JP5309725B2 - Chloroprene latex and method for producing the same - Google Patents
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Description
本発明は、接着物性が良好であり、特に、高温雰囲気下での接着強度が良好であるクロロプレンラテックス及びその製造方法に関するものである。なお、本発明における高温雰囲気下とは、８０℃を指す。 The present invention relates to a chloroprene latex having good adhesive properties, and particularly having good adhesive strength in a high temperature atmosphere, and a method for producing the same. In addition, the high temperature atmosphere in this invention points out 80 degreeC.
接着剤には、初期強度、耐熱強度、耐水強度等の接着強度が要求される。特に、工場等のラインでは高温にて加熱乾燥された状態で貼り合わされるため、貼り合せの直後に剥がれないよう高温における初期耐熱強度が要求される、一方、現場等では常温乾燥にて貼り合せをおこなうことが多く、塗布後に貼り合せるまでの時間もまちまちであることから作業幅が要求される。 Adhesives are required to have adhesive strength such as initial strength, heat resistance strength, and water resistance strength. In particular, in lines such as factories, since they are bonded in a heated and dried state at a high temperature, initial heat-resistant strength at high temperatures is required so that they do not peel off immediately after bonding. Since the time required for pasting after application varies, the working width is required.
クロロプレンゴム等をベースとした溶剤系接着剤は、その良好な作業性や接着物性から各種用途に用いられてきた。しかし、使用される有機溶剤は地球環境や作業者の健康に悪影響を与え、時には作業場の火災等を引き起こす危険性を有している。そのため、脱溶剤の要求が高まっている。 Solvent-based adhesives based on chloroprene rubber and the like have been used for various applications because of their good workability and adhesive properties. However, the organic solvent used has an adverse effect on the global environment and the health of workers, and sometimes has a risk of causing a fire in the workplace. Therefore, the demand for solvent removal is increasing.
脱溶剤化の手法の一つとして、ラテックス系接着剤による代替が考えられている。 As one of the methods for removing the solvent, substitution with a latex adhesive is considered.
クロロプレンラテックスとしては各種のものが知られている（例えば、特許文献１〜特許文献４）。 Various types of chloroprene latex are known (for example, Patent Documents 1 to 4).
しかし、特許文献１，２に示されるように、ポリビニルアルコール等の水溶性高分子を用いた場合、その保護コロイド性から優れたラテックスの安定性を示す一方で、期待される接着物性が得られず、特に耐水接着強度が低くなる。一方、特許文献３，４に示されるように、ロジン酸の金属塩からなる乳化剤を用いた場合耐水性の問題は無く、耐熱接着強度はクロロプレンゴムを高分子量化し、ゲル分を含有させることで高くできるが、コンタクト性の低下を伴い、また、その強度も溶剤系の接着剤と比較すると不十分である。 However, as shown in Patent Documents 1 and 2, when a water-soluble polymer such as polyvinyl alcohol is used, the latex exhibits excellent latex stability due to its protective colloid properties, while the expected adhesive properties are obtained. In particular, the water-resistant adhesive strength is lowered. On the other hand, as shown in Patent Documents 3 and 4, there is no problem of water resistance when an emulsifier made of a metal salt of rosin acid is used, and the heat resistant adhesive strength is obtained by increasing the molecular weight of chloroprene rubber and adding a gel content. Although it can be increased, it is accompanied by a decrease in contact property and its strength is insufficient as compared with a solvent-based adhesive.
溶剤系の接着剤と比較すると水系接着剤の接着物性は依然として不十分であり、特に耐熱接着強度はその差が大きいため、コンタクト性を低下させることなくこれを向上させることはきわめて重要である。 Compared with solvent-based adhesives, the adhesive properties of water-based adhesives are still inadequate. Particularly, since the difference in heat-resistant adhesive strength is large, it is extremely important to improve this without reducing contact properties.
本発明はこの問題点に鑑みてなされたものであり、従来のクロロプレンラテックスのコンタクト性を損なうことなく、良好な耐熱接着強度を示すクロロプレンラテックス及びその製造方法を提供するものである。 This invention is made | formed in view of this problem, and provides the chloroprene latex which shows favorable heat-resistant adhesive strength, and its manufacturing method, without impairing the contact property of the conventional chloroprene latex.
本発明者らは、このような背景の下、上記課題を解決するため鋭意検討した結果、ラテックス中にクロロプレンと２，３−ジクロロブタジエンの共重合体を含み、結晶化した該共重合体のＤＳＣ測定曲線において、３７〜４５℃の間の吸熱ピークの他に５０〜１００℃の間に一本以上の吸熱ピークが存在するクロロプレンラテックスを用いることで、良好なコンタクト性と耐熱接着強度を示すことを見出し本発明を完成させるに至った。すなわち、本発明は、クロロプレン１００重量部に対して２，３−ジクロロブタジエン９〜１３０重量部である、クロロプレンと２，３−ジクロロブタジエンの共重合体を含有し、該共重合体のＤＳＣ測定曲線において、３７〜４５℃の間の吸熱ピークの他に５０〜１００℃の間に一本以上の吸熱ピークが存在することを特徴とするクロロプレンラテックス、及びその製造方法である。 Under these circumstances, the present inventors have intensively studied to solve the above problems. As a result, the latex contains a copolymer of chloroprene and 2,3-dichlorobutadiene, and crystallizes the copolymer. In DSC measurement curve, by using chloroprene latex having one or more endothermic peaks between 50 and 100 ° C. in addition to the endothermic peaks between 37 and 45 ° C., good contact properties and heat resistant adhesive strength are exhibited. As a result, the present invention has been completed. That is, the present invention contains a copolymer of chloroprene and 2,3-dichlorobutadiene that is 9 to 130 parts by weight of 2,3-dichlorobutadiene with respect to 100 parts by weight of chloroprene, and the DSC measurement of the copolymer In the curve, there are one or more endothermic peaks between 50 and 100 ° C. in addition to the endothermic peak between 37 and 45 ° C., and a process for producing the chloroprene latex.
