JPH07196997A - Production of water-dispersion type heat-sensitive adhesive - Google Patents
Production of water-dispersion type heat-sensitive adhesiveInfo
- Publication number
- JPH07196997A JPH07196997A JP35103493A JP35103493A JPH07196997A JP H07196997 A JPH07196997 A JP H07196997A JP 35103493 A JP35103493 A JP 35103493A JP 35103493 A JP35103493 A JP 35103493A JP H07196997 A JPH07196997 A JP H07196997A
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- JP
- Japan
- Prior art keywords
- water
- dispersed
- wax
- particles
- resin
- 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.)
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- Processes Of Treating Macromolecular Substances (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、エチレン−酢酸ビニ
ル共重合体と、粘着樹脂および／またはワックスとの溶
融混合物が水中に乳化分散されている乳化分散物（エマ
ルション）からなり、該乳化分散物を塗布して乾燥さ
せ、被着材と合わせて加熱溶融により接着を行うように
なっている水分散型感熱接着剤の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention comprises an emulsified dispersion (emulsion) in which a melt mixture of an ethylene-vinyl acetate copolymer and an adhesive resin and / or wax is emulsified and dispersed in water. The present invention relates to a method for producing a water-dispersible heat-sensitive adhesive, which is configured such that an object is applied, dried, and combined with an adherend by heating and melting.
【０００２】[0002]
【従来の技術】感熱接着剤は、ヒートシール剤、ディレ
ードタック剤、インモールドラベル、パートコート剤な
どに使われている。感熱接着剤は、常温で固体のもの
（いわゆるホットメルト接着剤）と液状のものとがあ
る。固体の感熱接着剤は塗布時に高温にして溶融させる
必要がある上、高粘度である。これに対し、液状の感熱
接着剤は、塗布時に高温にする必要はなく、しかも、低
粘度である。2. Description of the Related Art Heat-sensitive adhesives are used as heat seal agents, delayed tack agents, in-mold labels, part coat agents and the like. The heat-sensitive adhesive is classified into a solid one (so-called hot melt adhesive) and a liquid one at room temperature. A solid heat-sensitive adhesive needs to be heated at a high temperature to be melted at the time of application and has a high viscosity. On the other hand, the liquid heat-sensitive adhesive does not need to be heated to a high temperature during application and has a low viscosity.
【０００３】常温で液状の感熱接着剤は、接着剤用熱可
塑性樹脂の粒子（固体粒子または液滴）が水に分散して
なる水分散型のものと熱可塑性樹脂が溶剤に溶解または
分散してなる溶剤型のものとがある。水分散型感熱接着
剤は、有機溶剤を用いる必要がないので、溶剤型のもの
に比べると、公害がなく、安全性も高い。このため、水
分散型感熱接着剤が今後の主流になっていくと考えられ
る。Thermosensitive adhesives which are liquid at room temperature are water-dispersible type in which particles (solid particles or droplets) of a thermoplastic resin for adhesive are dispersed in water, and thermoplastic resins are dissolved or dispersed in a solvent. There is a solvent type. Since the water-dispersed heat-sensitive adhesive does not require the use of an organic solvent, it has less pollution than the solvent-based adhesive and is highly safe. For this reason, water-dispersed heat-sensitive adhesives are expected to become the mainstream in the future.
【０００４】水分散型感熱接着剤は、下記〜の方法
の単独もしくはそれらの組み合わせにより作られてい
る。 反転乳化法：熱溶融した接着剤用熱可塑性樹脂中に
水を分散してＷ／Ｏエマルションを作った後、Ｏ／Ｗエ
マルションに転相する。 常圧ホモミキサー法：接着剤用熱可塑性樹脂を通常
のホモミキサーで水に乳化してＯ／Ｗエマルションを作
った後、脱溶剤する。熱可塑性樹脂の軟化点（Ｓ．
Ｐ．）が１００℃以下でその粘度が著しく高くない場
合、溶剤に溶かさずそのままホモミキサーにかけられ
る。熱可塑性樹脂の軟化点（Ｓ．Ｐ．）が１００℃以上
かまたはその粘度が著しく高い場合には、溶剤で溶解も
しくは希釈してホモミキサーにかけられる。 耐圧ホモミキサー法：溶剤で溶解または希釈するこ
となく乳化するために、耐圧容器内で高圧力雰囲気にし
て水の沸点を上げ、軟化点１００℃以上の樹脂を含むか
または軟化点が１００℃以下でも粘度の高い樹脂を含む
接着剤用熱可塑性樹脂を加熱溶融した状態で水に乳化す
る。 高圧ホモジナイザー法：接着剤用熱可塑性樹脂を予
め水に乳化してなる予備乳化物（プレ乳化物）をホモジ
ナイザーにより２００〜５００kg／cm2 の高圧力で処理
する。 押し出しルーダー法：二軸押出機のホッパーに樹脂
を供給し、圧縮あるいは計量ゾーンに乳化剤を含んだ水
溶液を加圧して供給し、分散液を得る。The water-dispersible heat-sensitive adhesive is produced by any of the following methods (1) to (4) or a combination thereof. Inversion emulsification method: Water is dispersed in a heat-melted thermoplastic resin for adhesives to prepare a W / O emulsion, and then the phase is converted into an O / W emulsion. Normal pressure homomixer method: A thermoplastic resin for adhesives is emulsified in water with an ordinary homomixer to prepare an O / W emulsion, and then the solvent is removed. Softening point of thermoplastic resin (S.
P. When the viscosity is not higher than 100 ° C and the viscosity is not extremely high, it is not dissolved in a solvent and can be directly applied to a homomixer. When the softening point (SP) of the thermoplastic resin is 100 ° C. or higher or the viscosity thereof is extremely high, the thermoplastic resin is dissolved or diluted with a solvent and subjected to a homomixer. Pressure-resistant homomixer method: In order to emulsify without dissolving or diluting with a solvent, a high-pressure atmosphere is used in a pressure-resistant container to raise the boiling point of water, and a resin having a softening point of 100 ° C or higher is contained or a softening point of 100 ° C or lower. However, a thermoplastic resin for adhesives containing a resin with high viscosity is emulsified in water in a state of being heated and melted. High-pressure homogenizer method: A preliminary emulsion (pre-emulsion) obtained by previously emulsifying a thermoplastic resin for adhesives in water is treated with a homogenizer at a high pressure of 200 to 500 kg / cm 2 . Extrusion ruder method: A resin is supplied to a hopper of a twin-screw extruder, and an aqueous solution containing an emulsifier is pressurized and supplied to a compression or measurement zone to obtain a dispersion liquid.
