JPH06330011A - Two-pack type aqueous adhesive - Google Patents

Two-pack type aqueous adhesive

Info

Publication number
JPH06330011A
JPH06330011A JP12405893A JP12405893A JPH06330011A JP H06330011 A JPH06330011 A JP H06330011A JP 12405893 A JP12405893 A JP 12405893A JP 12405893 A JP12405893 A JP 12405893A JP H06330011 A JPH06330011 A JP H06330011A
Authority
JP
Japan
Prior art keywords
parts
weight
acrylic monomer
epoxy
core
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.)
Granted
Application number
JP12405893A
Other languages
Japanese (ja)
Other versions
JP3247915B2 (en
Inventor
Masao Kishi
岸  正夫
Isao Kato
勲 加藤
Katsura Nagata
桂 永田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Toatsu Chemicals Inc
Original Assignee
Mitsui Toatsu Chemicals Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsui Toatsu Chemicals Inc filed Critical Mitsui Toatsu Chemicals Inc
Priority to JP12405893A priority Critical patent/JP3247915B2/en
Publication of JPH06330011A publication Critical patent/JPH06330011A/en
Application granted granted Critical
Publication of JP3247915B2 publication Critical patent/JP3247915B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Graft Or Block Polymers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

PURPOSE:To obtain a two-pack type aqueous adhesive suitable for interior automotive trim, etc., having excellent viscosity change with time and storage stability under a high-temperature condition, by blending a specific epoxy- modified acrylic emulsion with an amine or a polyamide resin-based curing agent. CONSTITUTION:100 pts.wt. calculated as a solid content of an epoxy-modified acrylic emulsion having a core-shell structure comprising a core layer composed of a copolymer of an acrylic monomer and an epoxy resin and a shell layer composed of a copolymer of an acrylic monomer and an OH group-containing acrylic monomer are mixed with 2-25 pts.wt. calculated as a solid content of an amine or a polyamide resin-based curing agent to give the objective adhesive.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は静電植毛用接着剤に関す
る。詳しくは、コンソールボックス、グローブボック、
ピラー、リアーコーナー等の自動車内装材、エアーコン
ディショナーの風向き変更板、事務用機器の複写機の送
りロール等の静電植毛用の二液型水性接着剤であり、エ
ポキシ変性アクリルエマルションの貯蔵時の安定性が改
善された、接着力、耐水性、耐熱性、耐煮沸性、耐摩耗
性等に優れる二液型水性接着剤に関する。
FIELD OF THE INVENTION The present invention relates to an adhesive for electrostatic flocking. For details, see Console Box, Glove Box,
It is a two-component water-based adhesive for electrostatic flocking such as automobile interior materials such as pillars and rear corners, wind direction change plates for air conditioners, and feeder rolls for copiers for office equipment. The present invention relates to a two-component water-based adhesive having improved stability, excellent adhesive strength, water resistance, heat resistance, boiling resistance, abrasion resistance and the like.

【0002】[0002]

【従来の技術】従来、自動車内装材、弱電機器のエアー
コンディショナー、複写機の送りロール等の静電植毛用
接着剤は、溶剤型接着剤が主流であったが、近時、火
災、中毒等の安全衛生及び、環境汚染等の問題より、ア
クリルエマルション、エポキシ変性アクリルエマルショ
ン、エチレンー酢酸ビニル共重合体エマルション、エチ
レンー塩化ビニルー酢酸ビニル三元共重合体エマルショ
ン、スチレン又はメチルメチアクリレートーブタジエン
共重合体ラテックス、水性ウレタンディスパージョン等
の水性エマルションが用いられ、これ等は単独で又は水
溶性エポキシ樹脂、メラミン樹脂、フェノール樹脂、ポ
リウレタン系樹脂等と組合わせて用いられてきた。
2. Description of the Related Art Conventionally, solvent-type adhesives have been the mainstream for adhesives for electrostatic flocking such as automobile interior materials, air conditioners for light electric equipment, and feed rolls for copying machines, but recently, fire, poisoning, etc. Due to the problems of safety and health and environmental pollution, acrylic emulsion, epoxy modified acrylic emulsion, ethylene-vinyl acetate copolymer emulsion, ethylene-vinyl chloride-vinyl acetate terpolymer emulsion, styrene or methylmethacrylate-butadiene copolymer Aqueous emulsions such as latex and aqueous urethane dispersion have been used, and these have been used alone or in combination with water-soluble epoxy resin, melamine resin, phenol resin, polyurethane resin and the like.

【0003】[0003]

