族二重結合の好ましくは少なくとも９０％が水素添加されたものが好ましい。 When block B is composed of isoprene alone, in the polyisoprene block, preferably 70 to 100% by weight of isoprene has a 1,4-microstructure, and preferably at least aliphatic double bonds derived from isoprene. 90% hydrogenated is preferred.
また、重合体ブロックＡは、成分全体の５〜７０重量％の割合で存在するのが好ましい。さらに、成分全体の重量平均分子量は、３５０，０００以下であり、好ましくは３０，０００〜２５０，０００である。重量平均分子量が３５０，０００を超えると、成形性が悪化する。 Moreover, it is preferable that the polymer block A exists in the ratio of 5-70 weight% of the whole component. Furthermore, the weight average molecular weight of the whole component is 350,000 or less, Preferably it is 30,000-250,000. If the weight average molecular weight exceeds 350,000, the moldability deteriorates.
芳香族ビニル化合物−共役ジエン化合物ブロック共重合体の水添物及び／または部分水添物の具体例としては、スチレン−エチレン・ブテン共重合体（ＳＥＢ）、スチレン−エチレン・プロピレン共重合体（ＳＥＰ）、スチレン−エチレン・ブテン−スチレン共重合体（ＳＥＢＳ）、スチレン−エチレン・プロピレン−スチレン共重合体（ＳＥＰＳ）、スチレン−エチレン・エチレン・プロピレン−スチレン共重合体（ＳＥＥＰＳ）、スチレン−ブタジエン・ブチレン−スチレン共重合体（スチレン−ブタジエン−スチレン共重合体オ部分水添物、ＳＢＢＳ）、スチレン−イソプレン−スチレン共重合体の部分水添物、スチレン−イソプレン・ブタジエン−スチレン共重合体の部分水添物等を挙げることができる。本発明においては、該芳香族ビニル化合物−共役ジエン化合物ブロック共重合体の水素添加物及び／又は部分水素添加物は、単独で用いてもよく、２種以上を混合して用いてもよい。 Specific examples of the hydrogenated and / or partially hydrogenated aromatic vinyl compound-conjugated diene compound block copolymer include styrene-ethylene-butene copolymer (SEB), styrene-ethylene-propylene copolymer ( SEP), styrene-ethylene-butene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS), styrene-butadiene -Butylene-styrene copolymer (styrene-butadiene-styrene copolymer o partially hydrogenated product, SBBS), partially hydrogenated product of styrene-isoprene-styrene copolymer, styrene-isoprene-butadiene-styrene copolymer A partially hydrogenated product can be used. In the present invention, the hydrogenated product and / or the partial hydrogenated product of the aromatic vinyl compound-conjugated diene compound block copolymer may be used alone or in admixture of two or more.
これらの芳香族ビニル化合物を主体とする少なくとも１個の重合体ブロックＡと、共役ジエン化合物を主体とする少なくとも１個の重合体ブロックＢとからなるブロック共重合体を水素添加して得られるブロック共重合体の製造方法としては、数多くの方法が提案されているが、代表的な方法としては、例えば特公昭４０−２３７９８号公報に記載された方法により、リチウム触媒又はチーグラー型触媒を用い、不活性媒体中でブロック重合させて得ることができる。こうしたブロック共重合体の水素添加処理は、公知の方法により、不活性溶媒中で水素添加触媒の存在下に行うことができる。 A block obtained by hydrogenating a block copolymer comprising at least one polymer block A mainly composed of these aromatic vinyl compounds and at least one polymer block B mainly composed of a conjugated diene compound. As a method for producing a copolymer, a number of methods have been proposed. As a typical method, for example, a lithium catalyst or a Ziegler type catalyst is used by the method described in JP-B-40-23798. It can be obtained by block polymerization in an inert medium. Such a hydrogenation treatment of the block copolymer can be performed by a known method in the presence of a hydrogenation catalyst in an inert solvent.
また、上記共役ジエン化合物系ブロック共重合体の水添物としては、例えば、ブタジエンのブロック共重合体を水素添加して得られる結晶性エチレンブロックと非晶性エチレン−ブテンブロックを有するブロック共重合体（ＣＥＢＣ）、ブタジエンのブロック共重合体を水素添加して得られる結晶性エチレンブロックと非晶性エチレン−ブテンブロックと芳香族ビニル化合物から成るブロックを有するブロック共重合体（ＳＥＢＣ）等が挙げられる。本発明においては、水添共役ジエン化合物ブロック共重合体は、単独で用いてもよく、２種以上を混合して用いてもよい。
この共役ジエン化合物系ブロック共重合体の水添物の重量平均分子量は、好ましくは３５０，０００以下であり、より好ましくは３０，０００〜２５０，０００である。重量平均分子量が３５０，０００を超えると、成形性が悪化する。
Examples of the hydrogenated product of the conjugated diene compound block copolymer include a block copolymer having a crystalline ethylene block and an amorphous ethylene-butene block obtained by hydrogenating a block copolymer of butadiene. Examples thereof include a block copolymer (SEBC) having a block composed of a crystalline ethylene block, an amorphous ethylene-butene block and an aromatic vinyl compound obtained by hydrogenating a block copolymer of butadiene (CEBC) and butadiene. It is done. In the present invention, the hydrogenated conjugated diene compound block copolymer may be used alone or in combination of two or more.
The weight average molecular weight of the hydrogenated product of this conjugated diene compound-based block copolymer is preferably 350,000 or less, more preferably 30,000 to 250,000. If the weight average molecular weight exceeds 350,000, the moldability deteriorates.
