JP2016079380A - Aqueous adhesive production method - Google Patents

Aqueous adhesive production method Download PDF

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JP2016079380A
JP2016079380A JP2015060549A JP2015060549A JP2016079380A JP 2016079380 A JP2016079380 A JP 2016079380A JP 2015060549 A JP2015060549 A JP 2015060549A JP 2015060549 A JP2015060549 A JP 2015060549A JP 2016079380 A JP2016079380 A JP 2016079380A
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vinyl acetate
emulsion
monomer
polyvinyl alcohol
aqueous adhesive
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JP5869165B1 (en
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櫛田　貢
Mitsugi Kushida
貢 櫛田
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Aica Kogyo Co Ltd
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Aica Kogyo Co Ltd
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Priority to PCT/JP2015/079024 priority patent/WO2016060159A1/en
Priority to CN201580037417.8A priority patent/CN106471084B/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04—Homopolymers or copolymers of vinyl acetate

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous adhesive production method that solves the problem that: though an aqueous adhesive obtained by adding a water-proofing agent to an emulsion having a carboxylic group such as acetoacetyl group is known, it does not fulfill the DIN/EN204 D3 standard that exists as a water-proofing standard in Europe, etc; and also, even when D3 standard is fulfilled, there is a difficulty in storage stability.SOLUTION: The aqueous adhesive production method includes incorporating a metallic compound and a silane-based coupling agent to a vinyl acetate-based resin emulsion obtained by emulsion polymerizing a vinyl acetate monomer using a polyvinyl alcohol containing an acetoacetylated polyvinyl alcohol and an ethylene modified polyvinyl alcohol as a protective colloid, or by emulsion co-polymerizing a vinyl acetate monomer and a monomer comprising an acetoacetyl group in the presence of a chain transfer agent.SELECTED DRAWING: None

Description

本発明は、耐水性に優れる水性接着剤に関する。   The present invention relates to an aqueous adhesive having excellent water resistance.

従来耐水性の高い水性接着剤として、アセトアセチル化ポリビニルアルコールを保護コロイドとして用い、更にアセトアセチル基を有し、酢酸ビニルモノマーと共重合できるモノマーを酢酸ビニルモノマーと乳化共重合して合成した酢酸ビニル系接着剤（特許文献1）、分子内に炭素数４以下のα−オレフィン単位を１〜２０モル％含有し、けん化度９５モル％以上のビニルアルコール系重合体（Ａ）および分子内にカルボキシル基を含有するビニルアルコール系重合体（Ｂ）を分散剤とし、エチレン性不飽和単量体およびジエン系単量体から選ばれる少なくとも一種の単量体単位を含有する重合体を分散質とする水性エマルジョンおよびエポキシ化合物、アミノ基含有水性樹脂、アルミニウム化合物およびチタン化合物から選ばれる少なくとも一種の耐水化剤からなる水性エマルジョン（特許文献２）、カルボキシル基を有する重合体を含む水性高分子エマルジョンに、水溶性多価金属化合物［例えば、有機酸塩（酢酸カルシウムなど）、無機酸塩（硫酸鉄、硫酸カリウムアルミニウムなど）、ハロゲン化物（塩化カルシウムなど）など］から選択された少くとも一種を添加した水性接着剤（特許文献３）、アセトアセチル化ポリビニルアルコールを保護コロイドとして、酢酸ビニルモノマー又は酢酸ビニルモノマーとアセトアセチル基を含有するモノマーを共存させて、エマルジョン重合した合成樹脂エマルジョンあるいは少なくともポリビニルアルコール、セルロース類、界面活性剤等の存在下で酢酸ビニルモノマーとアセトアセチル基含有モノマーとを乳化共重合した合成樹脂エマルジョンに、炭酸カルシウムを配合してなるエマルジョン（特許文献４）、アセトアセチル化ポリビニルアルコールを含むポリビニルアルコールを保護コロイドとして、酢酸ビニルモノマーを乳化重合した、または酢酸ビニルモノマーとアセトアセチル基を有するモノマーとを乳化共重合した酢酸ビニル系樹脂エマルジョンに、金属化合物を配合する水性接着剤（特許文献５）などが知られている。   Acetic acid synthesized by emulsifying copolymerization of vinyl acetate monomer with acetoacetylated polyvinyl alcohol as protective colloid, and also having acetoacetyl group and copolymerizable with vinyl acetate monomer. Vinyl adhesive (Patent Document 1), vinyl alcohol polymer (A) having a saponification degree of 95 mol% or more containing 1 to 20 mol% of an α-olefin unit having 4 or less carbon atoms in the molecule and the molecule A vinyl alcohol polymer (B) containing a carboxyl group is used as a dispersant, and a polymer containing at least one monomer unit selected from ethylenically unsaturated monomers and diene monomers is used as a dispersoid. An aqueous emulsion and an epoxy compound, an amino group-containing aqueous resin, an aluminum compound and a titanium compound. An aqueous emulsion comprising a kind of water-resistant agent (Patent Document 2), an aqueous polymer emulsion containing a polymer having a carboxyl group, a water-soluble polyvalent metal compound [for example, an organic acid salt (such as calcium acetate), an inorganic acid salt Water-based adhesive (Patent Document 3) to which at least one selected from (iron sulfate, potassium aluminum sulfate, etc.), halide (calcium chloride, etc.) is added, vinyl acetate using acetoacetylated polyvinyl alcohol as a protective colloid A monomer resin or a vinyl acetate monomer and an acetoacetyl group-containing monomer coexisting with each other, an emulsion-polymerized synthetic resin emulsion, or at least a vinyl acetate monomer and an acetoacetyl group-containing monomer in the presence of polyvinyl alcohol, celluloses, surfactants, etc. Synthetic tree obtained by emulsion copolymerization Emulsion obtained by blending calcium carbonate into emulsion (Patent Document 4), vinyl acetate monomer emulsion polymerized using polyvinyl alcohol containing acetoacetylated polyvinyl alcohol as protective colloid, or monomer having vinyl acetate monomer and acetoacetyl group An aqueous adhesive (Patent Document 5) is known in which a metal compound is blended with a vinyl acetate resin emulsion obtained by emulsion copolymerization.