【発明が解決しようとする課題】水性エマルション系接
着剤を単独で用いた場合、プラスチック、金属板、塗装
板に対する濡れ性に欠け、現象としてハジキを生じた
り、密着性に欠けるため接着力、耐水性、耐熱性、耐煮
沸性等が低く、植毛加工品を摩耗試験に供した場合、容
易にパイルが脱落するという接着性能上の問題があっ
た。これらの問題点を解決するため、水性エマルション
系接着剤中の成分と反応する、各種硬化剤を併用した方
法が提案されているが、貯蔵時の安定性すなわち経時に
よる粘度の上昇、凝集物の発性、又はゲル化等の作業性
上の欠陥や接着力、耐水性、耐熱性、耐煮沸性、耐摩耗
性等の不備等が問題となっていた。これらの問題を解決
する手段として、特願昭63ー033875、特願昭6
3ー126911、特願平1ー314204、特願平1
ー315423及び特願平2ー118026各号公報に
記載のように、エポキシ変性アクリルエマルションをベ
ース樹脂として、硬化剤として変性脂肪族ポリアミン、
変性ポリアミド樹脂、水溶性アミン、イミダゾール系等
の硬化剤を用いて接着性能を向上させる一方、シランカ
ップリング剤の併用で耐煮沸性を向上させる方法や、粘
着付与樹脂の併用で対プラスチックとの密着性向上を計
った接着剤が提案されている。しかしながらエポキシ変
性アクリルエルションは、静電植毛用接着剤としては接
着力を始めとして、耐熱性等優れた接着物性が得られる
ものの、最大の問題としてエポキシ変性アクリルエマル
ション自体の貯蔵時の安定性に欠陥があった。即ち長時
間の保管もしくは高温保管で接着剤が異常に増粘し、場
合によってはゲル化する問題があった。
When an aqueous emulsion adhesive is used alone, it lacks wettability with respect to plastics, metal plates and coated plates, and causes cissing as a phenomenon, or lacks in adhesiveness, resulting in adhesive strength and water resistance. When the flocked product is subjected to an abrasion test, the piles easily fall off, which is a problem in terms of adhesion performance. In order to solve these problems, a method in which various curing agents are used in combination, which reacts with the components in the aqueous emulsion adhesive, has been proposed. However, stability during storage, that is, increase in viscosity over time, aggregates There have been problems such as defects in workability such as foamability or gelation and defects such as adhesive strength, water resistance, heat resistance, boiling resistance, and abrasion resistance. As a means for solving these problems, Japanese Patent Application Nos. 63-033875 and 6
3-126911, Japanese Patent Application 1-314204, Japanese Patent Application 1
No. 315423 and Japanese Patent Application No. 2-118026, an epoxy-modified acrylic emulsion is used as a base resin, and a modified aliphatic polyamine is used as a curing agent.
Modified polyamide resin, water-soluble amine, while improving the adhesion performance by using a curing agent such as imidazole-based, while improving the boiling resistance by the combined use of silane coupling agent, and by using a tackifying resin in combination with plastic Adhesives with improved adhesion have been proposed. Epoxy-modified acrylic emulsion, however, has excellent adhesive properties such as heat resistance as an adhesive for electrostatic flocking, but the biggest problem is the stability of the epoxy-modified acrylic emulsion itself during storage. There was a flaw. That is, there is a problem in that the adhesive abnormally thickens during long-term storage or high-temperature storage and gels in some cases.

【0004】[0004]

【課題を解決するための手段】本発明者はエポキシ変性
アクリルエマルションの安定性問題を解決すべく鋭意検
討を重ねた結果、前記エマルションは、アクリルモノマ
ー、エポキシ樹脂及び各種官能基モノマーの混合物を界
面活性剤、水及び重合開始剤中に連続投与し得たエマル
ションにつき、エマルション粒子界面もしくは粒子の表
層にエポキシ樹脂が介在しており、該エポキシ樹脂がエ
マルション重合に用いた、他官能基モノマー類又は増粘
剤類と反応し安定化に悪影響を及ぼしているものと考え
られるため、エマルション粒子の構造を異層化し、エポ
キシ樹脂をエマルション粒子内部、即ちコアー部に共重
合し、該粒子の外側をアクリルモノマー及び水酸基を有
するモノマーを共重合した、いわゆるシエル層で被服す
ることが貯蔵時の安定性向上に極めて有効であることを
見出し本発明を完成させるに至った。
Means for Solving the Problems As a result of intensive studies by the present inventor to solve the stability problem of epoxy-modified acrylic emulsion, the emulsion has a mixture of acrylic monomer, epoxy resin and various functional group monomers as an interface. For the emulsion which can be continuously administered in the activator, water and the polymerization initiator, the epoxy resin is present at the emulsion particle interface or the surface layer of the particles, and the epoxy resin is used for emulsion polymerization, other functional group monomers or Since it is considered that it reacts with the thickeners and adversely affects the stabilization, the structure of the emulsion particles is made different layers, the epoxy resin is copolymerized inside the emulsion particles, that is, the core part, and the outside of the particles is It is recommended to coat with a so-called shell layer, which is a copolymer of acrylic monomer and hydroxyl group-containing monomer. And we have completed the present invention found that it is extremely effective for qualitative improvement.

【0005】即ち本発明は次の通りである。 (1)コアー層がアクリルモノマーとエポキシ樹脂の共
重合体、シェル層がアクリルモノマーと水酸基を有する
アクリルモノマーの共重合体であるコアーシェル構造を
有するエポキシ変性アクリルエマルションの固形分10
0重量部に対して、アミン又はポリアミド樹脂系硬化剤
を固形分として2〜25重量部配合して成る二液型水性
接着剤。 (2)コアー層がアクリルモノマーとエポキシ樹脂の合
計量100重量部に対してエポキシ樹脂5〜50重量
部、シェル層がアクリル単量体モノマー100重量部に
対して水酸基を有するアクリルモノマー2〜30重量部
それぞれ共重合して得られることを特徴とする(1)記
載の二液型水性接着剤。 (3)コアー層とシェル層の構成比が重量比で1/9〜
7/3の範囲であることを特徴とする(1)記載の二液
型水性接着剤。
That is, the present invention is as follows. (1) Solid content 10 of epoxy-modified acrylic emulsion having a core-shell structure in which the core layer is a copolymer of an acrylic monomer and an epoxy resin, and the shell layer is a copolymer of an acrylic monomer and an acrylic monomer having a hydroxyl group.
A two-component water-based adhesive which is obtained by blending 2 to 25 parts by weight of an amine or polyamide resin-based curing agent as a solid content with respect to 0 parts by weight. (2) The core layer has 5 to 50 parts by weight of epoxy resin with respect to 100 parts by weight of the total amount of acrylic monomer and epoxy resin, and the shell layer has 2 to 30 parts of acrylic monomer having a hydroxyl group with respect to 100 parts by weight of acrylic monomer monomer. The two-part aqueous adhesive according to (1), which is obtained by copolymerizing each part by weight. (3) The weight ratio of the core layer and the shell layer is 1/9 to
The two-component water-based adhesive according to (1), which has a range of 7/3.

