JPH06340863A - Two-pack aqueous adhesive - Google Patents
Two-pack aqueous adhesiveInfo
- Publication number
- JPH06340863A JPH06340863A JP13037293A JP13037293A JPH06340863A JP H06340863 A JPH06340863 A JP H06340863A JP 13037293 A JP13037293 A JP 13037293A JP 13037293 A JP13037293 A JP 13037293A JP H06340863 A JPH06340863 A JP H06340863A
- Authority
- JP
- Japan
- Prior art keywords
- emulsion
- aqueous
- aqueous emulsion
- parts
- adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は水性二液型接着剤、更に
詳しくは、ウレタン系と塩素化ポリプロピレン系の混合
水性エマルジョン主剤と、ポリイソシアネート化合物硬
化剤から成り、特に被着体としてポリオレフィンフォー
ムに対しても、優れた初期接着特性および硬化後の耐熱
性を発揮することができる、非溶剤型硬化性の二液型接
着剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous two-component adhesive agent, more specifically, a mixed aqueous emulsion base agent of urethane type and chlorinated polypropylene type, and a polyisocyanate compound curing agent. Particularly, a polyolefin foam as an adherend. Also, the present invention relates to a non-solvent curable two-component adhesive capable of exhibiting excellent initial adhesive properties and heat resistance after curing.
【０００２】[0002]
【従来の技術と発明が解決しようとする課題】従来よ
り、一般に用いられている溶剤型接着剤の中でも、ウレ
タン系溶剤型接着剤は、各種の被着体に対し良好な接着
性を有し、また硬化剤使用により耐熱発現性に優れ、か
つ特異な感温特性により種々の貼り合せ条件に対する適
合性に優れることから、種々の分野で多用されている。
この溶剤型接着剤に用いられるポリウレタンは、分子量
が大きく、接着初期より良好な凝集力および耐熱性を発
揮することができる。しかして近年、地球環境改善の目
的から、溶剤型接着剤の水性化が検討されるようになっ
ており、たとえばアニオン系自己乳化型ウレタン水性エ
マルジョンの使用が試みられているが、その重合方法
(乳化方法)の特性上、高分子量化が望めず、初期接着特
性(初期凝集力や初期耐熱性)および硬化後の耐熱性が得
られないという欠点があった。2. Description of the Related Art Among solvent-based adhesives that have been generally used, urethane-based solvent-based adhesives have good adhesiveness to various adherends. Further, it is widely used in various fields because it exhibits excellent heat resistance by using a curing agent and excellent compatibility with various bonding conditions due to its unique temperature-sensitive property.
The polyurethane used for this solvent-based adhesive has a large molecular weight and can exhibit good cohesive strength and heat resistance from the initial stage of adhesion. However, in recent years, for the purpose of improving the global environment, water-based solvent type adhesives have been studied, and for example, the use of anionic self-emulsifying urethane aqueous emulsion has been attempted.
Due to the characteristics of (emulsification method), there is a drawback in that high molecular weight cannot be expected, and initial adhesive properties (initial cohesive strength and initial heat resistance) and heat resistance after curing cannot be obtained.
【０００３】このため、エチレン−酢酸ビニル共重合体
水性エマルジョンをブレンドする手立が採られている
が、上述の初期接着特性はある程度改善されるものの、
硬化後の耐熱性は逆に低下し、特にポリオレフィンフォ
ームに適用した場合にその傾向が顕著である。For this reason, a means of blending the ethylene-vinyl acetate copolymer aqueous emulsion is adopted, but although the above-mentioned initial adhesive property is improved to some extent,
On the contrary, the heat resistance after curing is lowered, and this tendency is particularly remarkable when applied to polyolefin foam.