以下、本発明について詳細に説明する。 The present invention will be described in detail below.
本発明のクロロプレンラテックスは、クロロプレンと２，３−ジクロロブタジエンの共重合体を含有するものである。クロロプレンと２，３−ジクロロブタジエンの共重合体を含有することで、耐熱接着強度を向上できる。 The chloroprene latex of the present invention contains a copolymer of chloroprene and 2,3-dichlorobutadiene. By containing a copolymer of chloroprene and 2,3-dichlorobutadiene, the heat-resistant adhesive strength can be improved.
クロロプレンと２，３−ジクロロブタジエンの共重合体におけるクロロプレンと２，３−ジクロロブタジエンの含有量は、クロロプレン１００重量部に対して２，３−ジクロロブタジエン９〜１３０重量部であり、好ましくは９〜１１０重量部であり、さらに好ましくは９〜５０重量部であり、最も好ましくは９〜２０重量部である。２，３−ジクロロブタジエンが９重量部未満の場合や１３０重量部を超える場合は、５０〜１００℃の間に一本以上の吸熱ピークが存在せず、コンタクト性の低下や、耐熱強度の不足が生じる。 The content of chloroprene and 2,3-dichlorobutadiene in the copolymer of chloroprene and 2,3-dichlorobutadiene is 9 to 130 parts by weight, preferably 9 to 130 parts by weight, per 100 parts by weight of chloroprene. -110 parts by weight, more preferably 9-50 parts by weight, and most preferably 9-20 parts by weight. When 2,3-dichlorobutadiene is less than 9 parts by weight or more than 130 parts by weight, one or more endothermic peaks do not exist between 50 and 100 ° C., resulting in poor contact properties and insufficient heat resistance. Occurs.
本発明のクロロプレンラテックスは、クロロプレンと２，３−ジクロロブタジエンの共重合体のＤＳＣ測定曲線において、３７〜４５℃の間の吸熱ピークの他に５０〜１００℃の間に一本以上の吸熱ピークが存在するものである。３７〜４５℃の間の吸熱ピークの他に５０〜１００℃の間に一本以上の吸熱ピークが存在することにより、良好な耐熱接着強度とコンタクト性を有するものである。 The chloroprene latex of the present invention has one or more endothermic peaks between 50 and 100 ° C. in addition to the endothermic peak between 37 and 45 ° C. in the DSC measurement curve of the copolymer of chloroprene and 2,3-dichlorobutadiene. Is something that exists. The presence of one or more endothermic peaks between 50 and 100 ° C. in addition to the endothermic peaks between 37 and 45 ° C. has good heat resistant adhesive strength and contact properties.
ここに、ＤＳＣにおける吸熱ピークは、ラテックス中よりゴム分を取り出し測定する。 Here, the endothermic peak in DSC is measured by extracting rubber from the latex.
本発明のクロロプレンラテックスの固形分は、特に限定するものではないが、増粘剤配合時の増粘性や、塗布・乾燥後の接着剤量を確保により、良好な接着物性を得るために５０％以上であることが好ましい。 The solid content of the chloroprene latex of the present invention is not particularly limited, but it is 50% in order to obtain good adhesive properties by ensuring thickening at the time of thickener blending and securing the amount of adhesive after coating and drying. The above is preferable.
本発明のクロロプレンラテックスは、良好な安定性と接着物性を得るため、乳化剤を含有することが好ましい。乳化剤としては、アニオン系乳化剤、ノニオン系乳化剤等があげられ、アニオン系乳化剤としては、例えば、ロジン酸のアルカリ金属塩、脂肪酸のアルカリ金属塩、アルケニルコハク酸のアルカリ金属塩、ポリカルボン酸のアルカリ金属塩の高分子化合物などのカルボン酸塩からなる乳化剤、アルカンスルホン酸のアルカリ金属塩、アルキルベンゼンスルホン酸塩などのスルホン酸からなる乳化剤、アルキル硫酸エステル塩、ポリオキシエチレンアルキルエーテル硫酸塩などの硫酸エステル塩等があげられ、ノニオン系乳化剤としては、例えば、ポリオキシエチレンアルキルエーテル、グリセリン脂肪酸エステル、ポリビニルアルコール等があげられる。これらのうち、より良好な安定性と接着物性を得るため、アニオン系乳化剤が好ましく、そのなかでも、ロジン酸のアルカリ金属塩が好ましい。 The chloroprene latex of the present invention preferably contains an emulsifier in order to obtain good stability and adhesive properties. Examples of the emulsifier include an anionic emulsifier and a nonionic emulsifier. Examples of the anionic emulsifier include an alkali metal salt of rosin acid, an alkali metal salt of fatty acid, an alkali metal salt of alkenyl succinic acid, and an alkali metal of polycarboxylic acid. Emulsifiers composed of carboxylates such as polymer compounds of metal salts, alkali metal salts of alkane sulfonic acids, emulsifiers composed of sulfonic acids such as alkylbenzene sulfonates, sulfuric acids such as alkyl sulfate esters, polyoxyethylene alkyl ether sulfates Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, glycerin fatty acid ester, and polyvinyl alcohol. Among these, an anionic emulsifier is preferable in order to obtain better stability and adhesive properties, and among them, an alkali metal salt of rosin acid is preferable.