【0006】本発明のコアーシェル構造を有するエポキ
シ変性アクリルエマルション(以下EPAEと略称す
る)は、まずアクリルモノマー中にエポキシ樹脂を溶解
せしめた混合モノマーを、蒸留水と若干量の界面活性剤
で予め乳化した、いわゆるプレ乳化モノマーを通常のア
クリルエマルションの乳化重合方法と同様の方法で重合
させることにより得られる。即ち、撹拌機付きフラスコ
内に蒸留水、界面活性剤を仕込み窒素置換し、約70℃
に温度調節された中に、重合開始剤を投与し、引続き前
記プレ乳化モノマーを連続滴下する方法で一定時間反応
させた後、更に残存モノマーを一定時間反応させること
により本発明のコアーとなるエマルション粒子を形成
し、次いで水酸基を有するモノマーとアクリルモノマー
の混合モノマーを、同様の方法で乳化し、前記系内に連
続滴下し、一定時間残存モノマーを反応させることによ
りコアーシェル構造を有するエポキシ変性アクリルエマ
ルションが得られる。反応終了後40℃以下に冷却し、
アンモニア水でPHを7〜8に調製し、100メッシュ
金網等で濾過し、ポリアクリル酸、ノニオン系界面活性
剤、ポリビニルアルコール等の水溶性高分子等で粘度を
約7、000cpsに調製し、本発明のEPAEが得ら
れる。
The epoxy-modified acrylic emulsion having a core-shell structure of the present invention (hereinafter referred to as EPAE) is prepared by first emulsifying a mixed monomer prepared by dissolving an epoxy resin in an acrylic monomer with distilled water and a small amount of a surfactant. It is obtained by polymerizing the so-called pre-emulsified monomer by a method similar to the usual emulsion polymerization method for acrylic emulsions. That is, distilled water and a surfactant were charged in a flask equipped with a stirrer and the atmosphere was replaced with nitrogen.
After the temperature is controlled, the polymerization initiator is administered, and then the pre-emulsified monomer is continuously dropped for a certain period of time, and then the residual monomer is further reacted for a certain period of time to form the core emulsion of the present invention. Epoxy-modified acrylic emulsion having a core-shell structure by forming particles, then emulsifying a mixed monomer of a monomer having a hydroxyl group and an acrylic monomer by the same method, continuously dropping into the system, and reacting the residual monomer for a certain period of time. Is obtained. After completion of the reaction, cool to 40 ° C or lower,
The pH is adjusted to 7 to 8 with ammonia water, filtered through a 100-mesh wire net, etc., and the viscosity is adjusted to about 7,000 cps with polyacrylic acid, nonionic surfactants, water-soluble polymers such as polyvinyl alcohol, and the like. The EPAE of the present invention is obtained.

【0007】本発明に用いるアクリルモノマーとして
は、下記のように硬質モノマー、軟質モノマー、官能基
モノマー等があげられる。硬質モノマーとしては、スチ
レン、αメチルスチレン、メチルメタアクリレート、エ
チルメタアクリレート、iーブチルメタアクリレート、
tertーブチルメタアクリレート、酢酸ビニル、アク
リロニトリル、2ヒドロキシエチルメタアクリレート等
があげられる。軟質単量体モノマーとしては、エチメル
アクリレート、iーブチルアクリレート、nーブチルア
クリレート、2エチルヘキシルアクリレート、2エチル
ヘキシルメタアクリレート、ラウリルメタアクリレート
等があげられる。
Examples of the acrylic monomer used in the present invention include hard monomers, soft monomers and functional group monomers as described below. As the hard monomer, styrene, α-methylstyrene, methylmethacrylate, ethylmethacrylate, i-butylmethacrylate,
Examples thereof include tert-butyl methacrylate, vinyl acetate, acrylonitrile, and 2hydroxyethyl methacrylate. Examples of the soft monomer monomer include ethimel acrylate, i-butyl acrylate, n-butyl acrylate, 2 ethylhexyl acrylate, 2 ethylhexyl methacrylate, lauryl methacrylate and the like.