特開２０００−２８２００４JP 2000-282004 A 特開２００１−０４０２３１JP2001-040231A 特開平１０−０４６１３２JP 10-0461132 A 特開平１１−２７９３６２JP 11-279362 A 特願２０１４−０６６７２４Japanese Patent Application No. 2014-066724

上記の特許文献１から４に示す接着剤は、アセトアセチル基のようなカルボキシ基を有するエマルジョンに耐水化剤を添加してなるものであるが、欧州等で耐水化規格としてある、ＤＩＮ／ＥＮ２０４ Ｄ３：常温１週間後の強度が１０Ｍｐａ以上、常温１週間＋２０℃水中４日間の強度が２Ｍｐａ以上、常温１週間＋２０℃水中４日間＋常温１週間後の強度が８Ｍｐａ以上、とする、いわゆるＤ３規格を満たすものではない。特許文献５に示す接着剤はＤ３規格を満たすものの、保存性、特に静置下や低温下での粘度上昇が高いものであった。   The adhesives described in Patent Documents 1 to 4 above are formed by adding a water-resistant agent to an emulsion having a carboxy group such as an acetoacetyl group. DIN / EN204, which is a water resistance standard in Europe and the like. D3: Strength after 10 weeks at room temperature, strength at 1 week at room temperature + 4 days in water at 20 ° C. is 2 Mpa or more, strength at room temperature for 1 week + 4 days in water at 20 ° C. + strength after 1 week at room temperature is 8 Mpa or more It does not meet the standards. Although the adhesive shown in Patent Document 5 satisfies the D3 standard, it has a high storage stability, in particular, a viscosity increase under standing or low temperature.

本発明は、このような実情に鑑みてなされたもので、接着性と耐水性、ならびに保存性に優れる水性接着剤を提供することを課題とする。   This invention is made | formed in view of such a situation, and makes it a subject to provide the water-based adhesive which is excellent in adhesiveness, water resistance, and preservability.

上記課題を解決するため、本発明の水性接着剤は、アセトアセチル化ポリビニルアルコールおよびエチレン変性ポリビニルアルコールを含むポリビニルアルコールを保護コロイドとして、酢酸ビニルモノマーを乳化重合した、または酢酸ビニルモノマーとアセトアセチル基を有するモノマーとを乳化共重合した酢酸ビニル系樹脂エマルジョンに、金属化合物を配合してなることを特徴とする。さらに、前記金属化合物がカルシウム化合物であり、前記酢酸ビニル系樹脂エマルジョンが、連鎖移動剤の存在下で乳化重合されたものであることを特徴とする。   In order to solve the above problems, the water-based adhesive of the present invention is obtained by emulsion polymerization of a vinyl acetate monomer or a vinyl acetate monomer and an acetoacetyl group using polyvinyl alcohol containing acetoacetylated polyvinyl alcohol and ethylene-modified polyvinyl alcohol as a protective colloid. It is characterized in that a metal compound is blended with a vinyl acetate resin emulsion obtained by emulsion copolymerization with a monomer having s. Furthermore, the metal compound is a calcium compound, and the vinyl acetate resin emulsion is emulsion-polymerized in the presence of a chain transfer agent.

金属化合物が水性高分子エマルジョンの耐水化剤となることは上記特許文献にも開示されているが、アセトアセチル基を有する酢酸ビニルエマルジョンに対して特定の金属化合物を添加することにより、より耐水性の高い水性接着剤となる。 Although it is also disclosed in the above-mentioned patent document that a metal compound is a water resistance agent for an aqueous polymer emulsion, it is more water resistant by adding a specific metal compound to a vinyl acetate emulsion having an acetoacetyl group. High water-based adhesive.

