JP4502628B2 - Adhesive composition - Google Patents
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- JP4502628B2 JP4502628B2 JP2003386282A JP2003386282A JP4502628B2 JP 4502628 B2 JP4502628 B2 JP 4502628B2 JP 2003386282 A JP2003386282 A JP 2003386282A JP 2003386282 A JP2003386282 A JP 2003386282A JP 4502628 B2 JP4502628 B2 JP 4502628B2
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Description
本願発明は、エチレン−ビニルエステル系水性エマルジョンに、平均粒子径が６μｍ以下の無機充填剤、ポリビニルアルコール（以後ＰＶＡと称す）、多価イソシアネート化合物を配合してなる、発泡性が低く、常態接着強度や煮沸繰り返し接着強度に優れた接着剤に関するものである。 The present invention comprises an ethylene-vinyl ester-based aqueous emulsion and an inorganic filler having an average particle size of 6 μm or less, polyvinyl alcohol (hereinafter referred to as PVA), and a polyvalent isocyanate compound. The present invention relates to an adhesive having excellent strength and boiling repeated adhesive strength.
本願発明でいう、エチレン−ビニルエステル系水性エマルジョンに、無機充填剤、ＰＶＡ、多価イソシアネート化合物を配合してなる接着剤は、一般的には水性高分子−イソシアネート系木材接着剤（以後「水性ビニルウレタン接着剤」と称す）と言われている。従来の水性ビニルウレタン接着剤では、ＰＶＡに多価イソシアネート化合物、無機充填剤を配合して接着剤を構成していた（例えば、特許文献１参照）。また、初期接着性を改良すべく、ＰＶＡを保護コロイドとして乳化共重合して得られた酢酸ビニル系エマルジョンに多価イソシアネート化合物を配合する接着剤も提唱されていた（例えば、特許文献２参照）。ところが、ＰＶＡを保護コロイドとした酢酸ビニル系エマルジョン（ＰＶＡ・酢ビ系エマルジョンと称す）を用いると、架橋剤として加えた多価イソシアネートが水と反応して二酸化炭素を発生し、接着剤層に多数の気泡が含まれてしまい、接着性能の低下を引き起こしてしまう。また、貼り合わせの際にはみ出た接着剤が発泡してしまい、接着剤が硬化した後にこれを取り除かなくてはならないという課題も抱えていた。 In the present invention, an adhesive comprising an ethylene-vinyl ester-based aqueous emulsion and an inorganic filler, PVA, and a polyvalent isocyanate compound is generally an aqueous polymer-isocyanate-based wood adhesive (hereinafter “water-based”). It is called “vinyl urethane adhesive”. In a conventional aqueous vinyl urethane adhesive, an adhesive is formed by blending a polyvalent isocyanate compound and an inorganic filler into PVA (for example, see Patent Document 1). In addition, in order to improve the initial adhesiveness, an adhesive has been proposed in which a polyvalent isocyanate compound is blended with a vinyl acetate emulsion obtained by emulsion copolymerization using PVA as a protective colloid (see, for example, Patent Document 2). . However, when a vinyl acetate emulsion using PVA as a protective colloid (referred to as a PVA / vinyl acetate emulsion) is used, the polyvalent isocyanate added as a cross-linking agent reacts with water to generate carbon dioxide, which is generated in the adhesive layer. A large number of bubbles are included, causing a decrease in adhesion performance. Moreover, the adhesive which protruded in the case of bonding foamed, and also had the subject that this had to be removed after an adhesive hardened | cured.
本願発明が解決しようとする課題は、この水性ビニルウレタン接着剤において、これまでと同等性能の常態接着強度や煮沸繰り返し接着強度を持ち、且つ接着剤の発泡性を低減することにある。 The problem to be solved by the present invention is that this aqueous vinyl urethane adhesive has normal adhesive strength and boiling repeated adhesive strength with the same performance as before, and reduces the foamability of the adhesive.
本願発明は、かかる課題の解決を達成すべく鋭意検討した結果、初期接着性改善目的でＰＶＡ・酢ビ系エマルジョンを使用した場合でも、粒子径が６μｍ以下の無機充填剤を添加することにより、二酸化炭素ガスの発生を抑制でき、従来の性能も併せ持つ水性ビニルウレタン接着剤が得られることを見出した。 As a result of intensive investigations to achieve a solution to such problems, the present invention is based on the addition of an inorganic filler having a particle size of 6 μm or less even when a PVA / vinyl acetate emulsion is used for the purpose of improving initial adhesiveness. It has been found that an aqueous vinyl urethane adhesive that can suppress the generation of carbon dioxide gas and has the conventional performance can be obtained.