本発明のクロロプレンラテックスは、クロロプレンラテックス単独でも良いが、複数のクロロプレンラテックスを混合したものでも良い。混合する場合は、全体に対する２，３−ジクロロブタジエンの割合が９〜６０重量％となるように混合することが好ましい。また、２，３−ジクロロブタジエンの割合が９重量％以下や６０重量％以上のラテックスに対し、２，３−ジクロロブタジエンを９重量％以上含むラテックスや、２，３−ジクロロブタジエンを含まないラテックスを混合し、上記の量となるよう調製することも可能である。 The chloroprene latex of the present invention may be chloroprene latex alone or a mixture of a plurality of chloroprene latexes. When mixing, it is preferable to mix so that the ratio of 2, 3- dichlorobutadiene with respect to the whole may be 9 to 60 weight%. Further, a latex containing 9% by weight or more of 2,3-dichlorobutadiene or a latex not containing 2,3-dichlorobutadiene with respect to a latex having a proportion of 2,3-dichlorobutadiene of 9% by weight or less or 60% by weight or more. It is also possible to prepare the above amount by mixing.
本発明のクロロプレンラテックスは、クロロプレン単量体と２，３−ジクロロブタジエン単量体を乳化重合することによって製造することができる。 The chloroprene latex of the present invention can be produced by emulsion polymerization of a chloroprene monomer and a 2,3-dichlorobutadiene monomer.
乳化重合は、上記の単量体、及び乳化剤を、重合開始剤、連鎖移動剤等と共に乳化し、所定温度にて行い、所定の転化率で重合停止剤を添加すれば良い。必要に応じてクロロプレンと共重合可能な他の単量体を更に１種類以上含んでも良い。重合方法としては特に制限のあるものではなく、例えば、クロロプレン単量体と２，３−ジクロロブタジエン単量体、又はクロロプレン単量体と２，３−ジクロロブタジエン単量体とクロロプレンと共重合可能なその他の単量体をラジカル共重合すればよい。また、重合中に各単量体を追加しても良い。 Emulsion polymerization may be carried out by emulsifying the above-mentioned monomer and emulsifier together with a polymerization initiator, a chain transfer agent, etc. at a predetermined temperature, and adding a polymerization terminator at a predetermined conversion rate. If necessary, it may further contain one or more other monomers copolymerizable with chloroprene. The polymerization method is not particularly limited. For example, chloroprene monomer and 2,3-dichlorobutadiene monomer, or chloroprene monomer, 2,3-dichlorobutadiene monomer and chloroprene can be copolymerized. Any other monomer may be radically copolymerized. Moreover, you may add each monomer during superposition | polymerization.
５０〜１００℃の間に一本以上の吸熱ピークが存在するクロロプレンラテックスを得るため、重合初期から２，３−ジクロロブタジエン単量体を仕込む場合の使用量は、クロロプレン単量体１００重量部に対して６０〜１３０重量部であり、好ましくは７５〜１１０重量部である。また、重合中に２，３−ジクロロブタジエン単量体を追加する場合は、重合転化率が６０〜８６％において２，３−ジクロロブタジエン単量体９〜５０重量部を下式を満たすように追加するものであり、好ましくは９〜２０重量部を下式を満たすように追加する。 In order to obtain a chloroprene latex having one or more endothermic peaks between 50 and 100 ° C., the amount used when 2,3-dichlorobutadiene monomer is charged from the initial stage of polymerization is 100 parts by weight of chloroprene monomer. It is 60-130 weight part with respect to it, Preferably it is 75-110 weight part. In addition, when 2,3-dichlorobutadiene monomer is added during the polymerization, 9 to 50 parts by weight of 2,3-dichlorobutadiene monomer satisfy the following formula when the polymerization conversion is 60 to 86%. 9 to 20 parts by weight are preferably added so as to satisfy the following formula.
（１００−Ｃ）×０．６≦Ｘ≦（１００−Ｃ）×１．３５
（式中、Ｘは追加する２，３−ジクロロブタジエン単量体の重量部を表し、Ｃは重合転化率を表す。）
これらの条件を外れると、５０〜１００℃の間には吸熱ピークが存在しない。
(100-C) × 0.6 ≦ X ≦ (100-C) × 1.35
(In the formula, X represents a part by weight of 2,3-dichlorobutadiene monomer to be added, and C represents a polymerization conversion rate.)
Outside these conditions, there is no endothermic peak between 50-100 ° C.
クロロプレンと共重合可能な他の単量体としては、例えば、アクリル酸、メタクリル酸、フマル酸、マレイン酸、クロトン酸、シトラコン酸、２−メタクリロイロキシエチルコハク酸等のカルボキシル基を含有する単量体、２，３−ジクロロ−１，３ブタジエン、ブタジエン、イソプレン、スチレン、アクリロニトリル、メチルメタクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルメタクリレート、ポリエチレングリコールモノアクリレート、ポリエチレングリコールモノメタクリレート、グリセリンモノメタクリレート等があげられる。 Other monomers copolymerizable with chloroprene include, for example, monomers containing a carboxyl group such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, citraconic acid, and 2-methacryloyloxyethyl succinic acid. Examples include a monomer, 2,3-dichloro-1,3 butadiene, butadiene, isoprene, styrene, acrylonitrile, methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, and glycerin monomethacrylate. .