さらに、前記水性接着剤にシラン系カップリング剤を添加することにより、得られる水性接着剤の耐水性が向上する。 Furthermore, by adding a silane coupling agent to the aqueous adhesive, the water resistance of the obtained aqueous adhesive is improved.

本発明の水性接着剤は、Ｄ３規格を満たす高い耐水性と良好な保存性を有する接着剤となり、本水性接着剤を使用した製品は、高多湿下の条件で使用されても高い耐久性を満たす。また、ＪＡＳ規格を採用していない海外でも高耐水性接着剤として用途が拡大する。   The water-based adhesive of the present invention becomes an adhesive having high water resistance satisfying the D3 standard and good storage stability, and products using this water-based adhesive have high durability even when used under conditions of high humidity. Fulfill. In addition, the use is expanded as a highly water-resistant adhesive even in foreign countries where the JAS standard is not adopted.

以下、本発明の水性接着剤について、実施例、比較例に基づき説明する。なお、本発明の水性接着剤は、以下の形態に限定されるものではなく、本発明の要旨を逸脱しない範囲において、当業者が行い得る変更、改良等を施した種々の形態にて実施することができる。   Hereinafter, the water-based adhesive of the present invention will be described based on examples and comparative examples. In addition, the water-based adhesive of the present invention is not limited to the following forms, and can be implemented in various forms with modifications, improvements, etc. that can be made by those skilled in the art without departing from the gist of the present invention. be able to.

本水性接着剤は、アセトアセチル化ポリビニルアルコールおよびエチレン変性ポリビニルアルコールを含むポリビニルアルコールを保護コロイドとして、酢酸ビニルモノマーを乳化重合し、または酢酸ビニルモノマーとアセトアセチル基を有するモノマーとを乳化共重合して、酢酸ビニル系樹脂エマルジョンとするものである。   This water-based adhesive is obtained by emulsion polymerization of vinyl acetate monomer or emulsion copolymerization of vinyl acetate monomer and monomer having acetoacetyl group using acetoacetylated polyvinyl alcohol and polyvinyl alcohol including ethylene-modified polyvinyl alcohol as protective colloid. Thus, a vinyl acetate resin emulsion is obtained.

保護コロイドとしては、接着剤の耐水性および耐熱性の両方を満足するという観点から、アセトアセチル化ポリビニルアルコール（以下、適宜「ＡＡ化ＰＶＡ」と称す）およびエチレン変性ポリビニルアルコール（以下、適宜「ＥＶＯＨ」と称す）を含むポリビニルアルコールを用いることが好ましい。ＡＡ化ＰＶＡは、ポリビニルアルコールとジケテンとを反応させて得られる変性ポリビニルアルコールである。ＡＡ化ＰＶＡのアセトアセチル化度は、０．０５〜２０モル％の範囲が好適である。市販品として日本合成化学工業株式会社のゴーセネックス（登録商標）Ｚなどがある。ＥＶＯＨは分子内にエチレン単位を１〜２０モル％含有し、けん化度９５モル％以上のビニルアルコール系重合体で、市販品として株式会社クラレのエクセバール（登録商標）などがある。保護コロイドのポリビニルアルコールは、ＡＡ化ＰＶＡ、ＥＶＯＨの他に、他の変性されていないポリビニルアルコール（未変性のポリビニルアルコール）を含んでいてもよい。未変性のポリビニルアルコールを併用することにより、酢酸ビニルモノマーの反応性を高めて、重合時間を短縮することができる。   As the protective colloid, from the viewpoint of satisfying both the water resistance and heat resistance of the adhesive, acetoacetylated polyvinyl alcohol (hereinafter referred to as “AA-modified PVA” as appropriate) and ethylene-modified polyvinyl alcohol (hereinafter referred to as “EVOH” as appropriate). It is preferable to use polyvinyl alcohol containing “ AA-PVA is a modified polyvinyl alcohol obtained by reacting polyvinyl alcohol and diketene. The degree of acetoacetylation of AA-modified PVA is preferably in the range of 0.05 to 20 mol%. As a commercial product, there is Goseinex (registered trademark) Z of Nippon Synthetic Chemical Industry Co., Ltd. EVOH is a vinyl alcohol polymer containing 1 to 20 mol% of ethylene units in the molecule and having a saponification degree of 95 mol% or more. Examples of commercially available products include KURARAY EXVAL (registered trademark). The protective colloid polyvinyl alcohol may contain other unmodified polyvinyl alcohol (unmodified polyvinyl alcohol) in addition to AA-PVA and EVOH. By using unmodified polyvinyl alcohol in combination, the reactivity of the vinyl acetate monomer can be increased and the polymerization time can be shortened.