【０００５】[0005]
【発明が解決しようとする課題】反転乳化法は、転相を
行うため酸価を持った樹脂をアルカリ存在下で乳化する
必要があるため酸価を持った樹脂しか使用できず、接着
剤の設計の自由度が小さい。接着剤の設計の自由度が小
さいと接着剤の接着性、ヒートシール性または耐ブロッ
キング性に制限がある。ベースポリマーを乳化するため
には乳化剤を多量に使用しなければならないので、接着
剤が乳化剤を多量に含有しており接着性、接着強度また
は耐水性に劣り、また、貯蔵安定性に劣っている。In the inversion emulsification method, it is necessary to emulsify a resin having an acid value in the presence of an alkali in order to carry out phase inversion, so that only a resin having an acid value can be used. The degree of freedom in design is small. If the degree of freedom in the design of the adhesive is small, the adhesiveness, heat sealability or blocking resistance of the adhesive is limited. Since an emulsifier must be used in a large amount in order to emulsify the base polymer, the adhesive contains a large amount of emulsifier and is inferior in adhesiveness, adhesive strength or water resistance, and inferior in storage stability. .
【０００６】常圧ホモミキサー法は、軟化点が１００℃
以下でも粘度が著しく高い樹脂や軟化点が１００℃以上
の樹脂は溶剤で溶解または希釈して乳化しなければなら
ず、その上、脱溶剤の工程が必要であり、また、貯蔵安
定性に劣っている。上述した、耐圧ホモミキサー法、高
圧ホモジナイザー法および押し出しルーダー法により得
られたエマルションは乳化安定性が悪く、クリーミング
を起こす。The atmospheric pressure homomixer method has a softening point of 100 ° C.
Resins having extremely high viscosities or resins having a softening point of 100 ° C. or higher must be dissolved or diluted with a solvent to emulsify, and in addition, a solvent removal step is required and storage stability is poor. ing. The emulsions obtained by the pressure resistant homomixer method, the high pressure homogenizer method and the extrusion ruder method described above have poor emulsion stability and cause creaming.
【０００７】水分散型感熱接着剤は、支持体に塗布して
乾燥した状態で製品化される場合が多い。感熱接着剤
は、加熱により溶融して被着材に対する濡れが発生した
後、冷却固化して接着するようになっている。このた
め、感圧接着剤とは異なり剥離シートは不要のはずであ
るが、接着性向上を図ると耐ブロッキング性が低下する
ことがある。耐ブロッキング性が低下すると、高温多湿
を避けるように保管条件が制限される。使用できる樹脂
の種類の制限がなければ接着性向上と耐ブロッキング性
向上の両立を図ることができる。Water-dispersed heat-sensitive adhesives are often commercialized in a dried state after being applied to a support. The heat-sensitive adhesive is adapted to be melted by heating and to wet the adherend, and then cooled and solidified to adhere. Therefore, unlike a pressure-sensitive adhesive, a release sheet should be unnecessary, but blocking resistance may be reduced when the adhesiveness is improved. When the blocking resistance is lowered, storage conditions are restricted so as to avoid high temperature and high humidity. If there is no restriction on the type of resin that can be used, both improved adhesion and improved blocking resistance can be achieved.
【０００８】この発明は、広範囲の接着剤用熱可塑性樹
脂をできるだけ脱溶剤工程なしに乳化して貯蔵安定性に
優れた水分散型感熱接着剤を得る製造方法を提供するこ
とを課題とする。It is an object of the present invention to provide a method for producing a water-dispersible heat-sensitive adhesive having excellent storage stability by emulsifying a wide range of thermoplastic resins for adhesives with as little solvent removal step as possible.
【０００９】[0009]
【課題を解決するための手段】この発明は、上記課題を
解決するために、ワックスおよび粘着樹脂のうちの少な
くとも１つとエチレン−酢酸ビニル共重合体（以下、
「ＥＶＡ」と言うことがある。）とを水中で軟化状態に
して保護コロイドの存在下に攪拌して得られた予備乳化
分散物を高圧ホモジナイザーにより１３００kg／cm2 以
上の圧力で攪拌することにより、前記ワックスおよび粘
着樹脂のうちの少なくとも１つとエチレン−酢酸ビニル
共重合体との溶融混合物からなる粒子が保護コロイドに
より水中に乳化分散されていて、分散粒子の平均粒径が
０．５〜４μｍで、分散粒子の５０重量％が２μｍ以下
の粒径を有する乳化分散物を生成させる水分散型感熱接
着剤の製造方法を提供する。SUMMARY OF THE INVENTION In order to solve the above problems, the present invention provides at least one of a wax and an adhesive resin and an ethylene-vinyl acetate copolymer (hereinafter,
Sometimes called "EVA". A) and a softening state in water and stirred in the presence of a protective colloid to obtain a pre-emulsified dispersion, which is stirred by a high-pressure homogenizer at a pressure of 1300 kg / cm 2 or more to obtain one of the wax and the adhesive resin. Particles consisting of a molten mixture of at least one and ethylene-vinyl acetate copolymer are emulsified and dispersed in water by a protective colloid, and the average particle diameter of the dispersed particles is 0.5 to 4 μm, and 50% by weight of the dispersed particles is Provided is a method for producing a water-dispersible heat-sensitive adhesive, which produces an emulsified dispersion having a particle size of 2 μm or less.
【００１０】前記ワックスおよび粘着樹脂のうちの少な
くとも１つとエチレン−酢酸ビニル共重合体はホットメ
ルト接着剤組成物であってもよい。この発明では、ベー
スポリマーとしてＥＶＡを使用する。これは感熱接着性
と接着強度を発現させるためである。ＥＶＡは、酢酸ビ
ニル単位１０〜５５重量％およびエチレン単位４５〜９
０重量％が好ましい。ただし、酢酸ビニル単位とエチレ
ン単位の合計は１００重量％である。酢酸ビニル単位の
比率が上記範囲を下回ると接着性が不充分になるおそれ
があり、上回ると耐ブロッキング性が悪くなるおそれが
ある。また、ＭＩ（メルトフローインデックス）または
ＭＦＲ（メルトフローレシオ）が０．５〜３，０００の
ＥＶＡが好ましい。この範囲を下回ると熱活性時の濡れ
が悪くなったり、溶融乳化時に粘度が高すぎて乳化しに
くいおそれがあり、上回ると凝集力が不足して耐熱性等
が悪くなるおそれがある。At least one of the wax and the tackifying resin and the ethylene-vinyl acetate copolymer may be a hot melt adhesive composition. In the present invention, EVA is used as the base polymer. This is to develop heat-sensitive adhesiveness and adhesive strength. EVA is 10 to 55% by weight of vinyl acetate units and 45 to 9 ethylene units.