乳化剤は、一般的に乳化重合に用いるものであれば特に限定するものではなく、アニオン系乳化剤、ノニオン系乳化剤等があげられ、アニオン系乳化剤としては、例えば、ロジン酸のアルカリ金属塩、脂肪酸のアルカリ金属塩、アルケニルコハク酸のアルカリ金属塩、ポリカルボン酸のアルカリ金属塩の高分子化合物などのカルボン酸塩からなる乳化剤、アルカンスルホン酸のアルカリ金属塩、アルキルベンゼンスルホン酸塩などのスルホン酸からなる乳化剤、アルキル硫酸エステル塩、ポリオキシエチレンアルキルエーテル硫酸塩などの硫酸エステル塩等があげられ、ノニオン系乳化剤としては、例えば、ポリオキシエチレンアルキルエーテル、グリセリン脂肪酸エステル、ポリビニルアルコール等があげられる。アルカリ金属塩としてはリチウム、ナトリウム、カリウム、セシウムなどがあげられる。これらのなかでも、重合の安定性や接着物性の観点からアニオン系乳化剤が好ましく、そのなかでもロジン酸のアルカリ金属塩が好ましい。使用量は特に限定するものではないが、通常これらを単量体１００重量部に対して３〜７重量部使用する。 The emulsifier is not particularly limited as long as it is generally used for emulsion polymerization, and examples thereof include an anionic emulsifier and a nonionic emulsifier. Examples of the anionic emulsifier include alkali metal salts of rosin acid, fatty acid It consists of emulsifiers consisting of carboxylates such as alkali metal salts, alkali metal salts of alkenyl succinic acid, alkali metal salts of polycarboxylic acids, alkali metal salts of alkane sulfonic acids, sulfonic acids such as alkylbenzene sulfonates, etc. Examples include emulsifiers, sulfates such as alkyl sulfates and polyoxyethylene alkyl ether sulfates, and examples of nonionic emulsifiers include polyoxyethylene alkyl ethers, glycerin fatty acid esters, and polyvinyl alcohol. Examples of the alkali metal salt include lithium, sodium, potassium, cesium and the like. Among these, anionic emulsifiers are preferable from the viewpoint of polymerization stability and adhesive properties, and among these, alkali metal salts of rosin acid are preferable. The amount used is not particularly limited, but usually 3 to 7 parts by weight of these are used per 100 parts by weight of the monomer.
また、ラテックス安定性の面から、ナフタレンスルホン酸塩とホルムアルデヒドの縮合物などの安定剤を併用するのが一般的である。安定剤の量は特に限定するものではない。 From the viewpoint of latex stability, it is common to use a stabilizer such as a condensate of naphthalene sulfonate and formaldehyde in combination. The amount of the stabilizer is not particularly limited.
重合開始剤としては、公知のフリーラジカル性物質、例えば、過硫酸カリウム、過硫酸アンモニウム等の過酸化物、過酸化水素、ターシャリーブチルヒドロパーオキサイド等の無機又は有機過酸化物等を用いることができる。また、これらは単独又は還元性物質、例えば、チオ硫酸塩、チオ亜硫酸塩、ハイドロサルファイト、有機アミン等との併用レドックス系で用いても良い。 As the polymerization initiator, a known free radical substance such as a peroxide such as potassium persulfate or ammonium persulfate, or an inorganic or organic peroxide such as hydrogen peroxide or tertiary butyl hydroperoxide may be used. it can. These may be used alone or in combination with a reducing substance, for example, a combined redox system with thiosulfate, thiosulfite, hydrosulfite, organic amine and the like.
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、硫黄等の分子量調節剤等があげられ、これらのうち、臭気及び作業性の面からｎ−ドデシルメルカプタンが好ましい。通常これらは重合する単量体と共に混合し反応を行うが、反応中に単独で追加しても良い。使用量は特に限定するものではないが、乳化剤にロジン酸のアルカリ金属塩を用いる場合は通常これらを単量体１００重量部に対して０．０１〜０．３重量部使用する。 Examples of the chain transfer agent include molecular weight regulators such as alkyl mercaptans, halogen hydrocarbons, alkyl xanthogen disulfides, and sulfur. Among these, n-dodecyl mercaptan is preferable from the viewpoint of odor and workability. Usually, these are mixed together with the monomer to be polymerized and reacted, but they may be added alone during the reaction. The amount used is not particularly limited, but when an alkali metal salt of rosin acid is used as the emulsifier, usually 0.01 to 0.3 parts by weight of these are used with respect to 100 parts by weight of the monomer.
重合温度は特に限定するものではないが、好ましくは１０〜５０℃の範囲である。 The polymerization temperature is not particularly limited, but is preferably in the range of 10 to 50 ° C.
重合終了時期は特に限定するものでないが、生産性、及び良好な接着物性を得るため、単量体の転化率が８０〜９５％まで重合を行うことが好ましい。 Although the completion | finish time of superposition | polymerization is not specifically limited, In order to obtain productivity and favorable adhesive property, it is preferable to superpose | polymerize until the conversion rate of a monomer is 80-95%.
重合停止剤としては、通常用いられる停止剤であれば特に限定するものでなく、例えば、フェノチアジン、２，６−ｔ−ブチル−４−メチルフェノール、ヒドロキシルアミン等が使用できる。 The polymerization terminator is not particularly limited as long as it is a commonly used terminator, and for example, phenothiazine, 2,6-tert-butyl-4-methylphenol, hydroxylamine and the like can be used.
また、ラテックスの安定性を更に良好にするため、重合中、及び重合終了後に上記の乳化剤のうち１種類以上を添加しても良い。 In order to further improve the stability of the latex, one or more of the above-mentioned emulsifiers may be added during and after the polymerization.
本発明のクロロプレンラテックスは、単独でも接着剤として使用可能であるが、粘着付与樹脂や架橋剤を添加したクロロプレンラテックス組成物とすることで接着物性が向上する。 The chloroprene latex of the present invention can be used alone as an adhesive, but the adhesive properties are improved by using a chloroprene latex composition to which a tackifier resin or a crosslinking agent is added.
粘着付与樹脂としては特に限定するものではなく、例えば、フェノール系樹脂、テルペン系樹脂、ロジン誘導体樹脂、石油系炭化水素等があげられ、例えば、重合ロジン、ロジン変性樹脂、ロジン変性フェノール樹脂、ロジンエステル、アルキルフェノール樹脂、テルペン樹脂、テルペンフェノール、水添ロジン、水添ロジンのペンタエリスリトールエステル、石油樹脂、クマロン樹脂等が使用される。 The tackifying resin is not particularly limited, and examples thereof include phenol resins, terpene resins, rosin derivative resins, petroleum hydrocarbons, and the like, such as polymerized rosin, rosin modified resin, rosin modified phenol resin, rosin. Esters, alkylphenol resins, terpene resins, terpene phenols, hydrogenated rosins, hydrogenated rosin pentaerythritol esters, petroleum resins, coumarone resins, and the like are used.