ＡＡ化ＰＶＡとＥＶＯＨの配合量は、１：０．２〜５が好ましく、酢酸ビニルモノマーの１００質量部に対して５質量部以上３０質量部以下であることが好ましい。ＡＡ化ＰＶＡが少ないと、耐水性向上効果が充分に得られない。反対に、ＡＡ化ＰＶＡが多すぎると、接着剤の貯蔵安定性が悪くなる。   As for the compounding quantity of AA-ized PVA and EVOH, 1: 0.2-5 are preferable, and it is preferable that they are 5 mass parts or more and 30 mass parts or less with respect to 100 mass parts of a vinyl acetate monomer. When there is little AA-ized PVA, the water-resistant improvement effect is not fully acquired. On the contrary, when there is too much AA-ized PVA, the storage stability of an adhesive agent will worsen.

酢酸ビニルモノマーと共重合するアセトアセチル基を有するモノマーとしては、例えば、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、アリルアルコール、メタクリルアルコール、２−ヒドロキシ−３−クロロプロピルメタクリレート、１，４−ブチレングリコールモノアクリレート、１，４−ブチレングリコールモノメタクリレート、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタクリルアミド、ヒドロキシスチレンなどのアセトアセチル化物が挙げられる。   Examples of the monomer having an acetoacetyl group copolymerized with vinyl acetate monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, allyl alcohol, methacryl alcohol, 2-hydroxy-3-chloropropyl methacrylate, Examples include acetoacetylated products such as 1,4-butylene glycol monoacrylate, 1,4-butylene glycol monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide, and hydroxystyrene.

アセトアセチル基を有するモノマーの配合量は、酢酸ビニルモノマーの１００質量部に対して、１質量部以上２０質量部以下であることが好ましい。酢酸ビニルモノマーに対してアセトアセチル基を有するモノマーが少ないと、耐水性向上効果が充分に得られない。反対に、アセトアセチル基を有するモノマーが多すぎると、接着剤の貯蔵安定性が悪くなる。   It is preferable that the compounding quantity of the monomer which has an acetoacetyl group is 1 to 20 mass parts with respect to 100 mass parts of a vinyl acetate monomer. If there are few monomers which have an acetoacetyl group with respect to a vinyl acetate monomer, the water-resistant improvement effect will not fully be acquired. On the contrary, when there are too many monomers which have an acetoacetyl group, the storage stability of an adhesive agent will worsen.

本水性接着剤の乳化重合は、連鎖移動剤の存在下で重合される。本発明の乳化重合において用いられる連鎖移動剤は、乳化重合の際、生成する重合体の分子量を適度に調節し、木材用接着剤として用いたときに、優れた濡れ性、親和性を発揮して、接着力を強化する作用がある。   The emulsion polymerization of the aqueous adhesive is polymerized in the presence of a chain transfer agent. The chain transfer agent used in the emulsion polymerization of the present invention exhibits excellent wettability and affinity when used as an adhesive for wood by appropriately adjusting the molecular weight of the polymer produced during emulsion polymerization. And has the effect of strengthening the adhesive force.

連鎖移動剤としては、上記作用を有するものであれば特に限定されないが、例えば、メルカプタン系化合物やアルコール等を用いることができる。前記メルカプタン系化合物には、ブチルメルカプタン、オクチルメルカプタン、ラウリルメルカプタン、ベンゼンチオエタノール、オクチルチオグリコレート等のチオール、２−メルカプトエチルアルコール等のメルカプト基含有アルコール、β−メルカプトプロピオン酸、メルカプトコハク酸などのメルカプトカルボン酸等が含まれる。前記アルコールには、メチルアルコール、エチルアルコール、ｎ−プロピルアルコール、イソプロピルアルコール、ｔ−ブチルアルコール等のＣ1−Ｃ6程度の脂肪族アルコール、ベンジルアルコール等のＣ7−Ｃ13程度の芳香族アルコールなどが含まれる。これらは単独で又は２種以上組み合わせて使用できる。例えば、メルカプタン系化合物とアルコールとを組み合わせて用いてもよい。 The chain transfer agent is not particularly limited as long as it has the above action, and for example, a mercaptan compound or alcohol can be used. Examples of the mercaptan compounds include butyl mercaptan, octyl mercaptan, lauryl mercaptan, thiol such as benzenethioethanol, octylthioglycolate, mercapto group-containing alcohols such as 2-mercaptoethyl alcohol, β-mercaptopropionic acid, mercaptosuccinic acid, etc. Of mercaptocarboxylic acid and the like. Wherein the alcohol, methyl alcohol, ethyl alcohol, n- propyl alcohol, isopropyl alcohol, C 1 -C 6 about an aliphatic alcohol such as t- butyl alcohol, C 7 -C 13 about aromatic alcohols such as benzyl alcohol Etc. are included. These can be used alone or in combination of two or more. For example, a mercaptan compound and alcohol may be used in combination.