【０００４】[0004]
【課題を解決するための手段】そこで、本発明者らは、
上記アニオン系自己乳化型ウレタン水性エマルジョンの
水性接着剤の初期接着特性および硬化後の耐熱性を、従
来のウレタン系溶剤型接着剤と同等もしくはそれ以上に
発現させるべく鋭意検討を進めたところ、塩素化ポリプ
ロピレン水性エマルジョンをブレンドし、さらに硬化剤
としてポリイソシアネート化合物を用いれば、所期目的
の水性接着剤(主剤と硬化剤の二液型)が得られることを
見出し、本発明を完成させるに至った。Therefore, the present inventors have
The initial adhesive properties and heat resistance after curing of the water-based adhesive of the anionic self-emulsifying urethane water-based emulsion were earnestly studied in order to develop the same or higher than the conventional urethane-based solvent-based adhesive. By blending a modified polypropylene aqueous emulsion and further using a polyisocyanate compound as a curing agent, it was found that an intended aqueous adhesive (two-component type of a main agent and a curing agent) can be obtained, and the present invention was completed. It was
【０００５】すなわち、本発明は、アニオン系自己乳化
型ウレタン水性エマルジョン(以下、ウレタンエマルジ
ョンと略す)および塩素化ポリプロピレン水性エマルジ
ョン(以下、塩素化ＰＰエマルジョンと略す)からなる主
剤と、ポリイソシアネート化合物からなる硬化剤から成
ることを特徴とする水性二液型接着剤を提供するもので
ある。That is, according to the present invention, a main agent comprising an anionic self-emulsifying urethane aqueous emulsion (hereinafter abbreviated as urethane emulsion) and a chlorinated polypropylene aqueous emulsion (hereinafter abbreviated as chlorinated PP emulsion) and a polyisocyanate compound are used. The present invention provides an aqueous two-component type adhesive characterized by comprising the following curing agent.
【０００６】本発明で用いるウレタンエマルジョンはそ
れ自体公知のもので、通常分子量５０００〜８００００
のポリウレタンが水性媒体中に安定に乳化もしくは水溶
化状態にあるエマルジョン(一般に固形分２０〜６０％)
を指称し、たとえばバイエル社から入手することができ
る。The urethane emulsion used in the present invention is known per se and usually has a molecular weight of 5,000 to 80,000.
Emulsion in which the polyurethane is stable emulsified or solubilized in an aqueous medium (generally 20 to 60% solid content)
Can be obtained from Bayer AG, for example.
【０００７】本発明で用いる塩素化ＰＰエマルジョンと
は、塩素化ポリプロピレン(通常、塩素化率１０〜３０
重量％)の有機溶剤溶液を水中に乳化した後、系中の有
機溶剤を除去して得られる水性エマルジョンを指称す
る。使用量(固形分換算で)は通常、上記ウレタンエマル
ジョンの固形分１００部(重量部、以下同様)に対して１
０〜１００部の範囲で選定すればよい。１０部未満で
は、所望の初期接着特性が得られず、また１００部を越
えると、初期強度、凝集力および耐熱性が低下する傾向
となる。The chlorinated PP emulsion used in the present invention is a chlorinated polypropylene (usually having a chlorination rate of 10 to 30).
An aqueous emulsion obtained by emulsifying an organic solvent solution (wt%) in water and then removing the organic solvent in the system is referred to. The amount used (in terms of solid content) is usually 1 with respect to 100 parts of solid content of the urethane emulsion (parts by weight, the same applies hereinafter).
It may be selected in the range of 0 to 100 parts. If it is less than 10 parts, the desired initial adhesive properties cannot be obtained, and if it exceeds 100 parts, the initial strength, cohesive strength and heat resistance tend to decrease.
【０００８】なお、上記塩素化ＰＰエマルジョン中の塩
素化ポリプロピレンとの相溶性良好な、前記エチレン−
酢酸ビニル共重合体水性エマルジョン(以下、ＥＶＡエ
マルジョンと略す)およびその変性体、すなわち、エチ
レンと酢酸ビニルとＮ−メチロール基含有共重合性モノ
マーを必須とする共重合体水性エマルジョン(以下、変
性ＥＶＡエマルジョンと略す)の群から選ばれる少なく
とも１種を添加してもよい。添加量は通常、上記ウレタ
ンエマルジョンの固形分１００部に対して１０００部以
下の範囲で選定すればよい。１０００部を越えると、硬
化後の耐熱性および各種被着体に対する密着性が低下す
る傾向となる。かかるＥＶＡエマルジョンや変性ＥＶＡ
エマルジョンの添加によって初期耐熱性を高めることが
でき、また特に変性ＥＶＡエマルジョンの場合、架橋性
官能基が導入されている点で、より優れた耐熱性効果が
期待される。[0008] The ethylene-based copolymer having good compatibility with the chlorinated polypropylene in the chlorinated PP emulsion is used.