さらに、上記芳香族ビニル化合物−共役ジエン化合物系ランダム共重合体の水添物としては、例えば、芳香族ビニル化合物（スチレン）と共役ジエン化合物（ブタジエン）を主体とするランダム共重合体の水素添加物（Ｈ−ＳＢＲ）が挙げられ、具体的な市販品としては、例えば、ＪＳＲ（株）製のダイナロン１３２０Ｐ（商品名）が挙げられる。 Furthermore, as a hydrogenated product of the above aromatic vinyl compound-conjugated diene compound-based random copolymer, for example, hydrogenation of a random copolymer mainly composed of an aromatic vinyl compound (styrene) and a conjugated diene compound (butadiene) Product (H-SBR), and as a specific commercial product, for example, Dynaron 1320P (trade name) manufactured by JSR Corporation may be mentioned.
成分（ｂ）を添加する場合の配合量は、成分（ａ）１００重量部に対して１〜８０重量部、好ましくは３〜５０重量部である。前記上限値を超えるとポリウレタンに熱融着しにくくなると同時に、粘度が高くなりすぎ、成形加工性が悪化する。前記下限値未満では添加効果（キシロール、ＭＥＫ、ＤＭＦなどの溶剤でペーストにした時の増粘効果、気泡生成抑制防止効果、均一膜厚形成効果）が充分でない。 The amount of component (b) added is 1 to 80 parts by weight, preferably 3 to 50 parts by weight, per 100 parts by weight of component (a). When the upper limit is exceeded, it becomes difficult to heat-seal the polyurethane, and at the same time, the viscosity becomes too high and the molding processability deteriorates. If the amount is less than the lower limit, the effect of addition (thickening effect when the paste is made with a solvent such as xylol, MEK, or DMF, the effect of inhibiting the formation of bubbles, and the effect of forming a uniform film thickness) is not sufficient.
必要に応じて添加する（ｃ）非芳香族系ゴム用軟化剤は軟化剤として機能し、より柔軟性が必要なＡ硬度６０以下、好ましくは５０以下の用途に用いられる場合に添加される。
成分（ｃ）としては、非芳香族系の鉱物油又は液状、若しくは、低分子量の合成軟化剤が挙げられる。一般にゴム用鉱物油軟化剤は、芳香族環、ナフテン環及びパラフィン鎖を組み合わせた混合物であって、飽和炭化水素鎖炭素数が全炭素数の５０％以上を占めるものをパラフィン系、ナフテン環炭素数が３０〜４０％を占めるものをナフテン系、芳香族炭素数が３０％以上を占めるものを芳香族系と呼び区別されている。本発明で用いられるゴム用鉱物油軟化剤は、上記のパラフィン系及びナフテン系が好ましい。芳香族系の軟化剤は、分散性が悪く好ましくない。
非芳香族炭化水素系ゴム用軟化剤として、パラフィン系の鉱物油軟化剤が特に好ましく、パラフィン系のなかでも芳香族環成分の少ないものが特に適している。
The (c) softener for non-aromatic rubber added as necessary functions as a softener and is added when used for an A hardness of 60 or less, preferably 50 or less, which requires more flexibility.
Examples of the component (c) include non-aromatic mineral oils or liquid or low molecular weight synthetic softeners. Generally, a mineral oil softener for rubber is a mixture of an aromatic ring, a naphthene ring and a paraffin chain, and has a saturated hydrocarbon chain carbon number of 50% or more of the total carbon number. Those that occupy 30 to 40% are called naphthenes, and those that occupy 30% or more aromatic carbons are called aromatics. The mineral oil softener for rubber used in the present invention is preferably the paraffinic and naphthenic types described above. Aromatic softeners are not preferred because of their poor dispersibility.
As the non-aromatic hydrocarbon rubber softening agent, a paraffinic mineral oil softening agent is particularly preferable, and paraffinic ones having a small aromatic ring component are particularly suitable.
パラフィン系軟化剤を構成している化合物としては、例えば、炭素数４〜１５５のパラフィン系化合物、好ましくは炭素数４〜５０のパラフィン系化合物が挙げられ、具体的には、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカン、ドデカン、テトラデカン、ペンタデカン、ヘキサデカン、ヘプタデカン、オクタデカン、ノナデカン、エイコサン、ヘンエイコサン、ドコサン、トリコサン、テトラコサン、ペンタコサン、ヘキサコサン、ヘプタコサン、オクタコサン、ノナコサン、トリアコンタン、ヘントリアコンタン、ドトリアコンタン、ペンタトリアコンタン、ヘキサコンタン、ヘプタコンタン等のｎ−パラフィン（直鎖状飽和炭化水素）、イソブタン、イソペンタン、ネオペンタン、イソヘキサン、イソペンタン、ネオヘキサン、２，３−ジメチルブタン、２−メチルヘキサン、３−メチルヘキサン、３−エチルペンタン、２，２−ジメチルペンタン、２，３−ジメチルペンタン、２，４−ジメチルペンタン、３，３−ジメチルペンタン、２，２，３−トリメチルブタン、３−メチルヘプタン、２，２−ジメチルヘキサン、２，３−ジメチルヘキサン、２，４−ジメチルヘキサン、２，５−ジメチルヘキサン、３，４−ジメチルヘキサン、２，２，３−トリメチルペンタン、イソオクタン、２，３，４−トリメチルペンタン、２，３，３−トリメチルペンタン、２，３，４−トリメチルペンタン、イソノナン、２−メチルノナン、イソデカン、イソウンデカン、イソドデカン、イソトリデカン、イソテトラデカン、イソペンタデカン、イソオクタデカン、イソナノデカン、イソエイコサン、４−エチル−５−メチルオクタン等のイソパラフィン（分岐状飽和炭化水素）及び、これらの飽和炭化水素の誘導体等を挙げることができる。これらのパラフィンは、混合物で用いられ、室温で液状であるものが好ましい。 