連鎖移動剤の乳化重合における使用量は、前記酢酸ビニルモノマーの総量に対して、０．１〜３．０重量％程度である。この使用量が０．１重量％未満の場合は、十分な接着力が得られにくく、３重量％を超えると、乳化重合速度が低下することにより残存モノマーが多量に生じ、臭気が発生するなど環境保護の点で好ましくなく、さらに重合体の分子量が低下しすぎるため、接着剤の耐水性、耐湿熱性、耐熱性等の低下を引き起こしやすく、好ましくない。   The amount of chain transfer agent used in the emulsion polymerization is about 0.1 to 3.0% by weight based on the total amount of the vinyl acetate monomer. When the amount used is less than 0.1% by weight, it is difficult to obtain a sufficient adhesive force, and when it exceeds 3% by weight, a large amount of residual monomer is produced due to a decrease in emulsion polymerization rate, and odor is generated. It is not preferable from the viewpoint of environmental protection, and further, the molecular weight of the polymer is too low, which is not preferable because it tends to cause deterioration of water resistance, moist heat resistance, heat resistance and the like of the adhesive.

酢酸ビニルモノマーの乳化重合または乳化共重合は、公知の反応助剤、重合開始剤などを用いて行えばよい。反応助剤としては、酒石酸、酢酸ナトリウム、炭酸ナトリウムなどが好適である。重合開始剤としては、過酸化水素、過硫酸アンモニウム、過硫酸ナトリウムなどが好適である。保護コロイドは、酢酸ビニルモノマーの重合開始前または重合中に添加すればよい。   Emulsion polymerization or emulsion copolymerization of vinyl acetate monomer may be performed using a known reaction aid, polymerization initiator or the like. As the reaction aid, tartaric acid, sodium acetate, sodium carbonate and the like are suitable. As the polymerization initiator, hydrogen peroxide, ammonium persulfate, sodium persulfate and the like are suitable. The protective colloid may be added before or during the polymerization of the vinyl acetate monomer.

本水性接着剤は、特定の金属化合物を含む。金属化合物としては、ベリリウム、ジルコニウム、チタニウム、クロム、カルシウム、マグネシウム、亜鉛、バリウム、ストロンチウム、アルミニウム、ビスマス、アンチモン、コバルト、鉄、ニツケル等の塩化物、酸化物、水酸化物、塩基性塩、酸性塩、中性塩、アミン複合体等が挙げられ、中でも前記金属化合物の炭酸塩が好ましく、充填剤としても働く炭酸カルシウムが好ましい。前記金属化合物の添加量は、酢酸ビニルエマルジョンの固形分１００質量部に対して、１０〜４０質量部であり、好ましくは１５〜２５質量部である。   The aqueous adhesive contains a specific metal compound. Metal compounds include beryllium, zirconium, titanium, chromium, calcium, magnesium, zinc, barium, strontium, aluminum, bismuth, antimony, cobalt, iron, nickel, and other chlorides, oxides, hydroxides, basic salts, Acid salts, neutral salts, amine complexes, and the like can be mentioned. Among these, carbonates of the metal compounds are preferable, and calcium carbonate that also functions as a filler is preferable. The addition amount of the metal compound is 10 to 40 parts by mass, preferably 15 to 25 parts by mass with respect to 100 parts by mass of the solid content of the vinyl acetate emulsion.

本水性接着剤は、さらなる耐水性向上のためにシラン系カップリング剤を含む。シラン系カップリング剤としてはビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−メタクリロキシプロピルトリメトキシシラン、ビニルトリアセトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、ビニルトリクロルシラン、γ−メルカプトプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−（β−アミノエチル）−γ−アミノプロピルトリメトキシシランなどがあり、これらの１種を単独で又は２種以上を混合して用いることができる。
これらシラン系カップリング剤の添加量は、酢酸ビニルエマルジョンの固形分１００質量部に対して、０．０１〜５質量部であり、好ましくは０．１〜３質量部であり、前記の金属化合物添加後に添加することが好ましい。カップリング剤を添加することにより、金属化合物の疎水化と被膜構成時でのエマルジョンの架橋が進むことにより耐水性が向上するものと思われる。 This water-based adhesive contains a silane coupling agent for further improvement of water resistance. As silane coupling agents, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ -Aminopropyltrimethoxysilane and the like, and one of these may be used alone or two or more of them may be used in combination.
The addition amount of these silane coupling agents is 0.01 to 5 parts by mass, preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the solid content of the vinyl acetate emulsion. It is preferable to add after the addition. By adding a coupling agent, it is considered that water resistance is improved by hydrophobizing the metal compound and cross-linking the emulsion at the time of coating formation.

本発明の接着剤は、酢酸ビニル系樹脂エマルジョンおよび金属化合物ならびにシラン系カップリング剤に加えて、顔料、増量剤、可塑剤、安定剤、防腐剤などを含んでいてもよい。本発明の接着剤は、家具、合板などの木材、紙、繊維などの高耐水性の接着剤として好適である。   The adhesive of the present invention may contain pigments, extenders, plasticizers, stabilizers, preservatives and the like in addition to the vinyl acetate resin emulsion and the metal compound and the silane coupling agent. The adhesive of the present invention is suitable as a highly water-resistant adhesive for wood such as furniture and plywood, paper, and fiber.