本願発明の水性ビニルウレタン系接着剤を使用することによって、多価イソシアネートを配合した後、この多価イソシアネートと水との反応が抑制されることにより、今まで以上の可使時間が確保され、更にははみ出した接着剤層の発泡による膨れも目立たず、少量のはみ出しであればこれを取り除く為の作業も必要でなくなり、作業効率の格段の改善が期待できる。 By using the aqueous vinyl urethane-based adhesive of the present invention, after blending the polyvalent isocyanate, by suppressing the reaction between the polyvalent isocyanate and water, a longer usable time than ever is ensured, Further, the swelling of the protruding adhesive layer due to foaming is not noticeable, and if it is a small amount of protrusion, the work for removing it is not necessary, and a marked improvement in work efficiency can be expected.
本願発明は接着剤の発泡による可使時間低下を抑制し、更には接着剤層の膨れも少なく、はみ出し部の発泡が少なくなる事から、その部分の除去にかかる手間も減り、産業上、非常に有効に利用できる技術である。 The present invention suppresses the reduction in usable time due to foaming of the adhesive, and further, the swelling of the adhesive layer is small and the foaming of the protruding portion is reduced. This technology can be used effectively.
本願発明を実施する上で、エチレン−ビニルエステル系水性エマルジョン、ＰＶＡ、無機充填剤、多価イソシアネート化合物が必須成分であるが、中でも無機充填剤の平均粒子径が接着剤の発泡性に大きく影響してくる。無機充填剤の平均粒子径は６μｍ以下、好ましくは０．５〜４μｍ、更に好ましくは０．５〜２μｍの範囲もののである。無機充填剤の平均粒子径が６μｍを超えると、多価イソシアネート化合物を加えた段階で大量の二酸化炭素が発生し、接着剤が発泡してしまう。これは無機充填剤の平均粒子径が大きいほど無機充填剤の総表面積が減り、加えた多価イソシアネート化合物が無機充填剤に含浸される割合が低くなり、より多くの多価イソシアネート化合物が水相で水と反応してしまう為に多量の二酸化炭素を発生するためと推測している。 In carrying out the invention of the present application, ethylene-vinyl ester aqueous emulsion, PVA, inorganic filler, and polyvalent isocyanate compound are essential components. Among them, the average particle size of the inorganic filler has a great influence on the foamability of the adhesive. Come on. The average particle diameter of the inorganic filler is 6 μm or less, preferably 0.5 to 4 μm, more preferably 0.5 to 2 μm. When the average particle diameter of the inorganic filler exceeds 6 μm, a large amount of carbon dioxide is generated at the stage where the polyvalent isocyanate compound is added, and the adhesive is foamed. This is because the larger the average particle size of the inorganic filler, the smaller the total surface area of the inorganic filler, the lower the proportion of the added polyvalent isocyanate compound impregnated in the inorganic filler, and the more polyvalent isocyanate compound is in the aqueous phase. It is assumed that a large amount of carbon dioxide is generated because it reacts with water.
無機充填剤の種類としては、炭酸カルシムや炭酸マグネシウム、水酸化アルミニウム、水酸化マグネシウム、水酸化バリウム、ケイ酸マグネシウム、タルク、シリカ、クレー、二酸化チタンといったものが幅広く使用できる。中でも炭酸カルシウムが好適に使用することができる。また無機充填剤の添加量は、接着剤の作業性や性能に悪影響を与えない程度であれば特に限定されない。 As a kind of inorganic filler, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, barium hydroxide, magnesium silicate, talc, silica, clay, titanium dioxide and the like can be widely used. Of these, calcium carbonate can be preferably used. The amount of the inorganic filler added is not particularly limited as long as it does not adversely affect the workability and performance of the adhesive.
エチレン及びビニルエステルを必須成分とする共重合体エマルジョンを含む水性エマルジョンのビニルエステル単位としては、例えば、酢酸ビニル、酪酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、ラウリン酸ビニル、バーサチック酸ビニル等のビニルエステルが挙げられ、２種類以上のビニルエステル単位を使用しても構わない。これらビニルエステル単位の中では酢酸ビニルが最も好適に使用できる。 Examples of the vinyl ester unit of an aqueous emulsion including a copolymer emulsion containing ethylene and vinyl ester as essential components include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl pivalate, vinyl laurate, vinyl versatate, and the like. An ester may be mentioned, and two or more kinds of vinyl ester units may be used. Of these vinyl ester units, vinyl acetate is most preferably used.