Examples of the compound constituting the paraffinic softener include paraffinic compounds having 4 to 155 carbon atoms, preferably paraffinic compounds having 4 to 50 carbon atoms, and specifically, butane, pentane, hexane. , Heptane, octane, nonane, decane, undecane, dodecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosan, heneicosan, docosan, tricosan, tetracosan, pentacosan, hexacosan, heptacosan, octacosan, triacotan, henakosan, triacontane, N-paraffins (linear saturated hydrocarbons) such as Contan, Dotriacontane, Pentatriacontane, Hexacontane, Heptacontane, etc., Isobutane, Isopentane, Neopentane, Isohexane, Pentane, neohexane, 2,3-dimethylbutane, 2-methylhexane, 3-methylhexane, 3-ethylpentane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3, 3-dimethylpentane, 2,2,3-trimethylbutane, 3-methylheptane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,4 -Dimethylhexane, 2,2,3-trimethylpentane, isooctane, 2,3,4-trimethylpentane, 2,3,3-trimethylpentane, 2,3,4-trimethylpentane, isononane, 2-methylnonane, isodecane, Isoundecane, isododecane, isotridecane, isotetradecane, isopentadecane, isoeo Tadekan, Isonanodekan, isoeicosane, 4-ethyl-5-isoparaffins methyl octane (branched saturated hydrocarbons) and can include derivatives of these saturated hydrocarbons. These paraffins are used in a mixture and are preferably liquid at room temperature.
室温で液状であるパラフィン系軟化剤の市販品としては、日本油脂株式会社製のＮＡソルベント（イソパラフィン系炭化水素油）、出光興産株式会社製のＰＷ−９０（ｎ−パラフィン系プロセスオイル）、出光石油化学株式会社製のＩＰ−ソルベント２８３５（合成イソパラフィン系炭化水素、９９．８重量％以上のイソパラフィン）、三光化学工業株式会社製のネオチオゾール（ｎ−パラフィン系プロセスオイル）等が挙げられる。 Commercially available paraffinic softeners that are liquid at room temperature include NA Solvent (isoparaffinic hydrocarbon oil) manufactured by Nippon Oil & Fats, PW-90 (n-paraffinic process oil) manufactured by Idemitsu Kosan Co., Ltd., and Idemitsu. Examples include IP-solvent 2835 (synthetic isoparaffinic hydrocarbon, 99.8% by weight or more isoparaffin) manufactured by Petrochemical Co., Ltd., and neothiozole (n-paraffinic process oil) manufactured by Sanko Chemical Co., Ltd.
また、非芳香族系炭化水素軟化剤には、少量の不飽和炭化水素及びこれらの誘導体が共存していても良い。不飽和炭化水素としては、エチレン、プロピレン、１−ブテン、２−ブテン、イソブチレン、１−ペンテン、２−ペンテン、３−メチル−１−ブテン、３−メチル−１−ブテン、２−メチル−２−ブテン、１−ヘキセン、２，３−ジメチル−２−ブテン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン等のエチレン系炭化水素、アセチレン、メチルアセチレン、１−ブチン、２−ブチン、１−ペンチン、１−ヘキシン、１−オクチン、１−ノニン、１−デシン等のアセチレン系炭化水素を挙げることができる。 Moreover, a small amount of unsaturated hydrocarbons and derivatives thereof may coexist in the non-aromatic hydrocarbon softener. Unsaturated hydrocarbons include ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2 -Ethylene hydrocarbons such as butene, 1-hexene, 2,3-dimethyl-2-butene, 1-heptene, 1-octene, 1-nonene, 1-decene, acetylene, methylacetylene, 1-butyne, 2- Examples thereof include acetylene hydrocarbons such as butyne, 1-pentyne, 1-hexyne, 1-octyne, 1-nonine and 1-decyne.
成分（ｃ）を添加する場合の配合量は、成分（ａ）１００重量部に対して１〜１００重量部、好ましくは３〜６０重量部である。前記上限値を超えると軟化剤のブリードアウトを生じやすく最終製品に粘着性を与え、成形体の機械的性質も低下せしめる。前記下限値未満では添加効果が充分でない。 The amount of component (c) added is 1 to 100 parts by weight, preferably 3 to 60 parts by weight per 100 parts by weight of component (a). When the above upper limit is exceeded, the softening agent tends to bleed out, giving the final product tackiness, and also reducing the mechanical properties of the molded product. Below the lower limit, the effect of addition is not sufficient.
更に必要に応じて本発明組成物には（ｄ）石油樹脂を含有することができる。
成分（ｄ）は、得られる組成物のポリウレタン接着性をさらに向上すること、さらなる柔軟性をもたせること、また機械特性を向上させ、さらにバランスのよい柔軟性と風合いを付与する機能を果たす成分である。
成分（ｄ）としては、石油精製工業、石油化学工業の各種工程、特にナフサの分解工程で得られる不飽和炭化水素を原料として共重合して得られる樹脂であって、Ｃ５留分を原料とした脂肪族系石油樹脂、Ｃ９留分を原料とした芳香族系石油樹脂、ジシクロペンタジエンを原料とした脂環族系石油樹脂、並びにテルペン系樹脂およびこれら２種以上が共重合した共重合系石油樹脂、さらにこれらを水素化した水素化石油樹脂などが例示できる。上記した樹脂の水素添石油樹脂は、上記の樹脂を当業者に公知の方法により水素添加して得られる。具体的には、出光石油化学（株）製のアイマーブ（水素化石油樹脂）、荒川化学工業（株）製のアルコン（水素化石油樹脂）、ヤスハラケミカル（株）製のクリアロン（水素化テルペン樹脂）、トーネックス（株）製のエスコレッツ（脂肪族系炭化水素樹脂）、などの市販品を用いることができる。
Furthermore, (d) petroleum resin can be contained in this invention composition as needed.