0% by weight is preferred. However, the total of vinyl acetate units and ethylene units is 100% by weight. If the ratio of vinyl acetate units is less than the above range, the adhesiveness may be insufficient, and if it exceeds the above range, the blocking resistance may be deteriorated. EVA having an MI (melt flow index) or MFR (melt flow ratio) of 0.5 to 3,000 is preferable. If it is less than this range, wetting may be poor during thermal activation, or the viscosity may be too high during melt emulsification, making it difficult to emulsify. If it exceeds this range, the cohesive force may be insufficient and heat resistance and the like may be deteriorated.
【００１１】この発明では、粘着樹脂とワックスのうち
のいずれか一方または両方が使用される。粘着樹脂は、
特に限定しないが、ＪＩＳ Ｋ５９０３に準拠して測定
された軟化点が５０〜１６０℃の、ロジン、テルペン系
樹脂、Ｃ5 および／またはＣ9 系石油樹脂およびその水
素添加物、クマロン・インデン樹脂等が好ましい。粘着
樹脂の軟化点が上記範囲を下回ると耐ブロッキング性が
悪くなるおそれがあり、上回るとヒートシール性が悪く
なるおそれがある。In the present invention, either or both of the adhesive resin and the wax are used. The adhesive resin is
Although not particularly limited, rosin, terpene resin, C 5 and / or C 9 petroleum resin and hydrogenated products thereof, coumarone indene resin, etc., having a softening point of 50 to 160 ° C. measured according to JIS K5903 Is preferred. If the softening point of the pressure-sensitive adhesive resin is below the above range, the blocking resistance may be deteriorated, and if it exceeds the above range, the heat sealability may be deteriorated.
【００１２】ワックスは、特に限定しないが、融点５０
〜１２０℃の、パラフィンワックス、マイクロクリスタ
リンワックス、カルナウバロウ、フィッシャートロプシ
ュワックス、ポリエチレンワックス、および、それらの
酸化ワックス等が好ましい。ワックスの融点が上記範囲
を下回ると耐ブロッキング性と耐熱性が劣るおそれがあ
り、上回るとヒートシール性が悪くなるおそれがある。The wax is not particularly limited, but has a melting point of 50.
Paraffin wax, microcrystalline wax, carnauba wax, Fischer-Tropsch wax, polyethylene wax, and waxes thereof having a temperature of up to 120 ° C. are preferable. If the melting point of the wax is below the above range, the blocking resistance and heat resistance may be poor, and if it is above the melting range, the heat sealability may be poor.
【００１３】ＥＶＡと、粘着樹脂および／またはワック
スとの比率は、ＥＶＡの１００重量部に対して粘着樹脂
２０〜２００重量部および／またはワックス２０〜２０
０重量部の割合が好ましい。粘着樹脂の割合が上記範囲
を下回ると接着性が発現しにくいおそれがあり、上回る
と耐ブロッキング性が悪くなるおそれがある。ワックス
の割合が上記範囲を下回るとヒートシール後の強度発現
速度が遅くなるおそれがあり、上回ると凝集力が不足す
るおそれがある。The ratio of EVA to the adhesive resin and / or wax is 20 to 200 parts by weight of the adhesive resin and / or 20 to 20 parts of wax with respect to 100 parts by weight of EVA.
A proportion of 0 parts by weight is preferred. If the proportion of the adhesive resin is less than the above range, the adhesiveness may be difficult to develop, and if it exceeds the above range, the blocking resistance may be deteriorated. If the proportion of the wax is less than the above range, the rate of strength development after heat sealing may be slow, and if it is more than the above range, the cohesive force may be insufficient.
【００１４】ＥＶＡと、粘着樹脂および／またはワック
スとの溶融混合物は、分散媒に溶解せず粒子（すなわち
固体粒子または液滴）となって分散媒中に分散されてい
る。溶融混合物粒子は、平均粒径０．５〜４μｍかつ５
０重量％の粒子が２μｍ以下の粒径を有する必要があ
り、平均粒径１〜２μｍかつ５０重量％の粒子が１．５
μｍ以下の粒径を有することが好ましい。溶融混合物粒
子の平均粒径が上記範囲を下回ると粘度が高くなりすぎ
るという問題があり、上回ると貯蔵安定性が著しく低下
するという問題がある。溶融混合物粒子の５０重量％が
上記範囲を上回ると貯蔵安定性が著しく低下する。すな
わち、平均粒径および粒径分布は小さいほど好ましい。The melted mixture of EVA and the adhesive resin and / or wax is not dissolved in the dispersion medium but becomes particles (that is, solid particles or droplets) and is dispersed in the dispersion medium. The molten mixture particles have an average particle size of 0.5 to 4 μm and 5
It is necessary that 0% by weight of the particles have a particle size of 2 μm or less, and an average particle size of 1 to 2 μm and 50% by weight of the particles are 1.5
It is preferable to have a particle size of μm or less. If the average particle diameter of the melted mixture particles is below the above range, there is a problem that the viscosity becomes too high, and if it exceeds the above range, there is a problem that the storage stability is significantly reduced. If 50% by weight of the particles of the molten mixture exceeds the above range, the storage stability will be significantly reduced. That is, the smaller the average particle size and the particle size distribution, the more preferable.
【００１５】上記溶融混合物の分散媒は水である。溶融
混合物と水との比率は、溶融混合物の比率があまり高い
と水分散化（乳化）が困難になり、貯蔵安定性が低下
し、また、その比率が低すぎると接着剤塗工時の乾燥性
が遅くなるという理由から、水１００重量部に対して溶
融混合物２５〜１５０重量部の割合が好ましく、溶融混
合物５０〜１００重量部の割合がより好ましい。The dispersion medium of the molten mixture is water. Regarding the ratio of the melt mixture and water, if the ratio of the melt mixture is too high, water dispersion (emulsification) becomes difficult and the storage stability decreases, and if the ratio is too low, drying during adhesive coating The ratio of the molten mixture is preferably from 25 to 150 parts by weight, more preferably from 50 to 100 parts by weight, based on 100 parts by weight of water, because the property becomes slow.