接着剤中のエチレン及びビニルエステルを必須成分とする共重合体エマルジョンの量は、接着剤の作業性や性能に悪影響を与えなければ、特に規定されない。この共重合体エマルジョンのエチレン含量は５〜３０質量％が好ましく、更に好ましくは１０〜２０質量％である。エチレン含量が５質量％よりも少ないと、得られた接着剤の耐水性、特に煮沸繰り返し接着強度が低下してしまう。エチレン含量が３０質量％を超えると、得られた接着剤の常態接着強度が低下してしまう。 The amount of the copolymer emulsion containing ethylene and vinyl ester as essential components in the adhesive is not particularly specified as long as it does not adversely affect the workability and performance of the adhesive. The ethylene content of this copolymer emulsion is preferably 5 to 30% by mass, more preferably 10 to 20% by mass. When the ethylene content is less than 5% by mass, the water resistance of the obtained adhesive, particularly the boiling repeated adhesive strength, is lowered. When ethylene content exceeds 30 mass%, the normal adhesive strength of the obtained adhesive will fall.
接着剤中のＰＶＡには、部分鹸化タイプ、完全鹸化タイプ、カルボン酸変性タイプ、ビニルエーテル変性タイプ等の様々な種類のＰＶＡが使用可能だが、部分鹸化タイプのＰＶＡが最も好ましい。ＰＶＡの鹸化度、重合度、添加量は、接着剤の作業性や性能に極端に悪影響を及ぼさなければ、特に限定されるものではない。 Various types of PVA, such as a partially saponified type, a fully saponified type, a carboxylic acid modified type, and a vinyl ether modified type, can be used for the PVA in the adhesive, but the partially saponified PVA is most preferable. The saponification degree, polymerization degree, and addition amount of PVA are not particularly limited as long as the workability and performance of the adhesive are not adversely affected.
接着剤中の多価イソシアネート化合物としては、分子中に２個以上のイソシアネート基を有するものであり、例えば、トリレンジイソシアネート（ＴＤＩ）、水素化ＴＤＩ、トリフェニルメタントリイソシアネート、メチレンビスジフェニルイソシアネート（ＭＤＩ）、水素化ＭＤＩ、重合ＭＤＩ、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、４，４−ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネートが挙げられる。また、これらのプレポリマーを用いても良い。多価イソシアネート化合物の添加量は、接着剤の作業性や性能に極端に悪影響を及ぼさなければ、特にこれに限定しない。 The polyvalent isocyanate compound in the adhesive has two or more isocyanate groups in the molecule. For example, tolylene diisocyanate (TDI), hydrogenated TDI, triphenylmethane triisocyanate, methylenebisdiphenyl isocyanate ( MDI), hydrogenated MDI, polymerized MDI, hexamethylene diisocyanate, xylylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, isophorone diisocyanate. Moreover, you may use these prepolymers. The addition amount of the polyvalent isocyanate compound is not particularly limited as long as it does not extremely adversely affect the workability and performance of the adhesive.
本願発明の接着剤には、必要であれば本願発明の効果を損なわない範囲で各種添加剤や他のエマルジョン、ラテックスを添加しても良い。各種添加剤としては、消泡剤や防腐剤、防黴剤、防錆剤、濡れ剤、粘度調整剤、増粘剤、難燃剤などが挙げられる。他のエマルジョン、ラテックスにはスチレン−ブタジエン共重合体ラテックス、スチレン−アクリルエマルジョン、アクリルエマルジョン等が挙げられる。また、必要に応じてヒドロキシエチルセルロースやメチルセルロース、カルボキシメチルセルロースといった水溶性高分子や、従来既知のアニオン性、カチオン性又はノニオン性界面活性剤を使用しても構わない。 If necessary, various additives, other emulsions and latex may be added to the adhesive of the present invention as long as the effects of the present invention are not impaired. Examples of the various additives include antifoaming agents, antiseptics, antifungal agents, rust inhibitors, wetting agents, viscosity modifiers, thickeners, flame retardants, and the like. Other emulsions and latexes include styrene-butadiene copolymer latex, styrene-acrylic emulsion, acrylic emulsion and the like. Moreover, you may use water-soluble polymer, such as a hydroxyethyl cellulose, methylcellulose, and carboxymethylcellulose, and a conventionally well-known anionic, cationic, or nonionic surfactant as needed.