【0008】官能基モノマーとして、本発明の必須成分
である水酸基を有するモノマーとしては、ヒドロキシエ
チルアクリレート、ヒドロキシエチルメタアクリレー
ト、ヒドロキシプロピルアクリレート等があげられる。
更に他官能基含有モノマーとして、カルボキシル基を有
するものとしてアクリル酸、メタアクリル酸、イタコン
酸、マレイン酸、フマール酸等が、アミド基を有するも
のとしてアクリルアミド、メタアクリルアミド、マレイ
ミド等が、N−メチロールアクリルアミド基を有するも
のとしてはN−メチロールアクリルアミド等があげられ
る。コアー層に用いるエポキシ樹脂としては、ビスフェ
ノールA−エピクロルヒドリン樹脂であり、例えばエポ
キシ当量180〜270、粘度5〜150ポイズ(25
℃)のエポキシ樹脂があげられる。
Examples of the functional group monomer having a hydroxyl group, which is an essential component of the present invention, include hydroxyethyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl acrylate.
Further, as the other functional group-containing monomer, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid or the like having a carboxyl group, acrylamide, methacrylamide, maleimide or the like having an amide group, N-methylol Examples of those having an acrylamide group include N-methylol acrylamide. The epoxy resin used for the core layer is a bisphenol A-epichlorohydrin resin, for example, an epoxy equivalent of 180 to 270 and a viscosity of 5 to 150 poise (25
C) epoxy resin.

【0009】EPAE中、コアー層中のエポキシ樹脂は
アクリルモノマー(含むエポキシ樹脂)100重量部
中、5〜50重量部の範囲、より好ましくは10〜30
重量部の範囲である。5重量部より少い場合は接着力、
耐熱性、耐煮沸性等が得られず、50重量部より多い場
合は乳化重合に支障があり実用性に欠ける。一方シェル
層中の水酸基の量は、アクリルモノマー100重量部中
2〜30重量部の範囲、より好ましくは5〜20重量部
の範囲である。2重量部より少い場合は貯蔵安定性の向
上が見られず、3O重量部より多い場合は乳化重合時に
ゲル化等を起こし実用性に欠ける。EPAEのコアー/
シェルの構成比は、重量比で1/9〜7/3、より好ま
しくは3/7〜5/5の範囲である。コアー層の比率が
1より小さい場合接着力、耐熱性、耐煮沸性等が得られ
ず、7より大きい場合はコアー層の完全被覆が不可能で
貯蔵時の安定性に問題を生ずる。
In EPAE, the epoxy resin in the core layer is in the range of 5 to 50 parts by weight, more preferably 10 to 30 parts, per 100 parts by weight of the acrylic monomer (containing epoxy resin).
The range is parts by weight. Adhesive strength if less than 5 parts by weight,
If heat resistance and boiling resistance are not obtained and the amount is more than 50 parts by weight, emulsion polymerization is hindered and practicality is impaired. On the other hand, the amount of hydroxyl groups in the shell layer is in the range of 2 to 30 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the acrylic monomer. When it is less than 2 parts by weight, the storage stability is not improved, and when it is more than 30 parts by weight, gelation or the like occurs during emulsion polymerization, which is not practical. EPAE core /
The composition ratio of the shell is 1/9 to 7/3 by weight, and more preferably 3/7 to 5/5. When the ratio of the core layer is less than 1, adhesive strength, heat resistance, boiling resistance and the like cannot be obtained, and when it is more than 7, complete coverage of the core layer is impossible and problems occur in stability during storage.

【0010】EPAEのコアーとシェル層のポリマーの
ガラス転移温度(以下Tgと略称する)は特に限定しな
いが、コア層とシェル層の温度差が10℃〜 80℃の
範囲であった方が、コアーシェル層の形成上好ましく、
コアー層、シェル層のいずれのTgが高くても良いが、
好ましくは各種被着体への接着性からコアー層のTgが
高い方が望ましい。但し、本発明のコアー層のTg表現
はエポキシ樹脂を除外して算出したものとする。具体的
なTgの例としては、コアー層が−20〜+40℃、シ
ェル層が−40〜+20℃である。本発明の好ましいコ
アーの構成割合は、スチレン25〜50重量部、nーブ
チルアクリレート25〜50重量部、エポキシ樹脂5〜
50重量部、アクリルアマイド1〜5重量部、ヒドロキ
シエチルメタアクリレート1〜5重量部、場合によって
はメタアクリル酸1〜5重量部であり、シェルの構成割
合はスチレン20〜40重量部、nーブチルアクリレー
ト30〜60重量部、メタアクリル酸1〜10重量部、
アクリルアマイド1〜5重量部、ヒドロキシエチルアク
リレート又はヒドロキシエチルメタアクリレート2〜3
0重量部である。
The glass transition temperature (hereinafter abbreviated as Tg) of the polymer of the core and shell layers of EPAE is not particularly limited, but when the temperature difference between the core layer and the shell layer is in the range of 10 ° C to 80 ° C, From the viewpoint of forming the core-shell layer,
Either Tg of the core layer or the shell layer may be high,
It is desirable that the core layer has a high Tg in terms of adhesion to various adherends. However, the Tg expression of the core layer of the present invention is calculated by excluding the epoxy resin. As a specific example of Tg, the core layer has a temperature of −20 to + 40 ° C., and the shell layer has a temperature of −40 to + 20 ° C. The preferred composition ratio of the core of the present invention is 25 to 50 parts by weight of styrene, 25 to 50 parts by weight of n-butyl acrylate, 5 to 50 parts of epoxy resin.
50 parts by weight, 1 to 5 parts by weight of acrylic amide, 1 to 5 parts by weight of hydroxyethyl methacrylate, and 1 to 5 parts by weight of methacrylic acid in some cases, and the composition ratio of the shell is 20 to 40 parts by weight of styrene, n- Butyl acrylate 30-60 parts by weight, methacrylic acid 1-10 parts by weight,
Acrylic amide 1-5 parts by weight, hydroxyethyl acrylate or hydroxyethyl methacrylate 2-3
0 parts by weight.