次に、実施例、比較例を挙げて本発明をより具体的に説明する。   Next, the present invention will be described more specifically with reference to examples and comparative examples.

＜水性接着剤の調製＞
［実施例１］
ＡＡ化ＰＶＡ（日本合成化学工業（株）製「ゴーセネックスＺ−２１０」）３７質量部およびＥＶＯＨ（（株）クラレ製「エクセバールＲＳ−２１１７」）３７質量部を水１２０３質量部に分散し、８０℃にて１時間撹拌することにより溶解した。この水溶液に、酒石酸の１０％水溶液３質量部と、過酸化水素の１．４％水溶液１質量部と、を加えた後、酢酸ビニルモノマー１０００質量部と、過酸化水素の１．４％水溶液５質量部と、オクチルチオグリコレート２質量部と、を３時間で滴下して乳化重合を行った。重合後、そのまま８０℃にて１時間熟成し、冷却後、炭酸カルシウム２００質量部を添加・攪拌して、酢酸ビニル樹脂エマルジョン系水性接着剤（樹脂分５０％）を得た。 <Preparation of water-based adhesive>
[Example 1]
37 parts by mass of AA-PVA (Nippon Synthetic Chemical Co., Ltd. “GOHSEX Z-210”) and EVOH (Kuraray Co., Ltd. “Exeval RS-2117”) 37 parts by mass are dispersed in 1203 parts by mass of water. It melt | dissolved by stirring at 1 degreeC for 1 hour. After adding 3 parts by weight of a 10% aqueous solution of tartaric acid and 1 part by weight of a 1.4% aqueous solution of hydrogen peroxide to this aqueous solution, 1000 parts by weight of a vinyl acetate monomer and a 1.4% aqueous solution of hydrogen peroxide 5 parts by mass and 2 parts by mass of octylthioglycolate were added dropwise over 3 hours to carry out emulsion polymerization. After polymerization, the mixture was aged at 80 ° C. for 1 hour, and after cooling, 200 parts by mass of calcium carbonate was added and stirred to obtain a vinyl acetate resin emulsion-based aqueous adhesive (resin content: 50%).

［実施例２］
実施例１において、モノマーに酢酸ビニルモノマー９５０質量部と２−アセトアセトキシエチルメタクリレート（ＡＡＥＭ）５０質量部とし、乳化共重合を行い、酢酸ビニル樹脂エマルジョン系水性接着剤（樹脂分４５％）を得た。 [Example 2]
In Example 1, 950 parts by mass of vinyl acetate monomer and 50 parts by mass of 2-acetoacetoxyethyl methacrylate (AAEM) are used as monomers, and emulsion copolymerization is performed to obtain a vinyl acetate resin emulsion-based aqueous adhesive (resin content 45%). It was.

［実施例３］
実施例1において、炭酸カルシウム添加後に、３−グリシドキシプロピルトリメトキシシランであるエボニック社製ダイナシランＧＬＹＭＯ（商品名）１質量部を添加・攪拌して、酢酸ビニル樹脂エマルジョン系水性接着剤（樹脂分約５０％）を得た。 [Example 3]
In Example 1, after adding calcium carbonate, 1 part by weight of Dynasilane GLYMO (trade name) manufactured by Evonik, which is 3-glycidoxypropyltrimethoxysilane, was added and stirred, and a vinyl acetate resin emulsion-based aqueous adhesive (resin About 50%).

［比較例１］
ＡＡ化ＰＶＡ（日本合成化学工業（株）製「ゴーセネックスＺ−２００」）１４０質量部を水１３９０質量部に分散し、８０℃にて１時間撹拌することにより溶解した。この水溶液に、酒石酸の１０％水溶液３質量部と、過酸化水素の１．４％水溶液１質量部と、を加えた後、酢酸ビニルモノマー１０００質量部と、２−アセトアセトキシエチルメタクリレート（ＡＡＥＭ）５０質量部と、過酸化水素の１．４％水溶液５質量部と、を３時間で滴下して乳化共重合を行った。重合後、そのまま８０℃にて１時間熟成し、冷却後、塩化アルミニウムの２０％水溶液４２０質量部を添加して、アセトアセチル基を有する酢酸ビニル樹脂エマルジョン系水性接着剤（樹脂分４２％）を得た。 [Comparative Example 1]
140 parts by mass of AA-PVA (“GOHSEX Z-200” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was dispersed in 1390 parts by mass of water and dissolved by stirring at 80 ° C. for 1 hour. After adding 3 parts by weight of a 10% aqueous solution of tartaric acid and 1 part by weight of a 1.4% aqueous solution of hydrogen peroxide to this aqueous solution, 1000 parts by weight of vinyl acetate monomer and 2-acetoacetoxyethyl methacrylate (AAEM) 50 parts by mass and 5 parts by mass of a 1.4% aqueous solution of hydrogen peroxide were added dropwise over 3 hours to carry out emulsion copolymerization. After polymerization, the mixture is aged at 80 ° C. for 1 hour, and after cooling, 420 parts by mass of a 20% aqueous solution of aluminum chloride is added to obtain a vinyl acetate resin emulsion-based aqueous adhesive having an acetoacetyl group (resin content 42%). Obtained.