Component (d) is a component that functions to further improve the polyurethane adhesion of the resulting composition, to provide further flexibility, to improve mechanical properties, and to provide a more balanced flexibility and texture. is there.
Component (d) is a resin obtained by copolymerization using unsaturated hydrocarbons obtained in various processes in the petroleum refining industry and petrochemical industry, particularly in the naphtha decomposition process, with C5 fraction as the raw material. Aliphatic petroleum resin, aromatic petroleum resin made from C9 fraction, alicyclic petroleum resin made from dicyclopentadiene, terpene resin, and copolymerization system of these two or more Examples thereof include petroleum resins and hydrogenated petroleum resins obtained by hydrogenating these. The hydrogenated petroleum resin of the above-described resin can be obtained by hydrogenating the above resin by a method known to those skilled in the art. Specifically, Imabe (hydrogenated petroleum resin) manufactured by Idemitsu Petrochemical Co., Ltd., Alcon (hydrogenated petroleum resin) manufactured by Arakawa Chemical Industries, Ltd., and Clearon (hydrogenated terpene resin) manufactured by Yashara Chemical Co., Ltd. Commercial products such as Escorez (aliphatic hydrocarbon resin) manufactured by Tonex Co., Ltd. can be used.
成分（ｄ）を添加する場合の配合量は、成分（ａ）１００重量部に対して１〜５０重量部、好ましくは３〜２０重量部である。前記上限値を超えるとディッピング成形性が悪化し、ベタツキ性が顕著になる。前記下限値未満では柔軟性付与効果、ポリウレタン接着付与効果が充分でない。 The amount of component (d) added is 1 to 50 parts by weight, preferably 3 to 20 parts by weight per 100 parts by weight of component (a). When the upper limit is exceeded, the dipping formability deteriorates and the stickiness becomes remarkable. If it is less than the lower limit, the effect of imparting flexibility and the effect of imparting polyurethane adhesion are not sufficient.
必要に応じて添加される成分（ｅ）テルペン系オイルは製品への柔軟性付与と溶剤ペーストの粘度低減の機能を有する。
テルペン系オイルは、主として北米や中国本土に産するアカマツ、クロマツの立木から採取した生松脂を水蒸気蒸留して得られる精油、また同木のパルプ生産の副生物のテレピン油、あるいはオレンジの皮から抽出される精油またはこれらの精油から異性化反応等により誘導されたオレンジ油等から得られ、具体的には、炭素数１０からなるテルペン系炭化水素、テルペンエーテルが挙げられる。
The component (e) terpene oil added as necessary has functions of imparting flexibility to the product and reducing the viscosity of the solvent paste.
Terpene oil is derived from essential oils obtained by steam-distilling raw pine fat collected from red pine and black pine trees, mainly from North America and mainland China, and from turpentine oil or orange peel as a by-product of pulp production. It is obtained from extracted essential oils or orange oils derived from these essential oils by isomerization reaction or the like, and specifically includes terpene hydrocarbons and terpene ethers having 10 carbon atoms.
炭素数１０からなるテルペン系炭化水素としては、ミルセン（沸点１６７℃）、カレン（沸点１６７℃）、オシメン、ピネン（沸点１５５℃）、リモネン（沸点１７６℃）、カンフェン（沸点１６０℃）、テルピノレン（沸点１８７℃）、トリシクレン（沸点１５３℃）、テルピネン（沸点１７０〜１８０℃）、フェンチェン（沸点１５０〜１５５℃）、フェランドレン（沸点１７０〜１７５℃）、シルベストレン（沸点１７５℃）、サビネン（沸点１６３℃）、Ｐ−メンテン−１（カルボメンテン）（沸点１７６℃）、Ｐ−メンテン−３（沸点１６８℃）、Ｐ−サイメン、Ｐ−メンタン（沸点１６８℃）等が挙げられる。そのなかでも特に、α−ピネン、β−ピネン、リモネン、Ｐ−メンテン−１、Ｐ−メンテン−３、Ｐ−サイメン、Ｐ−メンタンが好ましい。 Terpenic hydrocarbons having 10 carbon atoms include myrcene (boiling point 167 ° C.), karene (boiling point 167 ° C.), osymene, pinene (boiling point 155 ° C.), limonene (boiling point 176 ° C.), camphene (boiling point 160 ° C.), terpinolene. (Boiling point 187 ° C.), tricyclene (boiling point 153 ° C.), terpinene (boiling point 170-180 ° C.), fenchen (boiling point 150-155 ° C.), ferrandrene (boiling point 170-175 ° C.), silbestrene (boiling point 175 ° C.), Sabinene (boiling point 163 ° C.), P-menten-1 (carbomentene) (boiling point 176 ° C.), P-menten-3 (boiling point 168 ° C.), P-cymene, P-menthane (boiling point 168 ° C.) and the like. Of these, α-pinene, β-pinene, limonene, P-menten-1, P-menten-3, P-cymene, and P-menthane are particularly preferable.