Vinyl acetate copolymer aqueous emulsion (hereinafter abbreviated as EVA emulsion) and its modified product, that is, a copolymer aqueous emulsion in which ethylene, vinyl acetate and an N-methylol group-containing copolymerizable monomer are essential (hereinafter modified EVA) At least one selected from the group of (emulsion) may be added. The addition amount is usually selected in the range of 1000 parts or less with respect to 100 parts of the solid content of the urethane emulsion. If it exceeds 1000 parts, the heat resistance after curing and the adhesion to various adherends tend to deteriorate. Such EVA emulsion and modified EVA
The initial heat resistance can be increased by adding the emulsion, and particularly in the case of the modified EVA emulsion, a more excellent heat resistance effect is expected in that the crosslinkable functional group is introduced.
【０００９】上記変性ＥＶＡエマルジョンは、エチレン
と酢酸ビニルとＮ−メチロール基含有共重合性モノマー
(たとえばＮ−メチロールアクリルアミド、Ｎ−メチロ
ールメタアクリルアミドなど)および必要に応じて他の
共重合性モノマー(たとえばアクリル酸メチル、アクリ
ル酸エチル、アクリル酸ブチル、アクリル酸２−エチル
ヘキシル、２−ヒドロキシエチルアクリレート、２−ヒ
ドロキシプロピルアクリレート、メチルメタクリレー
ト、n−ブチルメタアクリレート、ベンジルメタアクリ
レート、２−ヒドロキシエチルメタアクリレート、２−
ヒドロキシプロピルメタアクリレート、アクリロニトリ
ル、スチレン、ブタジエン、アクリル酸、メタクリル
酸、無水マレイン酸など)を水中に乳化重合することに
より製造され(固形分２０〜６０％)、通常、Ｎ−メチロ
ール基含有共重合性モノマーの共重合含量が１〜２０モ
ル％のものを使用すればよい。The above modified EVA emulsion comprises ethylene, vinyl acetate and an N-methylol group-containing copolymerizable monomer.
(For example, N-methylol acrylamide, N-methylol methacrylamide, etc.) and optionally other copolymerizable monomers (for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate). , 2-hydroxypropyl acrylate, methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-
Hydroxypropyl methacrylate, acrylonitrile, styrene, butadiene, acrylic acid, methacrylic acid, maleic anhydride, etc.) are produced by emulsion polymerization in water (solid content 20 to 60%), and usually N-methylol group-containing copolymer The copolymerizable content of the volatile monomer may be 1 to 20 mol%.
【００１０】本発明で硬化剤として用いるポリイソシア
ネート化合物としては、脂肪族系あるいは芳香族系のい
ずれも使用できる。たとえば、バイエル社製のＤesmodu
rＤＡ, Ｄesmodur ４４Ｖ２０(クルードＭＤＩ)および
活性イソシアネート基をブロックしたブロック化ポリイ
ソシアネートなどが挙げられる。The polyisocyanate compound used as the curing agent in the present invention may be either an aliphatic type or an aromatic type. For example, Desmodu from Bayer
Examples include rDA, Desmodur 44V20 (crude MDI) and blocked polyisocyanates blocked with active isocyanate groups.
【００１１】本発明に係る水性二液型接着剤は、上記所
定割合のウレタンエマルジョン、塩素化ＰＰエマルジョ
ンおよび必要に応じてＥＶＡエマルジョンや変性ＥＶＡ
エマルジョンから成る主剤と、ポリイソシアネート化合
物硬化剤との二液型で構成され、接着使用の直前に主剤
と硬化剤を計量混合する。必要に応じて、主剤に通常の
増粘剤を加えて、主剤粘度を通常１０００〜５０００cp
s／２０℃に調整してもよい。硬化剤の使用量は通常、
主剤成分全量に対して１〜１０重量％の範囲で選定すれ
ばよい。１重量％未満では、十分な硬化後の耐熱性が得
られず、また１０重量％を越えると、接着性の低下およ
びポットライフが短くなる傾向となる。The water-based two-component adhesive according to the present invention comprises a urethane emulsion, a chlorinated PP emulsion, and an EVA emulsion or a modified EVA, if necessary, in the above-specified proportions.