［比較例２］
比較例１において、塩化アルミニウムを添加せず、乳化重合後冷却し、炭酸カルシウム粉末（平均粒子径２μｍ）を１５０質量部添加し、アセトアセチル基を有する酢酸ビニル樹脂エマルジョン系水性接着剤（樹脂分４７％）を得た。 [Comparative Example 2]
In Comparative Example 1, aluminum chloride was not added, and after emulsion polymerization, cooling was performed, 150 parts by mass of calcium carbonate powder (average particle size 2 μm) was added, and a vinyl acetate resin emulsion-based aqueous adhesive having an acetoacetyl group (resin content) 47%).

＜接着剤の評価＞
実施例および比較例の各水性接着剤の保存性および接着性能を、以下の試験方法により評価した。 <Evaluation of adhesive>
The storage stability and adhesive performance of each aqueous adhesive in Examples and Comparative Examples were evaluated by the following test methods.

［試験方法／保存性］
５００ｍｌポリエチレン製広口瓶に入れた各水性接着剤３００ｇを５０℃恒温槽内に７日間静置し、その後２３℃まで静置し、容器を傾けるとすぐに流れ出す状態を○、容器を傾けるとゆっくり動き、軽く振るだけで元に戻る状態を△、容器を傾けても動かないが攪拌すると元に戻る状態を×として評価した。 [Test Method / Storage]
300g of each water-based adhesive placed in a 500ml polyethylene jar is left in a 50 ° C thermostatic bath for 7 days, then left to 23 ° C. It was evaluated as “△” when it moved and lightly shaken, and “x” when it was not stirred even if the container was tilted but returned to its original state after stirring.

［試験方法／接着性能］
常温にて、２枚の３００ｍｍ×１５０ｍｍのブナ柾目材の片面に、接着剤を１５０ｇ／ｍ２ずつ均一に塗布して、貼り合わせた。堆積時間を３０分間以内とし、その後１．０ＭＰａで４時間圧締後常温にて７日間養生して、試験体を製造した。各試験体はＤＩＮ／ＥＮ２０４Ｄ３の試験法に従い。（１）常態、および（２）室温水４日間浸漬、（３）室温水４日間浸漬後２３℃−５０％ＲＨの恒温恒湿槽内で７日間静置した後、引張せん断試験にて接着力を測定した。 [Test method / Adhesion performance]
At room temperature, 150 g / m 2 of an adhesive was uniformly applied to one side of two 300 mm × 150 mm beech mesh materials and bonded together. The deposition time was set to be within 30 minutes, after which it was pressed at 1.0 MPa for 4 hours and then cured at room temperature for 7 days to produce a test specimen. Each specimen follows the test method of DIN / EN204D3. (1) Normal state, (2) Room temperature water immersed for 4 days, (3) Room temperature water immersed for 4 days, left in a constant temperature and humidity chamber at 23 ° C.-50% RH for 7 days, then bonded by tensile shear test The force was measured.

［試験結果］
表１に、各水性接着剤の配合組成（表中の○は配合有りを示す）、および評価結果をまとめて示す。 [Test results]
Table 1 summarizes the composition of each water-based adhesive (circles in the table indicate blending) and evaluation results.

表から明らかなように、本水性接着剤は高い耐水性能を有する接着剤となる。   As is apparent from the table, the water-based adhesive is an adhesive having high water resistance.

＜水性接着剤の調製＞
［参考例１］
ＡＡ化ＰＶＡ（日本合成化学工業（株）製「ゴーセネックスＺ−２１０」）３７質量部およびＥＶＯＨ（（株）クラレ製「エクセバールＲＳ−２１１７」）３７質量部を水１２０３質量部に分散し、８０℃にて１時間撹拌することにより溶解した。この水溶液に、酒石酸の１０％水溶液３質量部と、過酸化水素の１．４％水溶液１質量部と、を加えた後、酢酸ビニルモノマー１０００質量部と、過酸化水素の１．４％水溶液５質量部と、オクチルチオグリコレート２質量部と、を３時間で滴下して乳化重合を行った。重合後、そのまま８０℃にて１時間熟成し、冷却後、炭酸カルシウム２００質量部を添加・攪拌して、酢酸ビニル樹脂エマルジョン系水性接着剤（樹脂分５０％）を得た。
<Preparation of water-based adhesive>
[Reference Example 1]
37 parts by mass of AA-PVA (Nippon Synthetic Chemical Co., Ltd. “GOHSEX Z-210”) and EVOH (Kuraray Co., Ltd. “Exeval RS-2117”) 37 parts by mass are dispersed in 1203 parts by mass of water. It melt | dissolved by stirring at 1 degreeC for 1 hour. After adding 3 parts by weight of a 10% aqueous solution of tartaric acid and 1 part by weight of a 1.4% aqueous solution of hydrogen peroxide to this aqueous solution, 1000 parts by weight of a vinyl acetate monomer and a 1.4% aqueous solution of hydrogen peroxide 5 parts by mass and 2 parts by mass of octylthioglycolate were added dropwise over 3 hours to carry out emulsion polymerization. After polymerization, the mixture was aged at 80 ° C. for 1 hour, and after cooling, 200 parts by mass of calcium carbonate was added and stirred to obtain a vinyl acetate resin emulsion-based aqueous adhesive (resin content: 50%).