炭素数１０からなるテルペンエーテルとしては、１，４−シネオール（沸点１７３℃）、１，８−シネオール（沸点１７３℃）、ピノール（沸点１８０℃）等が挙げられる。その中でも特に、１，４−シネオール、１，８−シネオールから選ばれた少なくとも１種類が好ましい。 Examples of the terpene ether having 10 carbon atoms include 1,4-cineole (boiling point 173 ° C.), 1,8-cineole (boiling point 173 ° C.), pinol (boiling point 180 ° C.), and the like. Among these, at least one selected from 1,4-cineole and 1,8-cineole is particularly preferable.
成分（ｅ）を添加する場合の配合量は、成分（ａ）１００重量部に対して、１〜７５重量部、好ましくは５〜５０重量部である。前記上限値を超えると成形時の発生ガスと臭気が烈しくなり、製品表面にブリード感が認められるようになる。前記下限値未満では製品への柔軟性付与と溶剤ペーストの粘度低減効果が充分でない。 The amount of component (e) added is 1 to 75 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of component (a). When the upper limit is exceeded, the gas and odor generated during molding become intense, and a bleed feeling is recognized on the product surface. If it is less than the said lower limit, the softness | flexibility provision to a product and the viscosity reduction effect of a solvent paste are not enough.
成分（ｆ）：酸化防止剤
酸化防止剤としては、例えば、２，６−ジ−ｔｅｒｔ−ｐ−ブチル−ｐ−クレゾール、２，６−ジ−ｔｅｒｔ−ブチルフェノール、２，４−ジメチル−６−ｔｅｒｔ−ブチルフェノール、４，４−ジヒドロキシジフェニル、トリス（２−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）ブタン等のフェノール系酸化防止剤、ホスファイト系酸化防止剤、チオエーテル系酸化防止剤等が挙げられる。このうちフェノール系酸化防止剤、ホスファイト系酸化防止剤が特に好ましい。
Component (f): Antioxidant Examples of the antioxidant include 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butylphenol, and 2,4-dimethyl-6. Phenolic antioxidants such as tert-butylphenol, 4,4-dihydroxydiphenyl, tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, phosphite antioxidants, thioether antioxidants, etc. Is mentioned. Of these, phenolic antioxidants and phosphite antioxidants are particularly preferred.
本発明の組成物においては、さらに、本発明の目的を損なわない範囲で、熱安定剤、酸化防止剤、光安定剤、紫外線吸収剤、結晶核剤、ブロッキング防止剤、シール性改良剤、ステアリン酸、シリコーンオイル等の離型剤、ポリエチレンワックス等の滑剤、着色剤、顔料、無機充填剤［アルミナ、タルク、炭酸カルシウム、マイカ、ウォラストナイト（ウァラステナイト）、クレー］、発泡剤（有機系、無機系）、難燃剤（水和金属化合物、赤燐、ポリりん酸アンモニウム、アンチモン、シリコーン）などを配合することができる。
また発泡剤としては、エクスパンセル（エクスパンセル社製）、マツモトマイクロスフィアー（松本油脂製薬社製）が好ましい。
In the composition of the present invention, a heat stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a crystal nucleating agent, an antiblocking agent, a sealability improver, a stearin, and the like, as long as the object of the present invention is not impaired. Release agents such as acids and silicone oils, lubricants such as polyethylene wax, colorants, pigments, inorganic fillers [alumina, talc, calcium carbonate, mica, wollastonite, clay], foaming agents (organic) Inorganic), flame retardant (hydrated metal compound, red phosphorus, ammonium polyphosphate, antimony, silicone) and the like can be blended.
As the foaming agent, EXPANSEL (manufactured by EXPANSEL) and Matsumoto Microsphere (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) are preferable.
（ａ）及び必要に応じて添加される（ｂ）〜（ｆ）を添加した熱可塑性エラストマー１００重量部を溶剤（例えばキシロール：ゴードー溶剤製）８０〜４００重量部に溶解することによりポリウレタン接着用ディッピング溶液若しくは溶剤ペーストが得られる。好ましくは溶剤１００〜３００重量％である。前記上限値を超えると粘度が低下し、気泡が発生しやすくなり、膜厚が薄くなる。前記下限値未満では粘度が高くなり、ペースト性が悪化し、ディッピング成形性が悪化する。 For polyurethane adhesion by dissolving 100 parts by weight of thermoplastic elastomer to which (a) and (b) to (f) added as necessary are dissolved in 80 to 400 parts by weight of a solvent (for example, xylol: manufactured by Gordo solvent) A dipping solution or solvent paste is obtained. The solvent is preferably 100 to 300% by weight. When the upper limit is exceeded, the viscosity decreases, bubbles tend to be generated, and the film thickness becomes thin. If it is less than the said lower limit, a viscosity will become high, paste property will deteriorate, and dipping moldability will deteriorate.
以下、本発明の樹脂組成物の製造方法について説明する。
本発明の組成物は上記成分（ａ）及び必要に応じて添加される（ｂ）〜（ｆ）を混練温度１８０〜２００℃で、適当な単軸押出機、二軸押出機、ロール、バンバリーミキサー又は各種のニーダー等を用いて溶融混練して得られたペレットもしくはブロックを、工業用キシロールなどの有機溶剤に固形分２０〜５５重量％で溶解させることで製造することができる。
あるいは、上記成分（ａ）及び必要に応じて添加される（ｂ）〜（ｆ）を、直接工業用キシロールなどの有機溶剤に固形分２０〜５５重量％で溶解させることで製造することができる。
Hereinafter, the manufacturing method of the resin composition of this invention is demonstrated.