It is composed of a two-part type of a main agent composed of an emulsion and a polyisocyanate compound curing agent, and the main agent and the curing agent are metered and mixed just before the adhesive is used. If necessary, an ordinary thickener may be added to the main agent so that the viscosity of the main agent is usually 1000 to 5000 cp.
You may adjust to s / 20 degreeC. The amount of curing agent used is usually
It may be selected in the range of 1 to 10% by weight with respect to the total amount of the main ingredient. If it is less than 1% by weight, sufficient heat resistance after curing cannot be obtained, and if it exceeds 10% by weight, the adhesiveness tends to be low and the pot life tends to be short.
【００１２】[0012]
【発明の効果】以上の構成から成る本発明接着剤は、従
来のウレタン系溶剤型接着剤と同等以上の初期接着特性
および硬化後の耐熱性を発揮し、かつ被着体の種類に制
限なく、各種のプラスチック材料、木質材料、金属板等
に用いることができる。特に、たとえば極性の低いポリ
オレフィンフォームの接着に有用で、また従来より汎用
されていたプライマーの使用を省略できる。EFFECT OF THE INVENTION The adhesive of the present invention having the above constitution exhibits the same or higher initial adhesive properties and heat resistance after curing as those of the conventional urethane solvent-based adhesives, and the type of adherend is not limited. It can be used for various plastic materials, wood materials, metal plates and the like. In particular, it is useful, for example, for bonding a polyolefin foam having low polarity, and it is possible to omit the use of a primer which has been widely used in the past.
【００１３】[0013]
【実施例】次に実施例および比較例を挙げて、本発明を
より具体的に説明する。 実施例１, ２および比較例１ (１)主剤 下記表１に示す部数のウレタンエマルジョン、ＥＶＡエ
マルジョン(実施例２は除く)、塩素化ＰＰエマルジョン
および増粘剤を配合して、主剤を得る。 (２)二液型接着剤 上記(１)の主剤に対し、表１に示す部数で硬化剤として
Ｄesmodur ＤＡ(バイエル社製)を混合して接着剤とする
(主剤１００／硬化剤５)。EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. Examples 1 and 2 and Comparative Example 1 (1) Main component A main component is obtained by blending the parts of urethane emulsion, EVA emulsion (excluding example 2), chlorinated PP emulsion and thickener shown in Table 1 below. (2) Two-component adhesive agent Desmodur DA (manufactured by Bayer) as a curing agent is mixed with the main agent of (1) above in the number of parts shown in Table 1 to obtain an adhesive agent.
(Main agent 100 / Curing agent 5).
【００１４】(３)接着試験 上記(２)の接着剤をよく撹拌混合してから、木質ボード
に８０g／m2の量でエアースプレー塗布し、８０℃で５
分間乾燥した後、これに予め１２０℃に加熱したポリオ
レフィンフォーム表皮材(東レ(株)製、トーレペフ)を
１．０kg／cm2の圧力で３０秒間圧締して、試験片を作
製する。次いで、下記試験項目に供し、結果を表１に併
記する。(3) Adhesion test The adhesive of the above (2) was thoroughly mixed by stirring, and then air-sprayed onto a wooden board in an amount of 80 g / m 2 and then at 5 ° C. at 5 ° C.
After drying for a minute, a polyolefin foam skin material (Toray Pef, manufactured by Toray Industries, Inc.) preheated to 120 ° C. is pressed at a pressure of 1.0 kg / cm 2 for 30 seconds to prepare a test piece. Next, the following test items are provided, and the results are also shown in Table 1.