【００１６】溶融混合物の水への分散状態を長期にわた
って安定に維持するために保護コロイドが使用される。
保護コロイドの使用量は、少なすぎる水分散化（乳化）
が困難になり、貯蔵安定性が低下し、また、多すぎると
接着剤の接着性が低下するという理由から、溶融混合物
１００重量部に対して０．５〜２０重量部の割合が好ま
しく、１〜１０重量部の割合がより好ましい。Protective colloids are used to maintain a stable state of dispersion of the molten mixture in water over a long period of time.
The amount of protective colloid used is too small. Water dispersion (emulsification)
Therefore, the ratio of 0.5 to 20 parts by weight is preferable with respect to 100 parts by weight of the molten mixture, because the storage stability becomes poor, and the storage stability decreases, and the adhesiveness of the adhesive decreases if the amount is too large. The ratio of 10 to 10 parts by weight is more preferable.
【００１７】保護コロイドは、構造中に親水性の部分と
疎水性の部分を適度なバランスで持ち、油、樹脂等の疎
水性の粒子表面に吸着して粒子同士の凝集沈殿を防ぐ機
能を持つ水溶性ポリマーである。保護コロイドの具体例
は、ポリビニルアルコール（ＰＶＡ）、カゼイン、ゼラ
チン、にかわ、大豆タンパク、卵白アルブミン、ホエー
タンパク（ＷＰＣ）、プラズマタンパクであり、その１
種以上が使用される。熱可塑性樹脂の乳化時は液温を上
げなければならず、６０〜７０℃で熱凝固するような蛋
白質類（アルブミン、グロブリン系統）は使用困難であ
るという理由から、ポリビニルアルコール、カゼイン、
ゼラチン、にかわから選ばれる少なくとも１種の保護コ
ロイドが好ましい。エマルションの貯蔵安定性のために
乳化剤を使用せず、保護コロイドを使用すると、保護コ
ロイドは乳化剤よりも高分子量であるため水に溶出しに
くい。このため、食品用途にも利用可能である。The protective colloid has a hydrophilic portion and a hydrophobic portion in the structure in a proper balance, and has a function of adsorbing on the surface of hydrophobic particles such as oil and resin to prevent aggregation and precipitation of particles. It is a water-soluble polymer. Specific examples of the protective colloid are polyvinyl alcohol (PVA), casein, gelatin, glue, soybean protein, ovalbumin, whey protein (WPC) and plasma protein.
More than one seed is used. Since the liquid temperature must be raised during the emulsification of the thermoplastic resin, and proteins (albumin, globulin series) that are thermally coagulated at 60 to 70 ° C. are difficult to use, polyvinyl alcohol, casein,
At least one protective colloid selected from gelatin and glue is preferable. When a protective colloid is used without using an emulsifier for storage stability of the emulsion, the protective colloid has a higher molecular weight than that of the emulsifier and is less likely to be eluted in water. Therefore, it can be used for food.
【００１８】溶融混合物の分散安定性を高めるために、
必要に応じて、ノニオン系、アニオン系のような各種界
面活性剤の少なくとも１種を乳化剤として使用すること
ができる。この発明では、その他、必要に応じてコロイ
ダルシリカ、炭酸カルシウム等の充填剤；消泡剤；濡れ
剤（界面活性剤）；防腐剤；増粘剤のような通常の感熱
接着剤に使用される添加剤が配合されてもよい。In order to improve the dispersion stability of the molten mixture,
If necessary, at least one kind of various surfactants such as nonionic and anionic surfactants can be used as an emulsifier. In the present invention, other fillers such as colloidal silica, calcium carbonate, etc., if necessary, defoaming agents, wetting agents (surfactants), preservatives, thickeners, and other ordinary heat-sensitive adhesives are used. Additives may be added.
【００１９】上述した、ＥＶＡ、粘着樹脂および／また
はワックス、保護コロイド、水、および、必要ならば上
記任意成分を樹脂の軟化点または融点以上の温度（樹脂
の軟化点または融点が水の融点よりも高い場合は溶剤に
溶解して）で攪拌してプレ乳化物（予備乳化分散物）を
作る。プレ乳化物を作るには、ホモミキサーのような攪
拌装置が使用される。このような通常の攪拌でも一時的
に均一乳化することは可能である。得られたプレ乳化物
を処理圧力（液圧）１３００kg／cm2 以上の高圧ホモジ
ナイザーで処理することにより、水分散型感熱接着剤が
得られる。プレ乳化物の液圧が１３００kg／cm2 未満だ
と平均粒径または粒径分布が大きくなり、貯蔵安定性が
低下すると言う問題がある。高圧ホモジナイザーで処理
するときのプレ乳化物の液圧が高すぎると処理速度が遅
くなり、生産性が低下するおそれがあるので、該液圧は
４０００kg／cm2 以下が好ましい。The above-mentioned EVA, adhesive resin and / or wax, protective colloid, water and, if necessary, the above optional components are added to the resin at a temperature above the softening point or melting point (where the softening point or melting point of the resin is higher than the melting point of water). If it is too high, dissolve in a solvent) and stir with to make a pre-emulsion (pre-emulsion dispersion). To make the pre-emulsion, a stirring device such as a homomixer is used. Even with such normal stirring, it is possible to temporarily uniformly emulsify. A water-dispersed heat-sensitive adhesive is obtained by treating the obtained pre-emulsion with a high-pressure homogenizer having a treatment pressure (liquid pressure) of 1300 kg / cm 2 or more. If the liquid pressure of the pre-emulsion is less than 1300 kg / cm 2 , there is a problem that the average particle size or particle size distribution becomes large and the storage stability decreases. If the liquid pressure of the pre-emulsion during the treatment with the high-pressure homogenizer is too high, the processing speed may be slowed down and the productivity may be lowered. Therefore, the liquid pressure is preferably 4000 kg / cm 2 or less.