（エチレン−酢酸ビニル共重合エマルジョンの製造方法．１）
攪拌機、加熱・冷却機能を持った内容積５Ｌのオートクレーブに、イオン交換水１３００ｇ、「デンカＰＶＡ Ｂ−０５（電気化学工業株式会社製ＰＶＡ，鹸化度８８ｍｏｌｅ％，重合度５００）」を６０ｇ、「デンカＰＶＡ Ｂ−１７（電気化学工業株式会社製ＰＶＡ，鹸化度８８ｍｏｌｅ％，重合度１７００）」を１５ｇ、ｐＨ調整剤として酢酸ナトリウム３ｇを加え、９５℃で３時間攪拌を継続してＰＶＡを溶解して重合原液を作製する。冷却して温度が５０℃以下になった段階で、ロンガリット３ｇ、硫酸第一鉄０．７５ｇをイオン交換水２００ｇに溶解し、オートクレーブ内に加える。攪拌しながら窒素でオートクレーブ内上方を置換し、酢酸ビニル１５００ｇを加える。これにエチレンを４５０ｇ加え、内温を６０℃とした上で０．５％の過硫酸アンモニウム水溶液を５０ｍｌ／Ｈｒの速度で５時間添加し続ける。その間は重合反応に伴う発熱を、オートクレーブのジャケット内部に冷却水を通じ、内温が６０℃一定となる様に制御して重合を完結する。冷却後、未反応のエチレンを除去した後、５０メッシュの金網で濾過して、不揮発分５４．５％、粘度２３００ｍＰａ・ｓ、エチレン含量２５質量％のエチレン−酢酸ビニル共重合エマルジョンを得た。
(Method for producing ethylene-vinyl acetate copolymer emulsion. 1)
In an autoclave with an internal volume of 5 L having a stirrer and a heating / cooling function, 1300 g of ion-exchanged water, 60 g of “Denka PVA B-05 (PVA manufactured by Denki Kagaku Co., Ltd., saponification degree 88 mole%, polymerization degree 500)” 15 g of Denka PVA B-17 (PVA manufactured by Denki Kagaku Kogyo Co., Ltd., saponification degree 88 mole%, polymerization degree 1700) and 3 g of sodium acetate as a pH adjuster were added, and stirring was continued at 95 ° C. for 3 hours to dissolve PVA. To prepare a polymerization stock solution. When the temperature is lowered to 50 ° C. or less after cooling, 3 g of Rongalite and 0.75 g of ferrous sulfate are dissolved in 200 g of ion-exchanged water and added to the autoclave. While stirring, the upper part of the autoclave is replaced with nitrogen, and 1500 g of vinyl acetate is added. To this was added 450 g of ethylene, the internal temperature was adjusted to 60 ° C., and 0.5% ammonium persulfate aqueous solution was continuously added at a rate of 50 ml / Hr for 5 hours. In the meantime, the heat generated by the polymerization reaction is controlled by passing cooling water through the jacket of the autoclave so that the internal temperature is kept constant at 60 ° C. to complete the polymerization. After cooling, unreacted ethylene was removed, followed by filtration through a 50 mesh wire mesh to obtain an ethylene-vinyl acetate copolymer emulsion having a nonvolatile content of 54.5%, a viscosity of 2300 mPa · s, and an ethylene content of 25% by mass.
（エチレン−酢酸ビニル共重合エマルジョンの製造方法．２）
エチレンの仕込量を３６０ｇとする以外は（エチレン−酢酸ビニル共重合エマルジョンの製造方法．１）と同様にして重合を行った。得られたエマルジョンは、不揮発分５５．２％、粘度３０００ｍＰａ・ｓ、エチレン含量１８質量％のエチレン−酢酸ビニル共重合エマルジョンであった。
(Method for producing ethylene-vinyl acetate copolymer emulsion. 2)
Polymerization was carried out in the same manner as in (Production method of ethylene-vinyl acetate copolymer emulsion 1) except that the amount of ethylene charged was 360 g. The obtained emulsion was an ethylene-vinyl acetate copolymer emulsion having a nonvolatile content of 55.2%, a viscosity of 3000 mPa · s, and an ethylene content of 18% by mass.