【0011】アミンもしくはポリアミド系硬化剤として
は、一般にエポキシ樹脂の硬化剤として用いられる、鎖
状脂肪族ポリアミン、環状脂肪族ポリアミン、変性脂肪
族ポリアミン、変性芳香族ポリアミン、変性ポリアミド
アミン、ポリアミド樹脂等が上げられ、これらの種類は
特には限定しないが、毒性、臭気、皮膚障害等の危険性
からすると、ポリアミド樹脂系が好ましい。更に、これ
ら硬化剤の性状は水性エマルションに配合する関係上、
水溶性もしくは水性ディスパージョン型が好ましい。該
アミンもしくはポリアミド樹脂系硬化剤の配合割合は、
EPAEの固形分100重量部に対して、固形分として
2〜25重量部の範囲である。好ましくは5〜10重量
部の範囲である。2重量部より少い場合硬化が不十分で
あり接着力を始めとする接着諸物性が低く、25重量部
より多い場合接着剤の臭気、皮膚障害等の危険性と共に
硬化物の黄褐色化、更には耐水性、耐煮沸性が低下する
等の問題が発生する。
As the amine- or polyamide-based curing agent, a chain aliphatic polyamine, a cycloaliphatic polyamine, a modified aliphatic polyamine, a modified aromatic polyamine, a modified polyamideamine, a polyamide resin or the like which is generally used as a curing agent for epoxy resins is used. The types are not particularly limited, but polyamide resins are preferred from the viewpoint of toxicity, odor, skin damage and the like. Furthermore, the properties of these curing agents are related to the addition to the aqueous emulsion,
A water-soluble or aqueous dispersion type is preferred. The mixing ratio of the amine or polyamide resin-based curing agent is
The solid content is in the range of 2 to 25 parts by weight with respect to 100 parts by weight of the solid content of EPAE. It is preferably in the range of 5 to 10 parts by weight. If the amount is less than 2 parts by weight, the curing is insufficient and adhesive properties such as adhesive strength are low, and if the amount is more than 25 parts by weight, the cured product becomes yellowish brown with the risk of odor and skin damage. Further, problems such as deterioration of water resistance and boiling resistance occur.

【0012】本発明のEPAEは、長時間保管もしくは
高温保管条件において、接着剤の異常増粘又はゲル化が
解消され、アミン又はポリアミド樹脂系硬化剤併用時の
安定性に優れ、静電植毛用接着剤の具備すべき、接着
力、耐水性、耐熱性、耐煮沸性、耐摩耗性等の接着物性
に優れ成型加工された基板の静電植毛加工部材用接着剤
用として、その実用価値は極めて高いものである。EP
AE二液型水性接着剤の使用に当たっては、必要に応じ
て着色剤、消泡剤、老化防止剤、紫外線吸収剤、レベリ
ング剤、シランカップリング剤等を添加して用いても良
い。
The EPAE of the present invention eliminates abnormal thickening or gelation of the adhesive under long-term storage or high-temperature storage conditions, has excellent stability when used in combination with an amine or polyamide resin-based curing agent, and is used for electrostatic flocking. Excellent adhesive properties such as adhesive strength, water resistance, heat resistance, boiling resistance, and abrasion resistance that adhesives must have, and its practical value as an adhesive for electrostatic flocking members of molded substrates It is extremely expensive. EP
In using the AE two-component water-based adhesive, a colorant, a defoaming agent, an antiaging agent, an ultraviolet absorber, a leveling agent, a silane coupling agent, etc. may be added, if necessary.

【0013】[0013]

【実施例】以下に本発明を更に具体的に説明するため、
製造例、実施例、比較例をあげて説明する。特に指定の
ない限り、部又は%は重量基準とする。
EXAMPLES In order to explain the present invention more specifically,
A description will be given with reference to production examples, examples and comparative examples. Parts or percentages are by weight unless otherwise specified.