架橋剤としては、例えば、ポリイソシアネート化合物、エポキシ樹脂、ポリアジリジン化合物、ポリオキサゾリン化合物等、クロロプレンラテックスに均一に混合できる多官能性化合物であれば何ら制限はなく使用できる。 As the crosslinking agent, for example, any polyfunctional compound that can be uniformly mixed with chloroprene latex, such as a polyisocyanate compound, an epoxy resin, a polyaziridine compound, and a polyoxazoline compound, can be used without any limitation.
クロロプレンラテックスを主成分とする接着剤の粘度は、各種増粘剤、例えば、ポリアルキレンオキサイド、ポリビニルアルコール、疎水化セルロース、会合型ノニオン界面活性剤等の水溶性ポリマー、及びカルボキシル基含有ポリマーから構成されるアルカリ可溶型の増粘剤、ヘクトライト等のシリケート化合物等の配合により所望の粘度に調整できる。 The viscosity of the adhesive mainly composed of chloroprene latex is composed of various thickeners, for example, water-soluble polymers such as polyalkylene oxide, polyvinyl alcohol, hydrophobic cellulose, associative nonionic surfactants, and carboxyl group-containing polymers. The viscosity can be adjusted to a desired level by blending an alkali-soluble thickener and a silicate compound such as hectorite.
クロロプレンラテックス組成物には、その他必要に応じて、例えば、増粘剤、老化防止剤、防腐剤、凍結防止剤、造膜助剤、可塑剤、クレー、ｐＨ調節剤等の添加剤を含有したものでも良い。 The chloroprene latex composition contained other additives such as a thickener, an anti-aging agent, an antiseptic, an antifreezing agent, a film-forming aid, a plasticizer, clay, and a pH adjuster as necessary. Things can be used.
本発明のクロロプレンラテックスは、上記の通りすることにより従来のクロロプレンラテックスのコンタクト性を損なうことなく、良好な耐熱接着強度を示す接着剤を提供することができる。 The chloroprene latex of this invention can provide the adhesive which shows favorable heat-resistant adhesive strength, without impairing the contact property of the conventional chloroprene latex by doing as mentioned above.
以下、本発明を実施例によって具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。ポリマーのＤＳＣ、接着剤配合物のコンタクト性および耐熱接着強度は以下の方法・条件で測定した。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to only these examples. The DSC of the polymer, the contact property and the heat-resistant adhesive strength of the adhesive composition were measured by the following methods and conditions.
＜ＤＳＣ測定＞
ラテックスをドライアイス／メタノール冷媒にて凍結後真空乾燥してゴムを取り出し、そのゴムを５℃以下で４８時間以上保管して結晶化させた後に、ＤＳＣ（ＳＥＩＫＯ Ｉ＆Ｅ製 示差操査熱量計ＤＳＣ２００）の測定を行った。測定は−１００℃から２００℃まで、５℃／分の昇温速度で行った。
<DSC measurement>
The latex is frozen in a dry ice / methanol refrigerant and then vacuum dried to remove the rubber. The rubber is stored at 5 ° C. or lower for 48 hours or longer to crystallize, and then DSC (SEIKO I & E differential differential calorimeter DSC200) Was measured. The measurement was performed from −100 ° C. to 200 ° C. at a heating rate of 5 ° C./min.
＜コンタクト性（室温接着強度）＞
９号帆布２枚（約１５０ｍｍ×６０ｍｍ）それぞれの片面に刷毛で接着剤組成物を約２５０ｇ／ｍ２塗布した後に室温で３０分乾燥し、ハンドローラーを用いて圧着した。１５０ｍｍ×２５ｍｍのサイズに切り出したものを測定用の試験片とした。貼り合わせ直後にテンシロン型引っ張り試験機を用いて室温雰囲気下にて１００ｍｍ／ｍｉｎの剥離速度で１８０°方向の引っ張りを行い、接着強度の測定を行なうことでコンタクト性を評価した。
<Contactability (room temperature adhesive strength)>
After applying about 250 g / m 2 of the adhesive composition with a brush to one side of each of No. 9 canvas (about 150 mm × 60 mm), it was dried at room temperature for 30 minutes and pressure-bonded using a hand roller. A test piece for measurement was cut into a size of 150 mm × 25 mm. Immediately after bonding, a Tensilon-type tensile tester was used to pull 180 ° at a peeling rate of 100 mm / min in a room temperature atmosphere, and the contact strength was measured by measuring the adhesive strength.
＜耐熱接着強度＞
９号帆布２枚（約１５０ｍｍ×６０ｍｍ）それぞれの片面に刷毛で接着剤組成物を約２５０ｇ／ｍ２塗布した後に７０℃で３．５分乾燥し、ハンドローラーを用いて圧着した。１５０ｍｍ×２５ｍｍのサイズに切り出したものを測定用の試験片とした。耐熱接着強度の測定は試験片を貼り合わせ直後に６０℃および８０℃の雰囲気下にて５分間状態調整を実施した後に、テンシロン型引っ張り試験機を用いて８０℃の雰囲気下にて１００ｍｍ／ｍｉｎの剥離速度で１８０°方向の引っ張りにて行った。
<Heat resistant adhesive strength>
After applying about 250 g / m 2 of the adhesive composition with a brush on one side of each of No. 9 canvas (about 150 mm × 60 mm), it was dried at 70 ° C. for 3.5 minutes and pressure-bonded using a hand roller. A test piece for measurement was cut into a size of 150 mm × 25 mm. The measurement of heat-resistant adhesive strength was performed after adjusting the condition for 5 minutes in an atmosphere of 60 ° C. and 80 ° C. immediately after bonding the test pieces, and then using a Tensilon type tensile tester at 100 ° C. in an atmosphere of 80 ° C. It was carried out by pulling in the 180 ° direction at a peeling speed of.