【００２０】ここで使用される高圧ホモジナイザーは、
プレ乳化物を通すための流路を２つの細い流路に分け、
分けられた流路を９０度横向きに曲げて合流する形状に
してあり、プレ乳化物をこれらの流路に通すうちに流路
壁に衝突させ、加速させた流体同士を超高速で衝突させ
ることにより微粒化、乳化、均一分散作用を引き起こす
装置であり、上述した他の方法に用いられる装置よりも
細かく均一な乳化物が得られる。従来の方法で使用され
ていた高圧ホモジナイザーは、隙間からディスクに液を
ぶつけることにより乳化分散を行っており処理圧力を１
３００kg／cm2以上にすることはできなかった。The high pressure homogenizer used here is
The flow path for passing the pre-emulsion is divided into two narrow flow paths,
The divided flow paths are bent sideways by 90 degrees so as to join, and the pre-emulsion is made to collide with the flow path wall while passing through these flow paths, and the accelerated fluids are made to collide at ultra-high speed. Is a device that causes atomization, emulsification, and uniform dispersion action, and a finer and more uniform emulsion can be obtained than the devices used in the other methods described above. The high-pressure homogenizer used in the conventional method carries out emulsification and dispersion by hitting the liquid against the disc through the gap, and the processing pressure is 1
It could not exceed 300 kg / cm 2 .
【００２１】この発明の方法によれば、高圧ホモジナイ
ザーで処理するプレ乳化物として、従来法で得られた貯
蔵安定性の悪い乳化物を使用することにより、貯蔵安定
性の良好な水分散型感熱接着剤とすることができる。こ
の発明の製造方法により得られた接着剤は、支持体に塗
布され、乾燥される。支持体は、フィルム、シート、テ
ープ、紙、金属箔などのシート状物や成形物などであ
り、その材質は、ポリ塩化ビニル（ＰＶＣ）、紙、ポリ
スチレン、ＡＢＳ樹脂（アクリロニトリル−ブタジエン
−スチレン共重合体）、ポリエチレン、ポリプロピレ
ン、アクリロニトリル−スチレン樹脂、ポリエステル
（ＰＥＴ）等である。塗布は、カーテンコーター、ロー
ルコーター、刷毛、スプレーガンのように通常の水分散
型感熱接着剤を塗布するための手段を用いて支持体の全
面にまたは部分的に行われる。接着剤塗膜の厚みは、乾
燥した状態で、０．５〜５０μｍが好ましく、３〜１０
μｍがより好ましい。塗膜厚みがこの範囲を下回ると充
分な接着強度が得られないおそれがあり、上回ると乾燥
速度が遅くなるおそれがある。乾燥は、たとえば、４０
〜１２０℃の温度で行われる。According to the method of the present invention, an emulsion having poor storage stability obtained by the conventional method is used as the pre-emulsion treated with the high-pressure homogenizer, whereby a water-dispersible heat-sensitive emulsion having good storage stability is obtained. It can be an adhesive. The adhesive obtained by the production method of the present invention is applied to a support and dried. The support is a sheet-like material such as a film, a sheet, a tape, a paper or a metal foil, or a molded product, and the material thereof is polyvinyl chloride (PVC), paper, polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer). Polymer), polyethylene, polypropylene, acrylonitrile-styrene resin, polyester (PET) and the like. The application is carried out on the whole surface or a part of the support using a means for applying a conventional water-dispersible heat-sensitive adhesive such as a curtain coater, a roll coater, a brush or a spray gun. The thickness of the adhesive coating film in the dried state is preferably 0.5 to 50 μm, and 3 to 10
μm is more preferable. If the coating film thickness is below this range, sufficient adhesive strength may not be obtained, and if it is above this range, the drying speed may be slow. Drying, for example, 40
It is carried out at a temperature of ~ 120 ° C.
【００２２】この発明の方法により得られた接着剤で被
着材に接着するときには接着剤表面を被着材に接触させ
て加熱溶融し、冷却固化により接着する。加熱溶融は、
ＥＶＡ、粘着樹脂やワックスの種類によるが通常５０〜
２００℃の温度で０．１〜５秒間程度である。被着材の
接着面にもその感熱接着剤を塗布して乾燥しておいても
よい。加熱溶融の際に０．１〜５．０kg／cm2 程度の圧
力をかけてもよい。When adhering to an adherend with the adhesive obtained by the method of the present invention, the surface of the adhesive is brought into contact with the adherend to be heated and melted, and then cooled and solidified. Heating and melting
Normally 50 to 50 depending on EVA, adhesive resin and wax type
The temperature is 200 ° C. and the time is about 0.1 to 5 seconds. The heat-sensitive adhesive may be applied to the adhesive surface of the adherend and dried. A pressure of about 0.1 to 5.0 kg / cm 2 may be applied during heating and melting.
【００２３】この発明の方法により得られた接着剤をシ
ート状の支持体に塗布して乾燥させて感熱ラベルが得ら
れる。この感熱ラベルは、耐ブロッキング性が良いので
剥離シートを接着剤面に被せておく必要がなく、しか
も、接着性が良好である。このため、インモールドラベ
ルなどに使用されうる。この発明の方法により得られた
接着剤は、上記感熱ラベル、ブリスターパック、ヒート
シール剤などの用途に使用される。The adhesive obtained by the method of the present invention is applied to a sheet-shaped support and dried to obtain a heat-sensitive label. Since this heat-sensitive label has good blocking resistance, it is not necessary to cover the release sheet with the release sheet, and the adhesive property is good. Therefore, it can be used as an in-mold label or the like. The adhesive obtained by the method of the present invention is used for the above-mentioned heat sensitive label, blister pack, heat sealant and the like.
【００２４】[0024]
【作用】この発明によれば、ＥＶＡと粘着樹脂および／
またはワックスとの溶融混合物を、保護コロイドを用い
て高圧ホモジナイザーで強制的に水媒体中に乳化分散す
ることにより、分散粒子の平均粒径０．５〜４μｍかつ
分散粒子の５０重量％が２μｍ以下の粒径を有する乳化
分散物を得る。このため、得られた乳化分散物は、低粘
度でもクリーミングを起こさず、貯蔵安定性が良好であ
る。しかも、乳化する樹脂の種類に限定がなく、広範囲
の樹脂が使用できる。ＥＶＡと、粘着樹脂および／また
はワックスとを溶融混合物を水中に乳化分散するので、
各成分の単独エマルションをブレンドした場合（各成分
の粒子が個々に水中に分散する。）に比べて優れたヒー
トシール性が得られる。According to the present invention, EVA and adhesive resin and / or
Alternatively, a molten mixture with wax is forcibly emulsified and dispersed in an aqueous medium by a high pressure homogenizer using a protective colloid, whereby the average particle diameter of the dispersed particles is 0.5 to 4 μm and 50% by weight of the dispersed particles is 2 μm or less. An emulsified dispersion having a particle size of is obtained. Therefore, the obtained emulsified dispersion does not cause creaming even at low viscosity and has good storage stability. Moreover, the type of resin to be emulsified is not limited, and a wide range of resins can be used. Since the melt mixture of EVA and the adhesive resin and / or wax is emulsified and dispersed in water,
Excellent heat-sealing properties can be obtained as compared with the case where a single emulsion of each component is blended (particles of each component are individually dispersed in water).