In the composition of the present invention, the above component (a) and (b) to (f), which are added as necessary, are kneaded at a temperature of 180 to 200 ° C., a suitable single screw extruder, twin screw extruder, roll, Banbury It can be produced by dissolving pellets or blocks obtained by melt-kneading using a mixer or various kneaders in an organic solvent such as industrial xylol at a solid content of 20 to 55% by weight.
Or it can manufacture by dissolving the said component (a) and (b)-(f) added as needed directly in organic solvents, such as an industrial xylol, at 20-55 weight% of solid content. .
以下実施例、比較例を用いて本発明を詳細に説明するが、本発明は、実施例のみに限定されるものではない。なお、実施例で用いた評価方法及び原料は以下の通りである。
評価方法
（１）比重：ＪＩＳ Ｋ 7１１２に準拠し、試験片は約０．５ｍｍ厚ディッピング成形シートを用いて測定を行なった。
ディッピング成形シートは以下のようにして製造した。
まず還流冷却器を取り付けた１０００ｃｃ丸底フラスコに６０ｍｍ×φ８ｍｍのマグネットスターラーと得られた手袋用組成物のペレット２００ｇと工業用キシロール３００ｇを投入し、約９５℃に保持されたスターラー付き高温槽で１時間攪拌を行なった。そのまま室温になるまで１２時間以上放置した後、１０分攪拌を行い、フェロタイプ板（１３０ｍｍ×１３０ｍｍ×１ｍｍ）を用いて１回ディッピングを行った。フェロタイプ板を室温で３０分放置した後、オーブン中で１２０℃×３０分熱処理を行った後、フェロタイプ板から剥離することにより得たものである。
（２）硬度：ＪＩＳ Ｋ ７２１５に準拠し、ディッピング成形シートを重ねて４．０ｍｍ厚にして、デュロメータ硬さ・タイプＡにて測定した。
EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, this invention is not limited only to an Example. The evaluation methods and raw materials used in the examples are as follows.
Evaluation Method (1) Specific gravity: Based on JIS K7112, the test piece was measured using a dipping molded sheet having a thickness of about 0.5 mm.
The dipping molded sheet was manufactured as follows.
First, in a 1000 cc round bottom flask equipped with a reflux condenser, a magnetic stirrer of 60 mm × φ8 mm, 200 g of the resulting glove composition pellets and 300 g of industrial xylol were charged, and a high temperature tank with a stirrer maintained at about 95 ° C. Stir for 1 hour. The mixture was allowed to stand for 12 hours or more until it reached room temperature, stirred for 10 minutes, and dipped once using a ferrotype plate (130 mm × 130 mm × 1 mm). This was obtained by leaving the ferrotype plate at room temperature for 30 minutes, then performing a heat treatment at 120 ° C. for 30 minutes in an oven, and then peeling it from the ferrotype plate.
(2) Hardness: Based on JIS K 7215, the dipping molded sheets were overlapped to a thickness of 4.0 mm and measured with durometer hardness / type A.
（３）引張強さ、１００％伸び応力、伸び：ＪＩＳ Ｋ ６３０１に準拠し、試験片は０．５ｍｍ厚ディッピング成形シートを、３号ダンベル型に打抜いて使用した。引張速度は５００ｍｍ／分とした。
（４）オイルブリード／タック性：ディッピング成形で得られた約６５ｍｍ×８０ｍｍ×０．５ｍｍ厚のシートをクラフト紙に挟んで、直径７０ｍｍ円盤状の５００ｇの重りをのせ、室温（２３℃）で１６８時間放置後のクラフト紙の状態を目視で観察し、次の基準で評価した。
○：クラフト紙が容易にシートから剥がれオイルブリードの痕跡が認められない。
△：クラフト紙が僅かにシートに密着しかすかにオイルブリードの痕跡が認められる。
×：クラフト紙がシートに密着しオイルブリードの痕跡が認められる。
(3) Tensile strength, 100% elongation stress, elongation: In accordance with JIS K 6301, a test piece was used by punching a 0.5 mm thick dipping molded sheet into a No. 3 dumbbell mold. The tensile speed was 500 mm / min.
(4) Oil bleed / tackiness: About 65 mm x 80 mm x 0.5 mm thick sheet obtained by dipping molding is sandwiched between kraft paper, and a weight of 70 g disk-shaped 500 g is placed on it at room temperature (23 ° C). The state of the kraft paper after standing for 168 hours was visually observed and evaluated according to the following criteria.
○: Kraft paper is easily peeled off from the sheet and no trace of oil bleed is observed.
Δ: A trace of oil bleed is observed with the kraft paper slightly adhering to the sheet.
X: Kraft paper is in close contact with the sheet and traces of oil bleed are observed.
（５）ディッピング性：還流冷却器を取り付けた１０００ｃｃ丸底フラスコに６０ｍｍ×φ８ｍｍのマグネットスターラーと熱可塑性エラストマーのペレット２００ｇと工業用キシロール３００ｇを投入し、約９５℃に保持されたスターラー付き高温槽で１時間攪拌を行なった。そのまま室温になるまで１２時間以上放置した後、１０分攪拌を行い、フェロタイプ板（１３０ｍｍ×１３０ｍｍ×１ｍｍ）を用いて１回ディッピングを行った。フェロタイプ板を室温で３０分放置した後、オーブン中で１２０℃×３０分熱処理を行い、その製膜状態を目視で観察し次の基準で評価した。
◎：ピンホール状の未溶融物もなく、膜厚も均一。
○：ピンホール状の未溶融物はないが、膜厚は不均一。
Δ：ピンホール状の未溶融物がある。
×：製膜ができない。
(5) Dipping performance: A 1000 cc round bottom flask equipped with a reflux condenser was charged with a magnetic stirrer of 60 mm × φ8 mm, 200 g of thermoplastic elastomer pellets and 300 g of industrial xylol, and a high temperature tank with a stirrer maintained at about 95 ° C. For 1 hour. The mixture was allowed to stand for 12 hours or more until it reached room temperature, stirred for 10 minutes, and dipped once using a ferrotype plate (130 mm × 130 mm × 1 mm). The ferrotype plate was allowed to stand at room temperature for 30 minutes, and then heat-treated in an oven at 120 ° C. for 30 minutes. The film formation state was visually observed and evaluated according to the following criteria.