実施例１
表１で示した割合のクロロプレン単量体、２，３−ジクロロブタジエン単量体、ｎ−ドデシルメルカプタン、ロジン酸カリウム（商品名：ロンヂスＫ−２５、荒川化学工業（株））、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（商品名：デモールＮ、花王（株））、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１５℃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、重合転化率が約９０％となった時点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重量部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及び濃縮によりラテックスの固形分を５５％に調整し、ラテックスＡを得た。
Example 1
Chloroprene monomer, 2,3-dichlorobutadiene monomer, n-dodecyl mercaptan, potassium rosinate (trade name: Longis K-25, Arakawa Chemical Co., Ltd.), naphthalenesulfonic acid in the proportions shown in Table 1 Polymerization was performed at 15 ° C. in a 10 L autoclave equipped with a stirrer using sodium and formaldehyde condensate (trade name: Demol N, Kao Corporation), sodium hydrosulfite, and pure water. Polymerization was carried out by continuously dropping a 0.35% by weight aqueous potassium persulfate solution under a nitrogen atmosphere, and 2,6-tertiarybutyl-4 as a polymerization terminator when the polymerization conversion reached about 90%. -The polymerization was stopped by adding 0.05 parts by weight of methylphenol. Thereafter, the solid content of the latex was adjusted to 55% by removing and concentrating unreacted monomers under reduced pressure to obtain Latex A.
使用するクロロプレン単量体および２，３−ジクロロブタジエン単量体の量を表１に示す量に変更した以外は、実施例１に従って重合を実施してラテックスＢを得て、ＤＳＣ測定および接着強度の測定を行った。結果を表３に示す。表３の結果より、接着強度は良好な値であった。
Except that the amounts of the chloroprene monomer and 2,3-dichlorobutadiene monomer used were changed to the amounts shown in Table 1, polymerization was carried out according to Example 1 to obtain latex B, DSC measurement and adhesive strength Was measured. The results are shown in Table 3. From the results in Table 3, the adhesive strength was a good value.
実施例３
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単量体、ロジン酸カリウム（商品名：ロンヂスＫ−２５、荒川化学工業（株））、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（商品名：デモールＮ、花王（株））、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１５℃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、重合転化率が７０％となった時点で２，３−ジクロロブタジエン単量体をクロロプレン単量体１００重量部に対し２０重量部追加し、追加した２，３−ジクロロブタジエンも含めた全体の重合転化率が約９０％となった時点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重量部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及び濃縮によりラテックスの固形分を５５％に調整しラテックスＣを得て、ＤＳＣ測定および接着強度の測定を行った。結果を表３に示す。表３の結果より、接着強度は良好な値であった。
Example 3
The proportions of chloroprene monomer, n-dodecyl mercaptan monomer, potassium rosinate (trade name: Longis K-25, Arakawa Chemical Industries, Ltd.), condensate of sodium naphthalenesulfonate and formaldehyde (shown in Table 1) Product name: Demol N, Kao Corporation), hydrosulfite sodium, and pure water were polymerized at 15 ° C. in a 10 L autoclave equipped with a stirrer. Polymerization was carried out by continuously dropping 0.35% by weight potassium persulfate aqueous solution in a nitrogen atmosphere, and when the polymerization conversion reached 70%, 2,3-dichlorobutadiene monomer was replaced with chloroprene monomer. When 20 parts by weight is added to 100 parts by weight and the total polymerization conversion rate including the added 2,3-dichlorobutadiene becomes about 90%, 2,6-tertiarybutyl-4- The polymerization was stopped by adding 0.05 parts by weight of methylphenol. Thereafter, the solid content of the latex was adjusted to 55% by removing and concentrating the unreacted monomer under reduced pressure to obtain latex C, and DSC measurement and adhesion strength measurement were performed. The results are shown in Table 3. From the results in Table 3, the adhesive strength was a good value.
実施例４
２，３−ジクロロブタジエン単量体を追加する重合転化率を８０％に変更した以外は実施例３に従って重合を実施してラテックスＤを得て、ＤＳＣ測定および接着強度の測定を行った。結果を表３に示す。表３の結果より、接着強度は良好な値であった。
Example 4
Latex D was obtained by carrying out polymerization according to Example 3 except that the polymerization conversion rate of adding 2,3-dichlorobutadiene monomer was changed to 80%, and DSC measurement and adhesive strength measurement were performed. The results are shown in Table 3. From the results in Table 3, the adhesive strength was a good value.
実施例５
２，３−ジクロロブタジエン単量体を追加する重合転化率を８５％に変更した以外は実施例３に従って重合を実施してラテックスＥを得て、ＤＳＣ測定および接着強度の測定を行った。結果を表３に示す。表３の結果より、接着強度は良好な値であった。
Example 5
Latex E was obtained by carrying out polymerization according to Example 3 except that the polymerization conversion rate of adding 2,3-dichlorobutadiene monomer was changed to 85%, and DSC measurement and adhesive strength measurement were performed. The results are shown in Table 3. From the results in Table 3, the adhesive strength was a good value.
実施例６
２，３−ジクロロブタジエン単量体を追加する重合転化率を８５％に、追加する量をクロロプレン単量体１００重量部に対し１０重量部に変更した以外は実施例３に従って重合を実施してラテックスＦを得て、ＤＳＣ測定および接着強度の測定を行った。結果を表３に示す。表３の結果より、接着強度は良好な値であった。
Example 6
Polymerization was carried out according to Example 3 except that the polymerization conversion rate of adding 2,3-dichlorobutadiene monomer was changed to 85% and the amount added was changed to 10 parts by weight with respect to 100 parts by weight of chloroprene monomer. Latex F was obtained and subjected to DSC measurement and adhesion strength measurement. The results are shown in Table 3. From the results in Table 3, the adhesive strength was a good value.