【0014】製造例1〜8 表−1に示す組成割合のコアー層及びシェル層用の混合
モノマー100部と連鎖移動剤との混合物を、各々蒸留
水50部、ドデシルベンゼンスルホン酸ソーダ0、5部
中に、撹拌条件下で連続的に添加しプレ乳化物モノマー
を作成した。別に、撹拌機付き1リッターフラスコに蒸
留水100部、ドデシルベゼンスルホン酸ソーダ0、2
部を仕込み、窒素シール下で撹拌しながら70℃に昇温
し、0、5部の過硫酸カリウムとエマルションの種とな
る、nブチルアクリレート1部、メチルメタアクリレー
ト1部、ヒドロキシエチルアクリレート0、5部からな
る混合モノマーを投与し、20分反応させ本発明のエマ
ルションの核を形成した。これに、前記コアー用プレ乳
化物モノマーを3時間かけて連続滴下し、更に同温度条
件下で2時間残存モノマーを反応させた後、シェル用プ
レ乳化モノマーを3時間かけて連続滴下し、残存モノマ
ーを3時間反応させた後、40℃以下まで冷却し、14
%濃度のアンモニア水でPHを7に調整し100メッシ
ュ金網で濾過し、固形分50%のEPAEを得た。次い
でポリアクリル酸(日本アクリル化学(株)、商品名プ
ライマルASE60、固形分24%)の、14%希釈水
溶液を用い粘度7000cps、固形分48%の本発明
のEPAE接着剤を得た。本製造例のコアー/シェル比
は、モノマーを200部用いることを前提とし、例えば
3/7の比率の場合、コアー層用/シェル層用が60/
140部であることを示す。
Production Examples 1 to 8 Mixtures of 100 parts of a mixed monomer for the core layer and shell layer having the composition ratios shown in Table 1 and a chain transfer agent were respectively distilled water 50 parts, sodium dodecylbenzenesulfonate 0, 5 A pre-emulsion monomer was prepared by continuously adding to the part under stirring conditions. Separately, in a 1-liter flask equipped with a stirrer, 100 parts of distilled water, 0, 2 of sodium dodecylbenzene sulfonate.
Parts, charged with stirring under a nitrogen blanket and heated to 70 ° C., and 0, 5 parts of potassium persulfate and seeds of emulsion, n-butyl acrylate 1 part, methyl methacrylate 1 part, hydroxyethyl acrylate 0, A mixed monomer consisting of 5 parts was administered and reacted for 20 minutes to form the core of the emulsion of the present invention. The pre-emulsified monomer for core was continuously added dropwise thereto over 3 hours, and the residual monomer was further reacted for 2 hours under the same temperature condition, and then the pre-emulsified monomer for shell was continuously added dropwise over 3 hours to leave the residual monomer. After reacting the monomers for 3 hours, cool to 40 ° C or below,
The pH was adjusted to 7 with ammonia water having a concentration of 100% and filtered through a 100-mesh wire net to obtain EPAE having a solid content of 50%. Then, an EPAE adhesive of the present invention having a viscosity of 7000 cps and a solid content of 48% was obtained using a 14% diluted aqueous solution of polyacrylic acid (Nippon Acrylic Chemical Co., Ltd., trade name Primal ASE60, solid content 24%). The core / shell ratio of this production example is based on the premise that 200 parts of the monomer is used. For example, in the case of the ratio of 3/7, the core layer / shell layer ratio is 60 /
It indicates that it is 140 copies.

【0015】[0015]

【表1】 [Table 1]

【0016】実施例1〜12 製造例1〜8で得た本発明のEPAE100部に対し、
表−2に示したアミン又はポリアミド樹脂系硬化剤を配
合し、本発明のEPAE二液水性接着剤を得た。得られ
た接着剤を次に示す方法で物性評価した。結果を表−3
に示す。
Examples 1 to 12 For 100 parts of the EPAE of the present invention obtained in Production Examples 1 to 8,
The amine or polyamide resin-based curing agent shown in Table 2 was blended to obtain the EPAE two-component water-based adhesive of the present invention. The obtained adhesive was evaluated for its physical properties by the following methods. The results are shown in Table-3.
Shown in.

【0017】[0017]

【表2】 [Table 2]

