JP2005281452A - Aqueous adhesive - Google Patents
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- JP2005281452A JP2005281452A JP2004096392A JP2004096392A JP2005281452A JP 2005281452 A JP2005281452 A JP 2005281452A JP 2004096392 A JP2004096392 A JP 2004096392A JP 2004096392 A JP2004096392 A JP 2004096392A JP 2005281452 A JP2005281452 A JP 2005281452A
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Abstract
Description
水系接着剤に関する。 It relates to an aqueous adhesive.
住宅、オフィスなどの建材用途や車両用途等に使用する接着剤において、従来はトルエン、メチルエチルケトン等の溶剤系接着剤が主であったが、近年の環境問題から無溶剤化の方向にあり、溶剤を含有しない水系接着剤等へ代替が進んでいる。既に一部用途において置き換えが進んでおり、例えばカルボキシル基を有するクロロプレンラテックスを用いた水系接着剤は、建材・家具用などの用途で使用されている。また、特許文献1には、カルボキシル基または水酸基を有する水系エマルジョンとアセチルアセトン金属塩との混合物による耐熱性を付与した水系接着剤が記載されている。
しかし、最近では、被着材料としては、プラスチック系基材料や表面に有機塗装を施した鋼板等、難接着材料も数多く使用されている。従来の水系接着剤は、溶剤系接着剤と比較し、上記の塗装鋼板面等に対する接着力が十分ではなく、特に高温・高湿度の環境下で応力のかかる部位に用いると、経時的に剥離する等の課題があった。本発明の目的は、塗装鋼板面等への接着性、耐湿・耐熱性が改善された水系接着剤を提供することにある。 However, recently, many difficult-to-adhere materials such as plastic base materials and steel plates with organic coating on the surface have been used as adherend materials. Conventional water-based adhesives do not have sufficient adhesion to the above-mentioned coated steel sheet surface compared to solvent-based adhesives, and will peel off over time, especially when used in areas subject to stress in high-temperature and high-humidity environments. There was a problem such as doing. An object of the present invention is to provide a water-based adhesive having improved adhesion to a coated steel sheet surface, moisture resistance and heat resistance.
水系接着剤において、熱膨張済マイクロカプセルを添加する。これにより、水系接着剤の塗装鋼板面等への接着性、耐湿・耐熱性を大幅に向上させることができる。 In a water-based adhesive, add thermally expanded microcapsules. Thereby, the adhesiveness to the coated steel plate surface of a water-system adhesive agent, moisture resistance, and heat resistance can be improved significantly.
本発明の水系接着剤は、接着性樹脂の水分散液(A)に、熱膨張済マイクロカプセル(B)が分散されていることを特徴とする。 The aqueous adhesive of the present invention is characterized in that the thermally expanded microcapsules (B) are dispersed in an aqueous dispersion (A) of an adhesive resin.
本発明で用いられる接着性樹脂の水分散液(A)は、クロロプレン樹脂を含有するクロロプレンラテックスの水分散液とすることが好ましい。 The aqueous dispersion (A) of the adhesive resin used in the present invention is preferably an aqueous dispersion of chloroprene latex containing a chloroprene resin.
本発明で用いられる熱膨張済マイクロカプセル(B)は、真比重が0.01〜0.05g/cm3、体積平均粒径が30〜100μm であることが好ましい。 The thermally expanded microcapsule (B) used in the present invention preferably has a true specific gravity of 0.01 to 0.05 g / cm 3 and a volume average particle size of 30 to 100 μm.
本発明で用いられる熱膨張済マイクロカプセル(B)は、 接着性樹脂100重量部に対して、5〜60重量部を配合することが好ましい。 The thermally expanded microcapsule (B) used in the present invention is preferably blended in an amount of 5 to 60 parts by weight with respect to 100 parts by weight of the adhesive resin.