A: There is no pinhole-like unmelted material and the film thickness is uniform.
○: There is no pinhole-shaped unmelted material, but the film thickness is not uniform.
Δ: There is a pinhole-shaped unmelted material.
X: The film cannot be formed.
（６）ポリウレタンとの接着性：（５）で得られた製膜後のフェロタイプを、さらにポリウレタンペーストを用いて１回ディッピングを行なった。フェロタイプを室温で３０分放置した後、オーブン中で１２０℃×３０分熱処理を行い、得られた膜をフェロタイプ板から剥がした。約０．５ｍｍ厚の膜を３号ダンベル型に打抜いて使用した。ＪＩＳ Ｋ ６３０１に準拠し、引張速度は５００ｍｍ／分とした。試験開始から破断状態までを目視で観察し次の基準で評価した。
○：１００％以上伸び、剥離することなく破断。
Δ：１００％以上伸び破断直前に剥離。
×：１００％未満の伸び、または引張始めから剥離。
(6) Adhesiveness with polyurethane: The ferrotype after film formation obtained in (5) was further dipped once using a polyurethane paste. The ferrotype was left at room temperature for 30 minutes, and then heat-treated in an oven at 120 ° C. for 30 minutes, and the resulting film was peeled from the ferrotype plate. A membrane having a thickness of about 0.5 mm was punched into a No. 3 dumbbell mold and used. In accordance with JIS K 6301, the tensile speed was 500 mm / min. From the start of the test to the rupture state was visually observed and evaluated according to the following criteria.
◯: Elongates 100% or more, breaks without peeling.
Δ: More than 100%, peeling immediately before breaking.
X: Elongation less than 100%, or peeling from the beginning of tension.
使用原料
成分（ａ）：リビングカチオン重合によって得られるスチレン−イソブチレン−スチレンブロック共重合体［ＳＩＢＳ：ＳＩＢＳＴＡＲ ０７３Ｔ（鐘淵化学工業株式会社製）］、スチレン含有量：３０重量％、数平均分子量：６０，０００、重量平均分子量：６５，０００、分子量分布：１．０８、硬さ：５７Ａ、不飽和結合：０％
成分（ｂ−１）：水添共重合体成分、セプトン２１０４（ＳＥＰＳ）（商標；クラレ株式会社製）、スチレン含有量６５重量％、数平均分子量７０，０００、重量平均分子量９１，０００、分子量分布１．３０、水素添加率９０％以上
成分（ｂ−２）：水添共重合体成分、クレイトンＥ−１８１８Ｅ（ＳＥＢＳ）（商標；クレイトンポリマージャパン株式会社製）、スチレン含有量３０重量％、数平均分子量１６０，０００、重量平均分子量２００，０００、分子量分布１．２５、水素添加率９０％以上
Raw material used Component (a): Styrene-isobutylene-styrene block copolymer [SIBS: SIBSTAR 073T (manufactured by Kaneka Chemical Co., Ltd.)] obtained by living cationic polymerization, styrene content: 30% by weight, number average molecular weight: 60,000, weight average molecular weight: 65,000, molecular weight distribution: 1.08, hardness: 57A, unsaturated bond: 0%
Component (b-1): Hydrogenated copolymer component, Septon 2104 (SEPS) (trademark; manufactured by Kuraray Co., Ltd.), styrene content 65% by weight, number average molecular weight 70,000, weight average molecular weight 91,000, molecular weight Distribution 1.30, hydrogenation rate 90% or more Component (b-2): Hydrogenated copolymer component, Kraton E-1818E (SEBS) (trademark; manufactured by Kraton Polymer Japan Co., Ltd.), styrene content 30% by weight, Number average molecular weight 160,000, weight average molecular weight 200,000, molecular weight distribution 1.25, hydrogenation rate 90% or more
成分（ｂ−３）：水添共重合体成分、セプトン４０７７（商標；クラレ株式会社製）、スチレン含有量３０重量％、数平均分子量２６０，０００、重量平均分子量３２０，０００、分子量分布１．２３、水素添加率９０％以上
成分（ｂ−４）：水添共重合体成分、ダイナロンＤＲ6201Ｂ（ＣＥＢＣ）（商標；ＪＳＲ株式会社製）、スチレン含有量０重量％、数平均分子量１８０，０００、重量平均分子量２３０，０００、分子量分布１．２７、水素添加率９０％以上
成分（ｃ）：非芳香族系ゴム軟化剤 ＮＡソルベント ＮＡＳ−５Ｈ （日本油脂（株）製）比重：０．８２３、種類：イソパラフィン系炭化水素油、粘度（４０℃）：１１．０ｃＳｔ、引火点：１４６℃
成分（ｄ）：石油樹脂、アイマーブＰ−１４０（商標；出光石油化学社製）、軟化点：１４０℃、平均分子量：９１０、密度：１．０３ｇ／ｃｍ3
Component (b-3): Hydrogenated copolymer component, Septon 4077 (trademark; manufactured by Kuraray Co., Ltd.), styrene content 30% by weight, number average molecular weight 260,000, weight average molecular weight 320,000, molecular weight distribution 23, Hydrogenation rate 90% or more Component (b-4): Hydrogenated copolymer component, Dynalon DR6201B (CEBC) (trademark; manufactured by JSR Corporation), styrene content 0% by weight, number average molecular weight 180,000, Weight average molecular weight 230,000, molecular weight distribution 1.27, hydrogenation rate 90% or more Component (c): Non-aromatic rubber softener NA Solvent NAS-5H (Nippon Yushi Co., Ltd.) Specific gravity: 0.823 Type: isoparaffinic hydrocarbon oil, viscosity (40 ° C.): 11.0 cSt, flash point: 146 ° C.