【0018】A: 物性評価方法 A−1 EPAEの経時粘度変化 本発明のEPAE接着剤(増粘品単品)を250ccポ
リビンに200g採取し、40℃恒温槽に2ヶ月間放置
し、粘度の上昇及びゲル化状態を観察し、下記の通り表
示した。 ◎ 全く異常なし ○ 元の粘度に対して10〜20%の粘度上昇、但し凝
集物はなし △ 若干の凝集物を発生 × ゲル化 A−2 硬化剤配合品の経時粘度変化 実施例で得た二液配合接着剤をA−1同様に採取し、4
0℃高温槽に24時間放置後の粘度の上昇及びゲル化状
態を観察しA−1同様に表示した。 A−3 常態接着力 ABS板に200g/m2 、実施例の接着剤を均一に塗
布し、直に綿布40番を張り合わせ、80℃熱風乾燥機
で30分乾燥する。24時間室温養生後、25mm幅、長
さ100mmに裁断し、インテスコ引っ張り試験機で18
0゜剥離試験に供し、その結果をKg/25mmで表示し
た。 A−4 耐熱接着力 A−3と同様の操作で、90℃雰囲気下で測定しA−3
同様に表示した。 B: 静電植毛加工品の物性評価方法 20×20cm角のABS板にエアースプレーを用い、
本発明の接着剤を200g/m2 の接着剤を均一に塗布
する。次いで、ナイロンパイル(3ディニール、長さ
0、5mm)を、30KVの電圧をかけて植毛し、80
℃乾燥機で30分乾燥後、室温で24時間養生した。本
試料を25mm幅に裁断し、学振型摩擦堅牢度試験機に
よる下記摩耗試験に供した。 B−1 常態摩耗試験 試験機の摩擦子に綿布40番を取り付け、荷重500
g、30回/分のスピードで、5000回摩擦し、植毛
面の変化の有無を下記の通り表示した。 ○ 異常なし △ 部分的に薄く脱毛が認められる。 × 対面積当り、50%以上の脱毛が認められる。 B−2 耐水摩耗試験 B−1同様の操作で、植毛面及び綿に予め3ccの水を
滴下し摩擦を開始し、500回毎に植毛面に2ccの水
を補充滴下しながら3000回摩擦し、植毛面の変化を
B−1同様に表示した。 B−3 耐煮沸性 前記植毛加工品を煮沸水に2時間浸漬し、取り出し直後
の植毛面の剥がれ、膨れ等を観察し下記の通り表示し
た。 ○ 異常を認めず △ 部分的な膨れ発生 × 煮沸中に植毛部が自然剥離
A: Physical property evaluation method A-1 Change in viscosity of EPAE over time 200 g of the EPAE adhesive of the present invention (a thickened product alone) was sampled in 250 cc polybin and allowed to stand in a constant temperature bath at 40 ° C. for 2 months to increase the viscosity. And the gelled state was observed and displayed as follows. ◎ No abnormality at all ○ Viscosity increase of 10 to 20% with respect to the original viscosity, but no agglomerates △ Some agglomerates were generated × Gelation A-2 Change in viscosity with time of curing agent compounded product Collect the liquid mixture adhesive in the same manner as A-1, and
The increase in viscosity and the gelation state after standing in a 0 ° C. high temperature tank for 24 hours were observed and displayed as in A-1. A-3 Normal Adhesion Force The adhesive of Example was uniformly applied to an ABS plate at 200 g / m 2 , and cotton cloth No. 40 was directly stuck to the ABS plate and dried at 80 ° C. for 30 minutes with a hot air dryer. After curing at room temperature for 24 hours, cut into a width of 25 mm and a length of 100 mm, and use an Intesco tensile tester to make 18
It was subjected to a 0 ° peel test and the result was expressed in Kg / 25 mm. A-4 Heat-resistant adhesive strength A-3 in the same operation as A-3, measured in an atmosphere of 90 ° C.
Displayed in the same way. B: Method for evaluating physical properties of electrostatic flocked product Using air spray on a 20 × 20 cm square ABS plate,
The adhesive of the present invention is uniformly applied with 200 g / m 2 of the adhesive. Then, a nylon pile (3 denier, length 0, 5 mm) was applied with a voltage of 30 KV to flock the hair to 80
After drying for 30 minutes in a ° C dryer, it was aged at room temperature for 24 hours. This sample was cut into a width of 25 mm and subjected to the following abrasion test using a Gakushin type friction fastness tester. B-1 Normal wear test Attach a cotton cloth No. 40 to the friction element of the tester and load 500
It was rubbed 5000 times at a speed of 30 times / min and the presence or absence of a change in the flocked surface was displayed as follows. ○ No abnormality △ Partial thinning of hair is observed. × Hair loss of 50% or more per area is observed. B-2 Water abrasion resistance test In the same manner as in B-1, 3 cc of water was dropped in advance on the flocked surface and cotton to start rubbing, and every 500 times, 2 cc of water was replenished and rubbed 3000 times while rubbing. The change in the flocked surface was displayed in the same manner as B-1. B-3 Boiling resistance The above-mentioned flocked product was immersed in boiling water for 2 hours, and the flocked surface was peeled off and swollen immediately after removal, and the results were displayed as follows. ○ No abnormalities were observed △ Partial swelling occurred × The flocked part spontaneously peeled off during boiling

【0019】[0019]

【表3】 [Table 3]

【0020】比較例1 製造例1のコアー層及びシェル層に用いた組成のモノマ
ーを混合して用い、製造例のコアー層の乳化重合に準じ
て48%のEPAEを作製し、実施例2と同様の硬化剤
を配合し、実施例同様に物性評価した。結果を表−3に
示す。 比較例2 製造例4のコアー層及びシェル層に用いた組成のモノマ
ーを混合して用い、比較例1と同様に48%のEPAE
を作製し、以下実施例2と同様の硬化剤を配合して物性
を評価した。結果を表−3に示す。 比較例3 製造例5のコアー層及びシエル層に用いた組成のモノマ
ーを混合して用い、比較例1と同様に48%のEPAE
を作製し、以下実施例2と同様の硬化剤を配合して物性
を評価した。結果を表−3に示す。 比較例4 製造例1のコアー/シェル比を0.5/9.5とした以
外は製造例1と同様にEPAEを作製し、以下実施例2
と同様の硬化剤を配合して物性を評価した。結果を表−
3に示す。 比較例5 製造例1のコアー/シェル比を8/2とした以外は製造
例1と同様にEPAEを作製し、以下実施例2と同様の
硬化剤を配合して物性を評価した。結果を表−3に示
す。 比較例6 実施例2の硬化剤量を1部(固形分として0.88部)
に減らした以外は、実施例2と同様に物性評価をした。
結果を表−3に示す。 比較例7 実施例2の硬化剤量を30部(固形分として26.5
部)に増やした以外は、実施例2と同様に物性評価をし
た。結果を表−3に示す。
Comparative Example 1 48% EPAE was prepared according to the emulsion polymerization of the core layer of Production Example by mixing and using the monomers having the compositions used for the core layer and shell layer of Production Example 1, and Example 2 and The same curing agent was added and the physical properties were evaluated in the same manner as in the examples. The results are shown in Table-3. Comparative Example 2 As in Comparative Example 1, 48% EPAE was used in the same manner as in Comparative Example 1, except that the monomers having the compositions used in the core layer and the shell layer of Production Example 4 were mixed and used.
Was prepared, and the same curing agent as in Example 2 was added, and the physical properties were evaluated. The results are shown in Table-3. Comparative Example 3 As in Comparative Example 1, 48% EPAE was used in the same manner as in Comparative Example 1, except that the monomers having the compositions used in the core layer and the shell layer of Production Example 5 were mixed and used.
Was prepared, and the same curing agent as in Example 2 was added, and the physical properties were evaluated. The results are shown in Table-3. Comparative Example 4 An EPAE was produced in the same manner as in Production Example 1 except that the core / shell ratio in Production Example 1 was changed to 0.5 / 9.5, and the following Example 2 was used.
A curing agent similar to the above was added and the physical properties were evaluated. Table of results
3 shows. Comparative Example 5 An EPAE was prepared in the same manner as in Production Example 1 except that the core / shell ratio in Production Example 1 was changed to 8/2, and the curing agent similar to that in Example 2 was blended to evaluate the physical properties. The results are shown in Table-3. Comparative Example 6 1 part of the curing agent of Example 2 (0.88 parts as solid content)
Physical properties were evaluated in the same manner as in Example 2 except that the amount was reduced to.
The results are shown in Table-3. Comparative Example 7 The amount of the curing agent of Example 2 was 30 parts (26.5 in terms of solid content).
Physical properties were evaluated in the same manner as in Example 2 except that the number of parts was increased. The results are shown in Table-3.