（エチレン−酢酸ビニル共重合エマルジョンの製造方法．３）
エチレンの仕込量を２７０ｇとする以外は（エチレン−酢酸ビニル共重合エマルジョンの製造方法．１）と同様にして重合を行った。得られたエマルジョンは、不揮発分５５．１％、粘度４０００ｍＰａ・ｓ、エチレン含量１５質量％のエチレン−酢酸ビニル共重合エマルジョンであった。
(Method for producing ethylene-vinyl acetate copolymer emulsion. 3)
Polymerization was carried out in the same manner as in (Manufacturing method of ethylene-vinyl acetate copolymer emulsion 1) except that the amount of ethylene charged was 270 g. The obtained emulsion was an ethylene-vinyl acetate copolymer emulsion having a nonvolatile content of 55.1%, a viscosity of 4000 mPa · s, and an ethylene content of 15% by mass.
（エチレン−酢酸ビニル共重合エマルジョンの製造方法．４）
エチレンの仕込量を２２５ｇとする以外は（エチレン−酢酸ビニル共重合エマルジョンの製造方法．１）と同様にして重合を行った。得られたエマルジョンは、不揮発分５４．０％、粘度３３００ｍＰａ・ｓ、エチレン含量１３質量％のエチレン−酢酸ビニル共重合エマルジョンであった。
(Method for producing ethylene-vinyl acetate copolymer emulsion. 4)
Polymerization was carried out in the same manner as in (Production method of ethylene-vinyl acetate copolymer emulsion 1) except that the amount of ethylene charged was 225 g. The obtained emulsion was an ethylene-vinyl acetate copolymer emulsion having a nonvolatile content of 54.0%, a viscosity of 3300 mPa · s, and an ethylene content of 13% by mass.
（エチレン−酢酸ビニル共重合エマルジョンの製造方法．３）で製造したエチレン含量１５質量％のエチレン−酢酸ビニル共重合エマルジョンを４５質量部、１５質量％のＰＶＡ水溶液（電気化学工業株式会社製「デンカＰＶＡ Ｂ−１７」（鹸化度８８ｍｏｌｅ％、重合度１７００の部分鹸化ＰＶＡ））を２０質量部、平均粒子径１．５μｍの炭酸カルシウムを３０質量部、及び調整水を３質量部加え、良く混合したものを主剤とした。この主剤１００質量部に対して、三井武田ケミカル株式会社製「コスモネート Ｍ−１００」（ポリメリックＭＤＩ）を１５質量部添加して、接着剤組成物とした。 45 parts by mass of an ethylene-vinyl acetate copolymer emulsion having an ethylene content of 15% by mass produced in (Manufacturing method of ethylene-vinyl acetate copolymer emulsion 3) and a 15% by mass PVA aqueous solution (“DENKA 20 parts by mass of PVA B-17 ”(partially saponified PVA having a saponification degree of 88 mole% and a polymerization degree of 1700), 30 parts by mass of calcium carbonate having an average particle size of 1.5 μm, and 3 parts by mass of adjusted water were added and mixed well. This was the main ingredient. 15 parts by mass of “Cosmonate M-100” (polymeric MDI) manufactured by Mitsui Takeda Chemical Co., Ltd. was added to 100 parts by mass of the main agent to obtain an adhesive composition.
実施例１において、平均粒子径が３．２μｍの炭酸カルシウムを使用した以外は、実施例１と同様にして接着剤組成物を作製した。 In Example 1, an adhesive composition was produced in the same manner as in Example 1 except that calcium carbonate having an average particle size of 3.2 μm was used.
実施例１において、（エチレン−酢酸ビニル共重合エマルジョンの製造方法．４）で製造したエチレン含量１３質量％のエチレン−酢酸ビニル共重合エマルジョンを使用した以外は、実施例１と同様にして接着剤組成物を作製した。 In Example 1, an adhesive was used in the same manner as in Example 1 except that the ethylene-vinyl acetate copolymer emulsion having an ethylene content of 13% by mass produced in (Ethylene-vinyl acetate copolymer emulsion production method 4) was used. A composition was prepared.