本発明で用いられる熱膨張済マイクロカプセルとは、予め熱膨張させた熱膨張性マイクロカプセルであって、例えば、ポリ塩化ビニリデン、ポリ塩化ビニリデンとポリアクリロニトリルの共重合体、ポリアクリロニトリル、アクリロニトリルとアクリル酸メチルの共重合体などからなる殻部分の内部に、ブタン、ヘキサン等の気体または液体の炭化水素を含有する熱膨張性マイクロカプセルを熱膨張させたものが挙げられる。熱膨張性マイクロカプセルの殻部分は、塗装鋼板面のエポキシ塗装面等の低極性面に対する塗れ性が改善され、接着性が向上する熱可塑性ポリマーからなることが好ましい。 The thermally expanded microcapsule used in the present invention is a thermally expandable microcapsule that has been thermally expanded in advance, such as polyvinylidene chloride, a copolymer of polyvinylidene chloride and polyacrylonitrile, polyacrylonitrile, acrylonitrile and acrylic. A thermally expandable microcapsule containing a gas or liquid hydrocarbon such as butane or hexane is thermally expanded inside a shell portion made of a copolymer of methyl acid. The shell portion of the thermally expandable microcapsule is preferably made of a thermoplastic polymer that improves the paintability of a coated steel plate surface to a low-polar surface such as an epoxy-coated surface and improves the adhesion.
熱膨張性マイクロカプセルとしては、市販の製品を使用することができる。例えばポリ塩化ビニリデン、ポリアクリロニトリル等の共重合体からなる予め熱膨張させた積水化学工業社製、商品名「アドバンセル EFS002W」等を使用できる。
A commercially available product can be used as the thermally expandable microcapsule. For example, a product name “ADVANCEL EFS002W” manufactured by Sekisui Chemical Co., Ltd., which has been previously thermally expanded and made of a copolymer such as polyvinylidene chloride and polyacrylonitrile can be used.
従来の水系接着剤は、接着剤の水分散液であって、特に水分子に起因するその高い極性から塗装鋼板面等に対する塗れが悪く接着性が不十分であり、また、硬化皮膜は、湿気を取り込みやすく接着界面で湿気の攻撃を受けやすい。本発明の水系接着剤では、熱可塑性樹脂の殻を有する熱膨張済みマイクロカプセルを添加する。これにより、塗装鋼板面等の低極性界面に対する塗れ性が改善され、また硬化被膜への湿気の進入を防ぐ等の効果があるので、接着性、耐湿熱性が向上するものと考えられる。 Conventional water-based adhesives are aqueous dispersions of adhesives, and in particular due to their high polarity due to water molecules, they are poorly applied to the coated steel plate surface and the like, and the adhesiveness is insufficient. It is easy to take in and is susceptible to moisture attack at the adhesive interface. In the aqueous adhesive of the present invention, thermally expanded microcapsules having a thermoplastic resin shell are added. As a result, the paintability to a low polarity interface such as a coated steel plate surface is improved, and there is an effect such as preventing moisture from entering the cured film. Therefore, it is considered that the adhesiveness and moist heat resistance are improved.
本発明で用いられる熱膨張済マイクロカプセルは、真比重が0.01〜0.05g/cm3、体積平均粒径が30〜100μmであることが好ましい。水系接着剤では、塗布前に水の沸点前後、またはそれ以上に加熱させることが困難であるため、予め熱膨張性マイクロカプセルを熱膨張させておく。また、接着剤を塗布した後で、硬化被膜内部で熱膨張性マイクロカプセルを熱膨張させると皮膜の破断をきたし、逆に剥離を促進させてしまう恐れがある。本発明で用いられる熱膨張性マイクロカプセルは、予め熱膨張させたて熱膨張済マイクロカプセルとしておくことで表面積が増大し、塗れ性改善等の効果を最大限に発現する。 The thermally expanded microcapsules used in the present invention preferably have a true specific gravity of 0.01 to 0.05 g / cm 3 and a volume average particle size of 30 to 100 μm. Since it is difficult for a water-based adhesive to be heated before or after the boiling point of water before application, or more, the thermally expandable microcapsules are previously thermally expanded. Further, if the thermally expandable microcapsules are thermally expanded inside the cured film after the adhesive is applied, the film may be broken, and conversely, peeling may be promoted. The heat-expandable microcapsule used in the present invention is preliminarily thermally expanded to be a heat-expanded microcapsule, so that the surface area is increased and the effect of improving the wettability is exhibited to the maximum.