【００２５】この発明によれば、溶融混合のための比較
的短時間の加熱だけですむため、加熱安定性が悪く、ホ
ットメルト原料として使用困難とされていた、生ロジン
のような材料も分解や変質を起こすことなく水分散型感
熱接着剤に使用できる。この発明によれば、高粘度であ
るため熱溶融によるアプリケーションが困難であったホ
ットメルトも水系化することにより低粘度流体となるの
で、容易に塗付できる。According to the present invention, since heating only for a relatively short time for melt mixing is required, heating stability is poor, and materials such as raw rosin, which have been considered difficult to use as a hot melt raw material, are decomposed. It can be used in water-dispersed heat-sensitive adhesives without causing deterioration. According to the present invention, hot melt, which has a high viscosity and is difficult to be applied by heat melting, becomes a low-viscosity fluid by making it water-based, and therefore can be easily applied.
【００２６】この発明の方法によれば、保護コロイドと
してゼラチンを使用すれば、平均粒径１〜１０μｍ程度
の微細な樹脂のマイクロカプセルを作ることができる。
水分散物を遠心分離、エバポレーター、限外ろ過去等の
方法で濃縮、分離した後、乾燥させることによりマイク
ロカプセルが得られる。According to the method of the present invention, if gelatin is used as the protective colloid, fine resin microcapsules having an average particle size of about 1 to 10 μm can be prepared.
Microcapsules can be obtained by concentrating and separating the aqueous dispersion by centrifugation, an evaporator, an ultrafiltration method, etc., and then drying.
【００２７】[0027]
【実施例】以下に、この発明の実施例と、この発明の範
囲を外れた比較例とを示すが、この発明は下記実施例に
限定されない。以下では、「部」は「重量部」、「％」
は「重量％」である。 （製造例１）三井・デュポンポリケミカル（株）製のＥ
ＶＡ（商品名エバフレックス２５０、酢酸ビニル含有量
２８％、ＭＩ＝１５）１５部、住友化学（株）製のＥＶ
Ａ（商品名スミテートＫＣ−１０、酢酸ビニル含有量２
８％、ＭＩ＝１５０）１５部、荒川化学工業（株）製の
ロジンエステル（商品名スーパーエステルＡ−１２５、
軟化点（Ｓ．Ｐ．）１２５℃）３０部、日本精蝋（株）
製のパラフィンワックス（パラフィンワックス１３５、
融点５８℃）４０部を溶融混合して、粘度２０００ｃｐ
ｓ（１８０℃）、軟化点（Ｓ．Ｐ．７５℃）のホットメ
ルト接着剤組成物を得た。EXAMPLES Examples of the present invention and comparative examples outside the scope of the present invention will be shown below, but the present invention is not limited to the following examples. In the following, "part" means "part by weight", "%"
Is "% by weight". (Production Example 1) E manufactured by Mitsui DuPont Polychemical Co., Ltd.
15 parts of VA (trade name Evaflex 250, vinyl acetate content 28%, MI = 15), EV manufactured by Sumitomo Chemical Co., Ltd.
A (trade name Sumitate KC-10, vinyl acetate content 2
8%, MI = 150) 15 parts, rosin ester (trade name Super Ester A-125, manufactured by Arakawa Chemical Industry Co., Ltd.,
Softening point (SP) 125 ° C) 30 parts, Nippon Seiro Co., Ltd.
Made paraffin wax (paraffin wax 135,
Melting and mixing 40 parts of melting point 58 ° C), viscosity 2000 cp
A hot melt adhesive composition having a s (180 ° C.) and a softening point (SP 75 ° C.) was obtained.
【００２８】（製造例２）三井・デュポンポリケミカル
（株）製のＥＶＡ（商品名エバフレックス２２０、酢酸
ビニル含有量２８％、ＭＩ＝１５０）５０部、荒川化学
工業（株）製のロジンエステル（商品名スーパーエステ
ルＡ−１２５、軟化点（Ｓ．Ｐ．）１２５℃）５０部を
溶融混合して、粘度２０００ｃｐｓ（１８０℃）、軟化
点（Ｓ．Ｐ．７５℃）のホットメルト接着剤組成物を得
た。(Production Example 2) 50 parts EVA (trade name: Evaflex 220, vinyl acetate content 28%, MI = 150) manufactured by Mitsui DuPont Polychemical Co., Ltd., rosin ester manufactured by Arakawa Chemical Industry Co., Ltd. (Trade name: Super Ester A-125, softening point (SP) 125 ° C.) 50 parts by melt mixing, hot melt adhesive having viscosity 2000 cps (180 ° C.) and softening point (SP 75 ° C.) A composition was obtained.
【００２９】（製造例３）三井・デュポンポリケミカル
（株）製のＥＶＡ（商品名エバフレックス２２０、酢酸
ビニル含有量２８％、ＭＩ＝１５０）５０部、日本精蝋
（株）製のパラフィンワックス（パラフィンワックス１
３５、融点５８℃）５０部を溶融混合して、粘度２００
０ｃｐｓ（１８０℃）、軟化点（Ｓ．Ｐ．７５℃）のホ
ットメルト接着剤組成物を得た。(Production Example 3) 50 parts EVA (trade name Evaflex 220, vinyl acetate content 28%, MI = 150) manufactured by Mitsui DuPont Polychemical Co., Ltd., paraffin wax manufactured by Nippon Seiro Co., Ltd. (Paraffin wax 1
35, melting point 58 ° C.) 50 parts by melt mixing to give a viscosity of 200
A hot melt adhesive composition having 0 cps (180 ° C.) and a softening point (SP 75 ° C.) was obtained.
【００３０】（実施例１〜２）表１に示す配合比で、水
にあらかじめ保護コロイド（ＰＶＡ−２１７Ｅ、クラレ
（株）製の部分ケン化ポバール、ケン化度８８）を溶解
させ、製造例１で得られたホットメルト接着剤組成物を
添加した。これを８０〜９０℃（樹脂の軟化点以上）ま
で昇温し、常圧ホモミキサー（特殊機化工業（株）製
Ｔ．Ｋホモミキサー）で攪拌し、プレ乳化物を得た。(Examples 1 and 2) Protective colloids (PVA-217E, partially saponified poval manufactured by Kuraray Co., Ltd., saponification degree 88) were dissolved in water at a compounding ratio shown in Table 1 to prepare a production example. The hot melt adhesive composition obtained in 1 was added. This was heated to 80 to 90 ° C. (above the softening point of the resin) and stirred with a normal pressure homomixer (TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain a pre-emulsion.