実施例１において、（エチレン−酢酸ビニル共重合エマルジョンの製造方法．２）で製造したエチレン含量１８質量％のエチレン−酢酸ビニル共重合エマルジョン使用した以外は、実施例１と同様にして接着剤組成物を作製した。 The adhesive composition was the same as in Example 1 except that the ethylene-vinyl acetate copolymer emulsion having an ethylene content of 18% by mass produced in (Ethylene-vinyl acetate copolymer emulsion production method 2) was used. A product was made.
実施例１において、（エチレン−酢酸ビニル共重合エマルジョンの製造方法．１）で製造したエチレン含量２５質量％のエチレン−酢酸ビニル共重合エマルジョンを使用した以外は、実施例１と同様にして接着剤組成物を作製した。 In Example 1, an adhesive was used in the same manner as in Example 1 except that the ethylene-vinyl acetate copolymer emulsion having an ethylene content of 25% by mass produced in (Process for producing ethylene-vinyl acetate copolymer emulsion. 1) was used. A composition was prepared.
［比較例］
実施例１において、平均粒子径が８．１μｍの炭酸カルシウムを使用した以外は、実施例１と同様にして接着剤組成物を作製した。
[Comparative example]
In Example 1, an adhesive composition was produced in the same manner as in Example 1 except that calcium carbonate having an average particle size of 8.1 μm was used.
本発明において実施した接着剤の測定・評価方法を以下に説明する。
（二酸化炭素発生量）
調整した接着剤をテフロン（登録商標）シート上に縦１００ｍｍ、横１００ｍｍ、厚さ０．５ｍｍとなる様にキャストし、テフロン（登録商標）シートごと臭化ナトリウム飽和水溶液で２３℃×５５ＲＨ％に湿度調整したデシケーター内に保管し、所定時間毎にデシケーター内部のガスをサンプリングし、二酸化炭素濃度をガスクロマトグラフィにて測定した。
（常態接着強度）
以下の条件で貼り合わせた試験体を作製後、ＪＩＳ Ｋ ６８５２に準じて圧縮剪断接着強度を測定した。
被着材：マサ目カバ材（含水率８％）同士
接着剤塗布量：２４０ｇ／ｍ2（両面塗布，片面では１２０ｇ／ｍ2）
堆積時間：１分
圧締条件：２０℃，圧力１０ｋｇ／ｃｍ2で２４時間
養生条件：解圧後、２０℃，７日間養生後
（煮沸繰り返し接着強度）
常態接着強度と同じ様にして得られた試験体を、沸騰水中に４時間浸漬した後、６０℃の空気中で２０時間養生し、更に沸騰水中に４時間浸漬してから、２０℃の水中に冷めるまで浸し、濡れたままの状態でＪＩＳ Ｋ ６８５２に準じて圧縮剪断接着強度を測定した。
The method for measuring and evaluating the adhesive carried out in the present invention will be described below.
(CO2 emissions)
The adjusted adhesive was cast on a Teflon (registered trademark) sheet so as to have a length of 100 mm, a width of 100 mm, and a thickness of 0.5 mm, and the entire Teflon (registered trademark) sheet was adjusted to 23 ° C. × 55 RH% with a saturated aqueous solution of sodium bromide. The sample was stored in a desiccator whose humidity was adjusted, the gas inside the desiccator was sampled every predetermined time, and the carbon dioxide concentration was measured by gas chromatography.
(Normal adhesive strength)
After preparing the test body bonded together under the following conditions, the compression shear adhesive strength was measured according to JIS K 6852.
Substrate: Massy birch (water content 8%) Adhesive coating amount: 240 g / m 2 (double-sided coating, single-sided 120 g / m 2 )
Deposition time: 1 minute Clamping condition: 20 ° C., pressure 10 kg / cm 2 for 24 hours Curing condition: After decompression, curing at 20 ° C. for 7 days (repeated boiling strength)
The specimen obtained in the same manner as the normal adhesive strength was immersed in boiling water for 4 hours, then cured in air at 60 ° C. for 20 hours, further immersed in boiling water for 4 hours, and then at 20 ° C. in water. It was soaked until cooled, and the compression shear adhesive strength was measured in accordance with JIS K 6852 while still wet.
炭酸カルシウムの平均粒子径は、株式会社堀場製作所製のレーザー回折／散乱式粒度分布測定装置ＬＡ−９２０を用いて、水に分散させた状態でメジアン径として測定した。 The average particle diameter of calcium carbonate was measured as a median diameter in a state of being dispersed in water using a laser diffraction / scattering particle size distribution analyzer LA-920 manufactured by Horiba, Ltd.