Component (d): Petroleum resin, Imabe P-140 (trademark; manufactured by Idemitsu Petrochemical Co., Ltd.), softening point: 140 ° C., average molecular weight: 910, density: 1.03 g / cm 3
成分（ｅ）：テルペン系オイル、ウッディリバー＃１０（ヤスハラケミカル（株）製）比重：０．８０、粘度（２５℃）：１.１４ｃＰ、沸点：１６７〜１７０℃、引火点：４１．５℃
成分（ｆ）：添加剤、酸化防止剤 ＨＰ２２１５（チバスペシャリティケミカルズ社）、構成成分：１５％ラクトン系と８５％ヒンダードフェノール系／フォスファイト系の複合酸化防止剤
Component (e): Terpene oil, Woody River # 10 (manufactured by Yashara Chemical Co., Ltd.) Specific gravity: 0.80, viscosity (25 ° C.): 1.14 cP, boiling point: 167-170 ° C., flash point: 41.5 ° C.
Ingredient (f): Additive, Antioxidant HP2215 (Ciba Specialty Chemicals), Constituent: 15% lactone and 85% hindered phenol / phosphite complex antioxidant
実施例１〜６、比較例１〜４
還流冷却器を取り付けた１０００ｃｃ丸底フラスコに６０ｍｍ×φ８ｍｍのマグネットスターラーと熱可塑性エラストマーのペレット２００ｇと工業用キシロール３００ｇを投入し、約９５℃に保持されたスターラー付き高温槽で１時間攪拌を行なった。そのまま室温になるまで１２時間以上放置した後、１０分攪拌を行い、フェロタイプ板（１３０ｍｍ×１３０ｍｍ×１ｍｍ）を用いて１回ディッピングを行った。フェロタイプ板を室温で３０分放置した後、オーブン中で１２０℃×３０分熱処理を行って試験用シートを得た。
Examples 1-6, Comparative Examples 1-4
A 1000 cc round bottom flask equipped with a reflux condenser was charged with a magnetic stirrer of 60 mm × φ8 mm, 200 g of thermoplastic elastomer pellets and 300 g of industrial xylol, and stirred for 1 hour in a high temperature tank with a stirrer maintained at about 95 ° C. It was. The mixture was allowed to stand for 12 hours or more until it reached room temperature, stirred for 10 minutes, and dipped once using a ferrotype plate (130 mm × 130 mm × 1 mm). The ferrotype plate was left at room temperature for 30 minutes, and then heat-treated in an oven at 120 ° C. for 30 minutes to obtain a test sheet.
表１の実施例１〜６より明らかなように、本発明の組成物は良好な特性を有していた。実施例１〜６の組成物における体積抵抗率は２×１０15Ω・ｃｍ〜５×１０15Ω・ｃｍの範囲であり、いずれも高い絶縁抵抗を有していた。
実施例２〜６では、成分（ｂ）を添加することによりディッピング成形性がさらに向上した。
実施例６では、任意成分である成分（ｃ）を使用し、硬度５０Ａ以下の柔軟な組成物を得ることができる。その際、成分（ｄ）を用いることにより製品への柔軟性付与とポリウレタンへの粘着性の性質がさらに付与され、成分（ｅ）を用いることによりペースト調整、ディッピング成形時の熱による組成物劣化を低減する性質が付与された。
また表２に示す比較例１〜４は、（ａ）成分を配合しなかったものである。表２より成分（ａ）を含まない場合は、ポリウレタン接着性が発現しないことが明らかである。
As is clear from Examples 1 to 6 in Table 1, the composition of the present invention had good characteristics. The volume resistivity at the compositions of Examples 1 to 6 is in the range of 2 × 10 15 Ω · cm~5 × 10 15 Ω · cm, both had high insulation resistance.
In Examples 2 to 6, the dipping moldability was further improved by adding the component (b).
In Example 6, a flexible composition having a hardness of 50 A or less can be obtained using the optional component (c). At that time, the use of component (d) further imparts flexibility to the product and the adhesive property to polyurethane, and the use of component (e) causes deterioration of the composition due to heat during paste adjustment and dipping molding. The property of reducing the property was imparted.
In Comparative Examples 1 to 4 shown in Table 2, the component (a) was not blended. From Table 2, it is clear that when component (a) is not included, polyurethane adhesiveness is not exhibited.
Claims (4)
（１）（ａ）イソブチレン系化合物ブロック及び芳香族ビニル系化合物ブロックから構成されるイソブチレン系ブロック共重合体を含有するペースト
（２）ポリウレタンペースト An isobutylene block comprising an isobutylene compound block and an aromatic vinyl compound block, wherein the paste of the following (1) and the paste of the following (2) are dipped in an arbitrary order on a mold: Adhesion method between polymer and polyurethane.
(1) (a) Paste containing an isobutylene block copolymer composed of an isobutylene compound block and an aromatic vinyl compound block
(2) Polyurethane paste
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