実施例７
２，３−ジクロロブタジエン単量体を追加する重合転化率を８０％に、追加する量をクロロプレン単量体１００重量部に対し１５重量部に変更した以外は実施例３に従って重合を実施してラテックスＧを得て、ＤＳＣ測定および接着強度の測定を行った。結果を表３に示す。表３の結果より、接着強度は良好な値であった。
Example 7
Polymerization was carried out according to Example 3 except that the polymerization conversion rate of adding 2,3-dichlorobutadiene monomer was changed to 80% and the amount added was changed to 15 parts by weight with respect to 100 parts by weight of chloroprene monomer. Latex G was obtained and subjected to DSC measurement and adhesion strength measurement. The results are shown in Table 3. From the results in Table 3, the adhesive strength was a good value.
実施例８
２，３−ジクロロブタジエン単量体を追加する重合転化率を６５％に、追加する量をクロロプレン単量体１００重量部に対し３５重量部に変更した以外は実施例３に従って重合を実施してラテックスＨを得て、ＤＳＣ測定および接着強度の測定を行った。結果を表３に示す。表３の結果より、接着強度は良好な値であった。
Example 8
Polymerization was carried out according to Example 3 except that the polymerization conversion rate of adding 2,3-dichlorobutadiene monomer was changed to 65% and the added amount was changed to 35 parts by weight with respect to 100 parts by weight of chloroprene monomer. Latex H was obtained, and DSC measurement and adhesion strength measurement were performed. The results are shown in Table 3. From the results in Table 3, the adhesive strength was a good value.
実施例９
ラテックスＣとラテックスＥを５０：５０の比でブレンドしてラテックスを調製し、ＤＳＣ測定および接着強度の測定を行った。結果を表３に示す。表３の結果より、接着強度は良好な値であった。
Example 9
Latex C and latex E were blended at a ratio of 50:50 to prepare a latex, and DSC measurement and adhesion strength measurement were performed. The results are shown in Table 3. From the results in Table 3, the adhesive strength was a good value.
実施例１０
表１に示すように、２，３−ジクロロブタジエン単量体を追加しない以外は、実施例１に従い重合を行いラテックスＩを得て、ラテックスＡとラテックスＩを３０：７０の比でブレンドしてラテックスを調製し、ＤＳＣ測定および接着強度の測定を実施した。結果を表３に示す。表３の結果より、接着強度は良好な値であった。
Example 10
As shown in Table 1, polymerization was performed according to Example 1 except that 2,3-dichlorobutadiene monomer was not added, and latex I was obtained, and latex A and latex I were blended at a ratio of 30:70. A latex was prepared, and DSC measurement and adhesion strength measurement were performed. The results are shown in Table 3. From the results in Table 3, the adhesive strength was a good value.
実施例１１
ラテックスＣとラテックスＩを３０：７０の比でブレンドしてラテックスを調製し、ＤＳＣ測定および接着強度の測定を実施した。結果を表３に示す。表３の結果より、接着強度は良好な値であった。
Example 11
Latex C was prepared by blending Latex C and Latex I in a ratio of 30:70, and DSC measurement and adhesive strength measurement were performed. The results are shown in Table 3. From the results in Table 3, the adhesive strength was a good value.
比較例１
ラテックスＩ単独についてＤＳＣ測定および接着強度の測定を実施した。結果を表４に示す。ＤＳＣ測定の結果、５０〜１００℃の間にピークは無く、耐熱接着強度も低かった。
Comparative Example 1
DSC measurement and adhesion strength measurement were performed on Latex I alone. The results are shown in Table 4. As a result of DSC measurement, there was no peak between 50 and 100 ° C., and the heat resistant adhesive strength was low.
表１に示すように、クロロプレン単量体の代わりに２，３−ジクロロブタジエン単量体を用いて重合を行いラテックスＪを得て、ＤＳＣ測定および接着強度の測定を行った。結果を表４に示す。ＤＳＣ測定の結果、５０〜１００℃の間にピークは無く、接着強度も低かった。
As shown in Table 1, polymerization was performed using 2,3-dichlorobutadiene monomer instead of chloroprene monomer to obtain latex J, and DSC measurement and adhesion strength measurement were performed. The results are shown in Table 4. As a result of DSC measurement, there was no peak between 50 and 100 ° C., and the adhesive strength was low.
比較例３
表１で示した割合のクロロプレン単量体、２，３−ジクロロブタジエン単量体、ｎ−ドデシルメルカプタン、ロジン酸カリウム（商品名：ロンヂスＫ−２５、荒川化学工業（株））、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（商品名：デモールＮ、花王（株））、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１５℃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、重合転化率が約９０％となった時点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重量部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及び濃縮によりラテックスの固形分を５５％に調整し、ラテックスＫを得て、ＤＳＣ測定および接着強度の測定を行った。結果を表４に示す。ＤＳＣ測定の結果、５０〜１００℃の間にピークは無く、耐熱接着強度も低かった。
Comparative Example 3
Chloroprene monomer, 2,3-dichlorobutadiene monomer, n-dodecyl mercaptan, potassium rosinate (trade name: Longis K-25, Arakawa Chemical Co., Ltd.), naphthalenesulfonic acid in the proportions shown in Table 1 Polymerization was performed at 15 ° C. in a 10 L autoclave equipped with a stirrer using sodium and formaldehyde condensate (trade name: Demol N, Kao Corporation), sodium hydrosulfite, and pure water. Polymerization was carried out by continuously dropping a 0.35% by weight aqueous potassium persulfate solution under a nitrogen atmosphere, and 2,6-tertiarybutyl-4 as a polymerization terminator when the polymerization conversion reached about 90%. -The polymerization was stopped by adding 0.05 parts by weight of methylphenol. Thereafter, the solid content of the latex was adjusted to 55% by removing and concentrating unreacted monomers under reduced pressure to obtain latex K, and DSC measurement and adhesion strength measurement were performed. The results are shown in Table 4. As a result of DSC measurement, there was no peak between 50 and 100 ° C., and the heat resistant adhesive strength was low.