［参考例２］
参考例１において、モノマーに酢酸ビニルモノマー９５０質量部と２−アセトアセトキシエチルメタクリレート（ＡＡＥＭ）５０質量部とし、乳化共重合を行い、酢酸ビニル樹脂エマルジョン系水性接着剤（樹脂分４５％）を得た。
 [Reference Example 2]
In Reference Example 1 , 950 parts by mass of vinyl acetate monomer and 50 parts by mass of 2-acetoacetoxyethyl methacrylate (AAEM) are used as monomers, and emulsion copolymerization is performed to obtain a vinyl acetate resin emulsion-based aqueous adhesive (resin content 45%). It was.

［実施例１］
参考例1において、炭酸カルシウム添加後に、３−グリシドキシプロピルトリメトキシ
シランであるエボニック社製ダイナシランＧＬＹＭＯ（商品名）１質量部を添加・攪拌して、酢酸ビニル樹脂エマルジョン系水性接着剤（樹脂分約５０％）を得た。
 [Example 1]
In Reference Example 1 , after adding calcium carbonate, 1 part by mass of Evonik's Dynasilane GLYMO (trade name), which is 3-glycidoxypropyltrimethoxysilane, was added and stirred, and a vinyl acetate resin emulsion-based aqueous adhesive (resin About 50%).

Claims (6)

アセトアセチル化ポリビニルアルコールおよびエチレン変性ポリビニルアルコールを含むポリビニルアルコールを保護コロイドとして、酢酸ビニルモノマーを乳化重合した、または酢酸ビニルモノマーとアセトアセチル基を有するモノマーとを乳化共重合した酢酸ビニル系樹脂エマルジョンに、金属化合物を配合してなることを特徴とする水性接着剤。   A vinyl acetate resin emulsion obtained by emulsion polymerization of a vinyl acetate monomer or emulsion copolymerization of a vinyl acetate monomer and a monomer having an acetoacetyl group using polyvinyl alcohol containing acetoacetylated polyvinyl alcohol and ethylene-modified polyvinyl alcohol as a protective colloid. An aqueous adhesive comprising a metal compound. アセトアセチル化ポリビニルアルコールおよびエチレン変性ポリビニルアルコールを含むポリビニルアルコールを保護コロイドとして、酢酸ビニルモノマーを乳化重合した、または酢酸ビニルモノマーとアセトアセチル基を有するモノマーとを乳化共重合した酢酸ビニル系樹脂エマルジョンに、金属化合物を配合した後にシラン系カップリング剤を配合してなることを特徴とする水性接着剤。   A vinyl acetate resin emulsion obtained by emulsion polymerization of a vinyl acetate monomer or emulsion copolymerization of a vinyl acetate monomer and a monomer having an acetoacetyl group using polyvinyl alcohol containing acetoacetylated polyvinyl alcohol and ethylene-modified polyvinyl alcohol as a protective colloid. An aqueous adhesive comprising a silane coupling agent after compounding a metal compound. 前記金属化合物がカルシウム化合物である請求項1または２に記載の水性接着剤。   The aqueous adhesive according to claim 1 or 2, wherein the metal compound is a calcium compound. 前記酢酸ビニルモノマーの乳化重合が、連鎖移動剤の存在下で重合される請求項１から３のいずれかにに記載の水性接着剤。   The aqueous adhesive according to any one of claims 1 to 3, wherein the emulsion polymerization of the vinyl acetate monomer is polymerized in the presence of a chain transfer agent. 前記連鎖移動剤がオクチルチオグリコレートである請求項４記載の水性接着剤。   The aqueous adhesive according to claim 4, wherein the chain transfer agent is octyl thioglycolate. 前記酢酸ビニル系樹脂エマルジョンが、酢酸ビニルモノマーとアセトアセチル基を有するモノマーとを乳化共重合する請求項１から４のいずれかに記載の水性接着剤。 The aqueous adhesive according to any one of claims 1 to 4, wherein the vinyl acetate resin emulsion is an emulsion copolymer of a vinyl acetate monomer and a monomer having an acetoacetyl group.
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