【００１５】初期剥離強度 貼合せ(圧締)１０分後に剥離強度(kg／２５mm)を測定す
る。常態剥離強度 養生(２０℃, ６５％ＲＨ×２４時間)後に剥離強度(kg
／２５mm)を測定する。耐熱クリープ 養生後、８０℃の雰囲気中表皮材側の一端に１００g／
２５mmの荷重を９０°角方向に加え、２４時間後の剥離
長さ(mm)を測定する。なお、表１中、ＭＢは表皮材の破
壊、ＡＦは表皮材からの界面破壊を示す。 Initial Peel Strength Peel strength (kg / 25 mm) is measured 10 minutes after lamination (pressing). Normal peel strength After curing (20 ℃, 65% RH x 24 hours), peel strength (kg
/ 25 mm) is measured. After heat-resistant creep curing, 100g / at one end on the skin side in an atmosphere of 80 ° C
A load of 25 mm is applied in the 90 ° angle direction, and the peel length (mm) after 24 hours is measured. In Table 1, MB indicates destruction of the skin material, and AF indicates interfacial destruction from the skin material.
【００１６】[0016]
【表１】 [Table 1]
【００１７】表１中、 注１) バイエル社製、Ｄispercoll ＫＡ−８４６４、
固形分４０％ 注２) クラレ(株)製、パンフレックスＯＭ−３３００、
固形分５１％ 注３) 東洋化成工業(株)製、ハードレン２Ａ−０１Ｉ
Ｊ、樹脂分３４．７％、Ｃl含有量５．３％ 注４) サンノプコ(株)製、サンノプコＡ−８１４In Table 1, Note 1) manufactured by Bayer Co., Dispercoll KA-8464,
Solid content 40% * 2) Kuraray Co., Ltd., Panflex OM-3300,
Solid content 51% * 3) Toyo Kasei Kogyo Co., Ltd., Hardlen 2A-01I
J, resin content 34.7%, Cl content 5.3% Note 4) San Nopco Ltd., San Nopco A-814
Claims (3)
ルジョンおよび塩素化ポリプロピレン水性エマルジョン
からなる主剤と、 ポリイソシアネート化合物からなる硬化剤から成ること
を特徴とする水性二液型接着剤。1. An aqueous two-component adhesive characterized by comprising a main agent comprising an anionic self-emulsifying urethane aqueous emulsion and a chlorinated polypropylene aqueous emulsion, and a curing agent comprising a polyisocyanate compound.
の使用量(固形分換算で)が、アニオン系自己乳化型ウレ
タン水性エマルジョンの固形分１００重量部に対し１０
〜１００重量部で、硬化剤の使用量が主剤成分全量に対
し１〜１０重量％である請求項１記載の水性二液型接着
剤。2. The amount of the chlorinated polypropylene aqueous emulsion used (in terms of solid content) is 10 per 100 parts by weight of the solid content of the anionic self-emulsifying urethane aqueous emulsion.
The aqueous two-component adhesive according to claim 1, wherein the amount of the curing agent used is 1 to 10% by weight based on the total amount of the main component in 100 parts by weight to 100 parts by weight.
水性エマルジョンおよびエチレンと酢酸ビニルとＮ−メ
チロール基含有共重合性モノマーを必須とする共重合体
水性エマルジョンの群から選ばれる少なくとも１種を添
加した請求項１または２記載の水性二液型接着剤。3. At least one selected from the group consisting of an ethylene-vinyl acetate copolymer aqueous emulsion and a copolymer aqueous emulsion containing ethylene, vinyl acetate and an N-methylol group-containing copolymerizable monomer as an essential ingredient. The aqueous two-component adhesive according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13037293A JPH06340863A (en) | 1993-06-01 | 1993-06-01 | Two-pack aqueous adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13037293A JPH06340863A (en) | 1993-06-01 | 1993-06-01 | Two-pack aqueous adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06340863A true JPH06340863A (en) | 1994-12-13 |
Family
ID=15032796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13037293A Pending JPH06340863A (en) | 1993-06-01 | 1993-06-01 | Two-pack aqueous adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06340863A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6656512B1 (en) | 1999-03-10 | 2003-12-02 | Mars Uk Limited | Pet food product with coconut endosperm fiber |
-
1993
- 1993-06-01 JP JP13037293A patent/JPH06340863A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6656512B1 (en) | 1999-03-10 | 2003-12-02 | Mars Uk Limited | Pet food product with coconut endosperm fiber |
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