比較例４
表１で示した割合に２，３−ジクロロブタジエン単量体を変更した以外は、実施例１に従って重合を行いラテックスＬを得て、ＤＳＣ測定および接着強度の測定を行った。結果を表４に示す。ＤＳＣ測定の結果、５０〜１００℃の間にピークは無く、室温接着強度が低くコンタクト性が悪かった。
Comparative Example 4
Except that the 2,3-dichlorobutadiene monomer was changed to the ratio shown in Table 1, polymerization was performed according to Example 1, latex L was obtained, and DSC measurement and adhesive strength measurement were performed. The results are shown in Table 4. As a result of DSC measurement, there was no peak between 50 and 100 ° C., and the room temperature adhesive strength was low and the contact property was poor.
比較例５
２，３−ジクロロブタジエン単量体を追加する重合転化率を８８％に変更した以外は実施例３に従って重合を実施してラテックスＭを得て、ＤＳＣ測定および接着強度の測定を行った。結果を表４に示す。ＤＳＣ測定の結果、５０〜１００℃の間にピークは無く、室温接着強度が低くコンタクト性が悪かった。
Comparative Example 5
Latex M was obtained by carrying out polymerization according to Example 3 except that the polymerization conversion rate of adding 2,3-dichlorobutadiene monomer was changed to 88%, and DSC measurement and adhesive strength measurement were performed. The results are shown in Table 4. As a result of DSC measurement, there was no peak between 50 and 100 ° C., and the room temperature adhesive strength was low and the contact property was poor.
比較例６
２，３−ジクロロブタジエン単量体を追加する量をクロロプレン１００重量部に対して５重量部に変更した以外は実施例３に従って重合を実施してラテックスＮを得て、ＤＳＣ測定および接着強度の測定を行った。結果を表４に示す。ＤＳＣ測定の結果、５０〜１００℃の間にピークは無く、耐熱接着強度が低かった。
Comparative Example 6
Polymerization was carried out according to Example 3 except that the amount of 2,3-dichlorobutadiene monomer added was changed to 5 parts by weight with respect to 100 parts by weight of chloroprene to obtain latex N. Measurements were made. The results are shown in Table 4. As a result of DSC measurement, there was no peak between 50 and 100 ° C., and the heat resistant adhesive strength was low.
比較例７
２，３−ジクロロブタジエン単量体を追加する量をクロロプレン１００重量部に対して６０重量部に変更した以外は実施例３に従って重合を実施してラテックスＯを得て、ＤＳＣ測定および接着強度の測定を行った。結果を表４に示す。ＤＳＣ測定の結果、５０〜１００℃の間にピークは無く、接着強度が低かった。
Comparative Example 7
Except that the amount of 2,3-dichlorobutadiene monomer added was changed to 60 parts by weight with respect to 100 parts by weight of chloroprene, polymerization was carried out according to Example 3 to obtain latex O. Measurements were made. The results are shown in Table 4. As a result of DSC measurement, there was no peak between 50 and 100 ° C., and the adhesive strength was low.
比較例８
２，３−ジクロロブタジエン単量体を追加する重合転化率を５０％に、追加する量をクロロプレン１００重量部に対して１５重量部に変更した以外は実施例３に従って重合を実施してラテックスＰを得て、ＤＳＣ測定および接着強度の測定を行った。結果を表４に示す。ＤＳＣ測定の結果、５０〜１００℃の間にピークは無く、耐熱接着強度が低かった。
Comparative Example 8
Latex P was polymerized in accordance with Example 3 except that the polymerization conversion rate of adding 2,3-dichlorobutadiene monomer was changed to 50% and the added amount was changed to 15 parts by weight with respect to 100 parts by weight of chloroprene. DSC measurement and adhesive strength measurement were performed. The results are shown in Table 4. As a result of DSC measurement, there was no peak between 50 and 100 ° C., and the heat resistant adhesive strength was low.
Claims (7)
（１００−Ｃ）×０．６≦Ｘ≦（１００−Ｃ）×１．３５
（式中、Ｘは追加する２，３−ジクロロブタジエン単量体の重量部を表し、Ｃは重合転化率を表す。） Polymerization was started using 100 parts by weight of chloroprene monomer and an alkali metal salt of rosin acid, and then 9 to 50 parts by weight of 2,3-dichlorobutadiene monomer at a polymerization conversion of 60 to 86% A copolymer of chloroprene and 2,3-dichlorobutadiene, which is 9-50 parts by weight of 2,3-dichlorobutadiene, and an alkali of rosin acid, obtained by adding 100 parts by weight of chloroprene. A chloroprene containing a metal salt and having one or more endothermic peaks between 50 and 100 ° C. in addition to an endothermic peak between 37 and 45 ° C. in a DSC measurement curve of the copolymer latex.
(100-C) × 0.6 ≦ X ≦ (100-C) × 1.35
(In the formula, X represents a part by weight of 2,3-dichlorobutadiene monomer to be added, and C represents a polymerization conversion rate.)
（１００−Ｃ）×０．６≦Ｘ≦（１００−Ｃ）×１．３５
（式中、Ｘは追加する２，３−ジクロロブタジエン単量体の重量部を表し、Ｃは重合転化率を表す。） Polymerization was started using 100 parts by weight of chloroprene monomer and an alkali metal salt of rosin acid, and then 9 to 50 parts by weight of 2,3-dichlorobutadiene monomer at a polymerization conversion of 60 to 86% The method for producing a chloroprene latex according to claim 2, wherein the chloroprene latex is added so as to satisfy.
(100-C) × 0.6 ≦ X ≦ (100-C) × 1.35
(In the formula, X represents a part by weight of 2,3-dichlorobutadiene monomer to be added, and C represents a polymerization conversion rate.)
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