【００３１】得られたプレ乳化物を高圧ホモジナイザー
（ナノマイザー（株）製ＬＡ−３１型）で処理圧力１，
３００kg／cm2 で処理し、水分散物を得た。 （実施例３）実施例１において、保護コロイドとして酸
カゼイン（ポーランド産）を使用し、これを溶解するた
めにＮＨ4 ＯＨ水溶液を用いたこと以外は実施例１と同
様にして水分散物を得た。The pre-emulsion thus obtained was treated with a high-pressure homogenizer (LA-31 type manufactured by Nanomizer Co., Ltd.) at a pressure of 1,
Treatment with 300 kg / cm 2 gave an aqueous dispersion. (Example 3) An aqueous dispersion was prepared in the same manner as in Example 1 except that acid casein (produced in Poland) was used as the protective colloid and an aqueous NH 4 OH solution was used to dissolve it. Obtained.
【００３２】（実施例４）表１に示す配合比で、水にあ
らかじめ保護コロイド（ＰＶＡ−２１７Ｅ、クラレ
（株）製の部分ケン化ポバール、ケン化度８８）を溶解
させ、製造例２で得られたホットメルト接着剤組成物を
添加した。これを８０〜９０℃（樹脂の軟化点以上）ま
で昇温し、常圧ホモミキサー（特殊機化工業（株）製
Ｔ．Ｋホモミキサー）で攪拌し、プレ乳化物を得た。Example 4 In Production Example 2, a protective colloid (PVA-217E, partially saponified poval manufactured by Kuraray Co., Ltd., saponification degree 88) was dissolved in water at the compounding ratio shown in Table 1 beforehand. The obtained hot melt adhesive composition was added. This was heated to 80 to 90 ° C. (above the softening point of the resin) and stirred with a normal pressure homomixer (TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain a pre-emulsion.
【００３３】得られたプレ乳化物を高圧ホモジナイザー
（ナノマイザー（株）製ＬＡ−３１型）で処理圧力１，
３００kg／cm2 で処理し、水分散物を得た。 （実施例５）表１に示す配合比で、水にあらかじめ保護
コロイド（ＰＶＡ−２１７Ｅ、クラレ（株）製の部分ケ
ン化ポバール、ケン化度８８）を溶解させ、製造例３で
得られたホットメルト接着剤組成物を添加した。これを
８０〜９０℃（樹脂の軟化点以上）まで昇温し、常圧ホ
モミキサー（特殊機化工業（株）製Ｔ．Ｋホモミキサ
ー）で攪拌し、プレ乳化物を得た。The obtained pre-emulsion is treated with a high-pressure homogenizer (LA-31 type manufactured by Nanomizer Co., Ltd.) at a pressure of 1,
Treatment with 300 kg / cm 2 gave an aqueous dispersion. (Example 5) A protective colloid (PVA-217E, partially saponified poval manufactured by Kuraray Co., Ltd., saponification degree 88) was dissolved in water in advance at the compounding ratio shown in Table 1 to obtain in Production Example 3. The hot melt adhesive composition was added. This was heated to 80 to 90 ° C. (above the softening point of the resin) and stirred with a normal pressure homomixer (TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain a pre-emulsion.
【００３４】得られたプレ乳化物を高圧ホモジナイザー
（ナノマイザー（株）製ＬＡ−３１型）で処理圧力１，
３００kg／cm2 で処理し、水分散物を得た。 （比較例１）実施例１において、高圧ホモジナイザーで
の処理を省略し、プレ乳化物である水分散物を得た。The obtained pre-emulsion is treated with a high-pressure homogenizer (LA-31 type manufactured by Nanomizer Co., Ltd.) at a pressure of 1,
Treatment with 300 kg / cm 2 gave an aqueous dispersion. (Comparative Example 1) In Example 1, the treatment with the high pressure homogenizer was omitted, and an aqueous dispersion which was a pre-emulsion was obtained.
【００３５】（比較例２）実施例１において、プレ乳化
物を従来の高圧ホモジナイザー（ＧＡＵＬＩＮ社製の１
５Ｍ−８ＴＡ）で８５０kg／cm2 の処理圧力で処理した
こと以外は実施例１と同様にして水分散物を得た。 （比較例３）実施例１で使用した熱可塑性樹脂を水分散
せず、熱溶融させてヒートシール強度を測定した。(Comparative Example 2) In Example 1, the pre-emulsion was mixed with a conventional high-pressure homogenizer (1 manufactured by GAULIN).
An aqueous dispersion was obtained in the same manner as in Example 1 except that the treatment was performed with 5M-8TA) at a treatment pressure of 850 kg / cm 2 . (Comparative Example 3) The thermoplastic resin used in Example 1 was heat-melted without being dispersed in water and the heat-sealing strength was measured.
【００３６】水分散物の分散粒子の平均粒径と累積粒子
５０重量％時の粒径を動的光散乱法により測定した。水
分散物の貯蔵安定性は、２３℃で３か月放置した後の状
態を観察し、○：分離なし、△：一部分離した、×：凝
集したで評価した。The average particle size of the dispersed particles of the aqueous dispersion and the particle size of the accumulated particles at the time of 50% by weight of the dispersed particles were measured by the dynamic light scattering method. The storage stability of the aqueous dispersion was evaluated by observing the state after standing at 23 ° C. for 3 months, ◯: no separation, Δ: partially separated, ×: aggregated.
【００３７】水分散物のヒートシール強度を次の方法で
調べた。アート紙にコーティングロッドＮｏ．９（２
０．６μｍφ、ウェット）で塗布し、５０℃で３分間乾
燥した。塗布面と硬質ポリ塩化ビニルフィルムまたはＰ
ＥＴと合わせ、１２０℃にて２kg／cm2 の圧力で１秒間
日理商事（株）製ヒートシーラーでヒートシールした。
ヒートシール物について島津製作所製万能引張り試験機
（オートグラフＡＧ−２０００Ｅ）にてＴ剥離強度（ク
ロスヘッドスピード３００mm／分）を求め、これをヒー
トシール強度とした。ただし、貯蔵安定性が×または△
の水分散物については測定しなかった。The heat seal strength of the water dispersion was investigated by the following method. Coating rod No. 9 (2
0.6 μmφ, wet), and dried at 50 ° C. for 3 minutes. Coating surface and hard polyvinyl chloride film or P
Together with ET, they were heat-sealed at 120 ° C. for 2 seconds at a pressure of 2 kg / cm 2 with a heat sealer manufactured by NRI Corporation.