熱膨張済マイクロカプセルの真比重が0.05g/cm3を超える、または体積平均粒径が30μm未満の場合は、熱膨張済マイクロカプセルの表面積が不足し、十分な接着強度が得られない。真比重が0.01g/cm3未満、または体積平均粒径が100μmを超えると、熱膨張済マイクロカプセルの粒子の強度が低下し、やはり十分な接着強度が得られない。 When the true specific gravity of the thermally expanded microcapsule exceeds 0.05 g / cm 3 or the volume average particle size is less than 30 μm, the surface area of the thermally expanded microcapsule is insufficient and sufficient adhesive strength cannot be obtained. When the true specific gravity is less than 0.01 g / cm 3 or the volume average particle diameter exceeds 100 μm, the strength of the particles of the thermally expanded microcapsule is lowered, and sufficient adhesive strength cannot be obtained.
熱膨張済マイクロカプセルの添加量は、接着性樹脂の固形分100重量部に対して、5〜60重量部が好ましい。5重量部未満では塗装鋼板等に対する接着性・耐水性が十分ではなく、60重量部を越えると接着性樹脂の割合が低下するため硬化皮膜の強度が大幅に低下する。 The addition amount of the thermally expanded microcapsules is preferably 5 to 60 parts by weight with respect to 100 parts by weight of the solid content of the adhesive resin. If it is less than 5 parts by weight, the adhesiveness and water resistance to the coated steel sheet and the like are not sufficient, and if it exceeds 60 parts by weight, the ratio of the adhesive resin is reduced, so that the strength of the cured film is greatly reduced.
本発明で用いられる接着性樹脂としては、接着剤として使用でき、水に混合した時水分散液になるものであれば、特に限定されず、例えば、ポリ酢酸ビニルホモポリマー、アクリル系ポリマー、エチレン-酢酸ビニル系ポリマー、スチレン‐ブタジエンエラストマー、ウレタン系ポリマー、シリコーン系ポリマー等が挙げられる。接着性樹脂として、各種ポリマーを含有するものを使用した場合にも、熱膨張済マイクロカプセルの添加効果を得ることができるが、高い皮膜柔軟性、幅広い被着体への接着性、優れたコンタクト接着性を有するクロロプレン系ポリマーを主成分とするクロロプレンラテックスが、耐久性やライン適性に優れており最も好ましい。 The adhesive resin used in the present invention is not particularly limited as long as it can be used as an adhesive and becomes an aqueous dispersion when mixed with water. For example, polyvinyl acetate homopolymer, acrylic polymer, ethylene -Vinyl acetate polymers, styrene-butadiene elastomers, urethane polymers, silicone polymers and the like. Even when resin containing various polymers is used as an adhesive resin, the effect of adding thermally expanded microcapsules can be obtained, but high film flexibility, wide adhesion to adherend, excellent contact A chloroprene latex mainly composed of an adhesive chloroprene-based polymer is most preferable because of its excellent durability and line suitability.
クロロプレンラテックスとしては、特に限定されず市販されている製品を使用できる。例えば、分子内にカルボキシル基を有し、PHが2〜9である東ソー社製、「GFL−890」、「GFL−280」、電気化学工業社製、「LC−501」等を使用することができる。これらクロロプレンラテックスは、1種類又は何種類かを混ぜた混合物として用いることができる。 The chloroprene latex is not particularly limited, and a commercially available product can be used. For example, Tosoh's “GFL-890”, “GFL-280”, Denki Kagaku Kogyo, “LC-501”, etc., having a carboxyl group in the molecule and having a pH of 2-9 are used. Can do. These chloroprene latexes can be used as a mixture of one kind or several kinds.