【0021】[0021]

【発明の効果】表−3から明らかな通り、本発明の二液
型水性接着剤は自動車内装材、弱電機器、事務用機器の
ような、成型加工板を基材とした静電植毛加工用接着剤
として用いた場合、エポキシ変性アクリルエマルション
自体の経時粘度変化及び高温保管条件下での貯蔵安定性
に優れ、かつ、二液配合時の粘度安定性も具備してお
り、接着性能としても、前記植毛加工部材が具備すべき
接着力、耐水性、耐熱性、耐摩耗性等に優れることか
ら、その実用価値は極めて高いものである。
As is apparent from Table 3, the two-component water-based adhesive of the present invention is used for electrostatic flocking using a molded plate as a base material such as automobile interior materials, light electric appliances and office equipment. When used as an adhesive, the epoxy-modified acrylic emulsion itself has excellent viscosity stability over time and storage stability under high-temperature storage conditions, and also has viscosity stability during two-component formulation, and also as adhesive performance, Since the flocked member has excellent adhesive strength, water resistance, heat resistance, wear resistance, etc., its practical value is extremely high.

Claims (3)

【特許請求の範囲】[Claims] 【請求項1】 コアー層がアクリルモノマーとエポキシ
樹脂の共重合体、シェル層がアクリルモノマーと水酸基
を有するアクリルモノマーの共重合体である、コアーシ
ェル構造を有するエポキシ変性アクリルエマルションの
固形分100重量部に対して、アミン又はポリアミド樹
脂系硬化剤を固形分として2〜25重量部配合して成る
二液型水性接着剤。
1. A solid content of 100 parts by weight of an epoxy-modified acrylic emulsion having a core-shell structure, wherein the core layer is a copolymer of an acrylic monomer and an epoxy resin, and the shell layer is a copolymer of an acrylic monomer and an acrylic monomer having a hydroxyl group. On the other hand, a two-pack type water-based adhesive comprising an amine or polyamide resin-based curing agent as a solid content in an amount of 2 to 25 parts by weight.
【請求項2】 コアー層がアクリルモノマーとエポキシ
樹脂の合計量100重量部に対してエポキシ樹脂5〜5
0重量部、シェル層がアクリルモノマー100重量部に
対して水酸基を有するアクリルモノマー2〜30重量部
をそれぞれ共重合して得た共重合体であることを特徴と
する請求項1記載の二液型水性接着剤。
2. The core layer comprises 5 to 5 epoxy resins per 100 parts by weight of the total amount of acrylic monomer and epoxy resin.
2. The two-part liquid according to claim 1, which is a copolymer obtained by copolymerizing 0 part by weight and 2 to 30 parts by weight of an acrylic monomer having a hydroxyl group with 100 parts by weight of the acrylic monomer in the shell layer. Mold water-based adhesive.
【請求項3】 コアー層とシェル層の構成比が重量比で
1/9〜7/3の範囲であることを特徴とする請求項1
記載の二液型水性接着剤。
3. The weight ratio of the core layer and the shell layer is in the range of 1/9 to 7/3.
The two-component water-based adhesive described.
JP12405893A 1993-05-26 1993-05-26 Two-component aqueous adhesive Expired - Fee Related JP3247915B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP12405893A JP3247915B2 (en) 1993-05-26 1993-05-26 Two-component aqueous adhesive

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP12405893A JP3247915B2 (en) 1993-05-26 1993-05-26 Two-component aqueous adhesive

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Publication Number Publication Date
JPH06330011A true JPH06330011A (en) 1994-11-29
JP3247915B2 JP3247915B2 (en) 2002-01-21

Family

ID=14875929

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Link
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007169663A (en) * 2007-03-26 2007-07-05 National Institute Of Advanced Industrial & Technology Method for producing anisotropic polymer fine particles having plural kinds of functional groups
CN115651582A (en) * 2022-12-07 2023-01-31 河北工业大学 Preparation method of heat-conducting toughening insulating epoxy resin structural adhesive

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007169663A (en) * 2007-03-26 2007-07-05 National Institute Of Advanced Industrial & Technology Method for producing anisotropic polymer fine particles having plural kinds of functional groups
CN115651582A (en) * 2022-12-07 2023-01-31 河北工业大学 Preparation method of heat-conducting toughening insulating epoxy resin structural adhesive
CN115651582B (en) * 2022-12-07 2023-09-22 河北工业大学 Preparation method of heat-conducting toughened insulating epoxy resin structural adhesive

Also Published As

Publication number Publication date
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