上記試験結果を、表１に示す。
表１から、本願発明の製造方法で得られる接着剤組成物は、二酸化炭素の発生量が少なく、且つ常態接着強度、煮沸繰り返し接着強度も充分な数値を示しており、
発泡性が少ない水性ビニルウレタン接着剤と評価される。
From Table 1, the adhesive composition obtained by the production method of the present invention has a small amount of generated carbon dioxide, and normal adhesive strength and boiling repeated adhesive strength are sufficient values,
It is evaluated as an aqueous vinyl urethane adhesive with low foaming property.
一方、平均粒子径が８．１μｍの炭酸カルシウムを使用した比較例１では、二酸化炭素の発生量が多く、接着剤層の発泡が激しいため、常態接着強度は充分な値が出てても、煮沸繰り返し接着強度が低下してしまう。 On the other hand, in Comparative Example 1 using calcium carbonate having an average particle diameter of 8.1 μm, the amount of carbon dioxide generated is large and the adhesive layer is severely foamed. Repeated boiling will reduce adhesive strength.
Claims (3)
該無機充填剤は平均粒子径が２μｍ以下の炭酸カルシウムからなり、
前記（Ａ）のエチレン− ビニルエステル系水性エマルジョンの共重合体のエチレン含量が１０〜２０質量％であることを特徴とする接着剤。 (A) An aqueous emulsion including a copolymer emulsion containing ethylene and vinyl ester as essential components, (B) polyvinyl alcohol, (C) an inorganic filler, and (D) an adhesive containing a polyvalent isocyanate compound. And
The inorganic filler is composed of calcium carbonate having an average particle size of 2 μm or less ,
The ethylene content of the copolymer of the ethylene-vinyl ester aqueous emulsion (A) is 10 to 20% by mass.
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|---|---|---|---|---|
| JPH04298593A (en) * | 1991-03-27 | 1992-10-22 | Sumitomo Durez Co Ltd | Adhesive composition |
| JPH0782540A (en) * | 1993-09-13 | 1995-03-28 | Sumitomo Chem Co Ltd | Water-resistant adhesive |
| JPH09188862A (en) * | 1996-01-08 | 1997-07-22 | Sumitomo Chem Co Ltd | Aqueous emulsion adhesive |
| JP2000327908A (en) * | 1999-05-21 | 2000-11-28 | Dyflex Corp | Urethane resin composition, coating material, sealing material and production of cured product |
| JP2001342339A (en) * | 2000-05-31 | 2001-12-14 | Dyflex Corp | Water curable urethane resin composition, coating, coating material, sealing medium, adhesive, and method of producing cured product |
| JP2002348339A (en) * | 2001-05-24 | 2002-12-04 | Sumitomo Chem Co Ltd | Ethylene/vinylester copolymer-containing water emulsion, and adhesive agent containing the same emulsion and polyvalent isocyanate compound |
| JP2002363401A (en) * | 2001-06-04 | 2002-12-18 | Konishi Co Ltd | Low-foaming one-part moisture curing type urethane resin composition |
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- 2003-11-17 JP JP2003386282A patent/JP4502628B2/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04298593A (en) * | 1991-03-27 | 1992-10-22 | Sumitomo Durez Co Ltd | Adhesive composition |
| JPH0782540A (en) * | 1993-09-13 | 1995-03-28 | Sumitomo Chem Co Ltd | Water-resistant adhesive |
| JPH09188862A (en) * | 1996-01-08 | 1997-07-22 | Sumitomo Chem Co Ltd | Aqueous emulsion adhesive |
| JP2000327908A (en) * | 1999-05-21 | 2000-11-28 | Dyflex Corp | Urethane resin composition, coating material, sealing material and production of cured product |
| JP2001342339A (en) * | 2000-05-31 | 2001-12-14 | Dyflex Corp | Water curable urethane resin composition, coating, coating material, sealing medium, adhesive, and method of producing cured product |
| JP2002348339A (en) * | 2001-05-24 | 2002-12-04 | Sumitomo Chem Co Ltd | Ethylene/vinylester copolymer-containing water emulsion, and adhesive agent containing the same emulsion and polyvalent isocyanate compound |
| JP2002363401A (en) * | 2001-06-04 | 2002-12-18 | Konishi Co Ltd | Low-foaming one-part moisture curing type urethane resin composition |
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