本発明の水系接着剤には、必要に応じて、以下の化合物が含有されてもよい。各種化合物としては、例えば、架橋剤、PH調整剤、充填剤、粘着付与剤、酸化防止剤、老化防止剤、防カビ剤、着色剤、増粘剤、消泡剤、難燃剤、香料等が挙げられる。 The water-based adhesive of the present invention may contain the following compounds as necessary. Examples of the various compounds include a crosslinking agent, a pH adjuster, a filler, a tackifier, an antioxidant, an anti-aging agent, a fungicide, a colorant, a thickener, an antifoaming agent, a flame retardant, and a fragrance. Can be mentioned.
本発明の水系接着剤では、熱膨張済マイクロカプセル(予め熱膨張させた熱膨張性マイクロカプセル)が含有されているので、水系接着剤の塗装鋼板面等への接着性、耐湿・耐熱性が大幅に向上する。 Since the aqueous adhesive of the present invention contains thermally expanded microcapsules (thermally expandable microcapsules previously thermally expanded), the adhesiveness of the aqueous adhesive to the coated steel plate surface, moisture resistance and heat resistance are excellent. Greatly improved.
(実施例)
クロロプレンラテックス水分散液(東ソー株式会社製、「GFL−280」、クロロプレンポリマーを固形分として100重量部含有)200重量部に、熱膨張済マイクロカプセル(積水化学工業株式会社製、「アドバンセル EFS002W」、真比重:0.03g/cm3、体積平均粒径:約50μm)20重量部、粘着付与樹脂(荒川化学工業株式会社製、「E−100」)100重量部、架橋剤(大崎工業株式会社製、水性亜鉛華「AZ−SW」)1重量部をミキサーにて配合・混合し、水系接着剤を得た。
(Example)
Chloroprene latex aqueous dispersion (manufactured by Tosoh Corporation, “GFL-280”, containing 100 parts by weight of chloroprene polymer as a solid content) in 200 parts by weight, thermally expanded microcapsules (manufactured by Sekisui Chemical Co., Ltd., “Advancel EFS002W”) ”, True specific gravity: 0.03 g / cm 3 , volume average particle size: about 50 μm) 20 parts by weight, tackifier resin (Arakawa Chemical Industries, Ltd.,“ E-100 ”) 100 parts by weight, crosslinking agent (Osaki Industry) 1 part by weight of water-based zinc white “AZ-SW” manufactured by Co., Ltd. was blended and mixed with a mixer to obtain an aqueous adhesive.
(実施例2)
実施例1に対し、熱膨張済マイクロカプセル(「アドバンセル EFS002W」)の添加量を30重量部にかえたこと以外は実施例1と同様にして水系接着剤を得た。
(Example 2)
A water-based adhesive was obtained in the same manner as in Example 1 except that the amount of thermally expanded microcapsules (“Advancel EFS002W”) added to Example 1 was changed to 30 parts by weight.
(比較例1)
熱膨張済マイクロカプセルである「アドバンセル EFS002W」を含有しなかったこと以外は実施例1と同様にして水系接着剤を得た。
(Comparative Example 1)
A water-based adhesive was obtained in the same manner as in Example 1 except that it did not contain “Advancel EFS002W”, which was a thermally expanded microcapsule.
(比較例2)
熱膨張済マイクロカプセル(「アドバンセル EFS002W」)の代わりに、熱膨張済マイクロカプセル(「アドバンセル EFS002W」)を熱膨張させる前の状態の熱膨張性マイクロカプセル(真比重:1.1g/cm3、体積平均粒径:14μm)を用い、これを添加したこと以外は実施例1と同様にして水系接着剤を得た。
(Comparative Example 2)
Instead of the thermally expanded microcapsule (“Advancel EFS002W”), the thermally expanded microcapsule (true specific gravity: 1.1 g / cm) in the state before thermally expanded the microexpanded microcapsule (“Advancel EFS002W”) 3 and a volume average particle size: 14 μm), and an aqueous adhesive was obtained in the same manner as in Example 1 except that this was added.
なお、熱膨張済マイクロカプセル性状の評価方法は下記の通り。
(1)真比重の測定
測定器:株式会社島津製作所製 マイクロメリテックス アキュピック1330
ガ ス:乾燥エアー
測定前の試料準備:60℃で12時間乾燥
水 分:3%以下(赤外線水分計、115℃に加熱1分後の乾燥重量から算出)
(2)粒径の測定
粒度分布測定器:日機装株式会社製 マイクロトラック
In addition, the evaluation method of thermally expanded microcapsule properties is as follows.
(1) Measuring device for true specific gravity: Micromeritex Accupic 1330 manufactured by Shimadzu Corporation
Gas: Sample preparation before dry air measurement: Dry water at 60 ° C for 12 hours: 3% or less (infrared moisture meter, calculated from dry weight after 1 minute heating to 115 ° C)
(2) Particle size measurement Particle size distribution measuring instrument: Nikkiso Co., Ltd. Microtrac
水系接着剤について、以下の試験方法により物性を評価した。
(評価方法)
(接着強度の測定)
水系接着剤をメラミン板及びエポキシ塗装を施した鋼板の表面にそれぞれスプレーで塗布量がそれぞれの面で80g/m2となるように塗布し、120℃で3分間乾燥させた後、直ちにロールプレスにより圧着し、23℃、50%RHの室内にて3日間養生した後測定に供した。
The physical properties of the water-based adhesive were evaluated by the following test methods.
(Evaluation methods)
(Measurement of adhesive strength)
A water-based adhesive is sprayed on the surface of a melamine plate and an epoxy-coated steel plate so that the coating amount is 80 g / m 2 on each side, dried at 120 ° C. for 3 minutes, and immediately rolled. The sample was subjected to pressure measurement and cured for 3 days in a room at 23 ° C. and 50% RH, and then subjected to measurement.
(常態接着強度)
上記の養生後試験片について、T字型治具をエポキシ接着剤貼り付け、引張速度10mm/min.にて平面に沿った方向で引張り試験を実施した。
(Normal adhesive strength)
For the post-curing test piece, a T-shaped jig was attached with an epoxy adhesive, and a tensile speed of 10 mm / min. The tensile test was carried out in the direction along the plane.
(湿熱後接着強度)
上記の養生後試験片を、さらに45℃、95%RHの条件下に48時間置き、取り出し後、直ちにT字型治具を貼り付け、引張速度10mm/min.にて平面に沿った方向で引張り試験を実施した。
(Adhesive strength after wet heat)
The test piece after curing was further placed under conditions of 45 ° C. and 95% RH for 48 hours, and after taking out, a T-shaped jig was immediately attached, and a tensile speed of 10 mm / min. The tensile test was carried out in the direction along the plane.
常態接着強度及び湿熱後接着強度の最大引張り強度について、表1に測定結果を示した。実用的には常態で100N/cm2以上、湿熱後で60N/cm2以上の接着強度が必要であり、実施例1、2が条件を満たしている。 Table 1 shows the measurement results for the normal tensile strength and the maximum tensile strength of the adhesive strength after wet heat. Practically, an adhesive strength of 100 N / cm 2 or more is required under normal conditions and 60 N / cm 2 or more after wet heat, and Examples 1 and 2 satisfy the conditions.
住宅、オフィス等に用いられる建材用途や車両用途等に使用する水系接着剤。
Water-based adhesive used for building materials and vehicles used in houses and offices.
Claims (4)
The water-based adhesive according to any one of claims 1 to 3, wherein the thermally expanded microcapsule (B) is blended in an amount of 5 to 60 parts by weight with respect to 100 parts by weight of the adhesive resin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP2004096392A JP2005281452A (en) | 2004-03-29 | 2004-03-29 | Aqueous adhesive |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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JP2004096392A JP2005281452A (en) | 2004-03-29 | 2004-03-29 | Aqueous adhesive |
Publications (1)
Publication Number | Publication Date |
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JP2005281452A true JP2005281452A (en) | 2005-10-13 |
Family
ID=35180204
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP2004096392A Withdrawn JP2005281452A (en) | 2004-03-29 | 2004-03-29 | Aqueous adhesive |
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Country | Link |
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JP (1) | JP2005281452A (en) |
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2004
- 2004-03-29 JP JP2004096392A patent/JP2005281452A/en not_active Withdrawn
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