For the heat-sealed product, T peel strength (cross head speed 300 mm / min) was determined with a universal tensile tester manufactured by Shimadzu Corporation (Autograph AG-2000E), and this was taken as the heat seal strength. However, storage stability is X or △
No measurement was made on the water dispersion of.
【００３８】結果を表１に示した。The results are shown in Table 1.
【００３９】[0039]
【表１】 [Table 1]
【００４０】表１にみるように、実施例１〜５の水分散
物は、貯蔵安定性が良好で、ヒートシール強度は、比較
例３のものと同等であった。As shown in Table 1, the aqueous dispersions of Examples 1 to 5 had good storage stability and the heat seal strength was the same as that of Comparative Example 3.
【００４１】[0041]
【発明の効果】この発明によれば、貯蔵安定性に優れ、
広範囲の熱可塑性樹脂を使用できる水分散型感熱接着剤
が提供される。ＥＶＡと粘着樹脂および／またはワック
スとの溶融混合物を使用するので接着剤の耐ブロッキン
グ性およびヒートシール性が向上する。According to the present invention, excellent storage stability,
A water-dispersed heat-sensitive adhesive that can use a wide range of thermoplastic resins is provided. Since the molten mixture of EVA and the tackifying resin and / or wax is used, the blocking resistance and heat sealability of the adhesive are improved.
Claims (2)
とも１つとエチレン−酢酸ビニル共重合体とを水中で軟
化状態にして保護コロイドの存在下に攪拌して得られた
予備乳化分散物を高圧ホモジナイザーにより１３００kg
／cm2 以上の圧力で攪拌することにより、前記ワックス
および粘着樹脂のうちの少なくとも１つとエチレン−酢
酸ビニル共重合体との溶融混合物からなる粒子が保護コ
ロイドにより水中に乳化分散されていて、分散粒子の平
均粒径が０．５〜４μｍで、分散粒子の５０重量％が２
μｍ以下の粒径を有する乳化分散物を生成させる水分散
型感熱接着剤の製造方法。1. A pre-emulsion dispersion obtained by stirring at least one of a wax and an adhesive resin and an ethylene-vinyl acetate copolymer in water in a softened state in water and stirring in the presence of a protective colloid using a high pressure homogenizer. 1300kg
By stirring at a pressure of at least 1 cm 2 / cm 2, particles comprising a molten mixture of at least one of the wax and the adhesive resin and an ethylene-vinyl acetate copolymer are emulsified and dispersed in water by a protective colloid, and dispersed. The average particle size of the particles is 0.5 to 4 μm, and 50% by weight of the dispersed particles is 2
A method for producing a water-dispersible heat-sensitive adhesive, which produces an emulsified dispersion having a particle size of not more than μm.
とも１つとエチレン−酢酸ビニル共重合体がホットメル
ト接着剤組成物である請求項１記載の方法。2. The method of claim 1, wherein at least one of the wax and the tackifying resin and the ethylene-vinyl acetate copolymer are a hot melt adhesive composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35103493A JP3298599B2 (en) | 1993-12-30 | 1993-12-30 | Method for producing water-dispersed heat-sensitive adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35103493A JP3298599B2 (en) | 1993-12-30 | 1993-12-30 | Method for producing water-dispersed heat-sensitive adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07196997A true JPH07196997A (en) | 1995-08-01 |
| JP3298599B2 JP3298599B2 (en) | 2002-07-02 |
Family
ID=18414599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35103493A Expired - Fee Related JP3298599B2 (en) | 1993-12-30 | 1993-12-30 | Method for producing water-dispersed heat-sensitive adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3298599B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005097353A (en) * | 2003-09-22 | 2005-04-14 | Dainippon Ink & Chem Inc | Delayed-tack pressure-sensitive adhesive composition and pressure-sensitive adhesive label |
| JP2011516621A (en) * | 2008-02-26 | 2011-05-26 | リクアメルト コーポレーション | Polymer composition capable of being pumped at room temperature activated by energy application and apparatus for activating and applying the composition |
| JP2012255084A (en) * | 2011-06-09 | 2012-12-27 | Toyo Adl Corp | Thermally peelable aqueous adhesive |
| JP2013091792A (en) * | 2005-07-07 | 2013-05-16 | Dow Global Technologies Llc | Aqueous dispersions |
| JP2016108364A (en) * | 2014-12-02 | 2016-06-20 | 住友精化株式会社 | ANIONIC AQUEOUS DISPERSION OF α-OLEFIN-VINYL ACETATE-BASED ELASTOMER PARTICLES, METHOD FOR PRODUCING THE SAME, MOLDED PRODUCT AND RESORCIN-FORMALIN-LATEX ADHESIVE AGENT |
| JP2018150444A (en) * | 2017-03-13 | 2018-09-27 | 東洋インキＳｃホールディングス株式会社 | Heat-melting composition and use of the same |
| CN112795336A (en) * | 2020-12-29 | 2021-05-14 | 德庆威斯达化工有限公司 | Water-based EVA hot melt adhesive, and preparation method and application thereof |
-
1993
- 1993-12-30 JP JP35103493A patent/JP3298599B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005097353A (en) * | 2003-09-22 | 2005-04-14 | Dainippon Ink & Chem Inc | Delayed-tack pressure-sensitive adhesive composition and pressure-sensitive adhesive label |
| JP2013091792A (en) * | 2005-07-07 | 2013-05-16 | Dow Global Technologies Llc | Aqueous dispersions |
| EP1899432B1 (en) | 2005-07-07 | 2015-06-17 | Dow Global Technologies LLC | Aqueous dispersions |
| JP2011516621A (en) * | 2008-02-26 | 2011-05-26 | リクアメルト コーポレーション | Polymer composition capable of being pumped at room temperature activated by energy application and apparatus for activating and applying the composition |
| JP2012255084A (en) * | 2011-06-09 | 2012-12-27 | Toyo Adl Corp | Thermally peelable aqueous adhesive |
| JP2016108364A (en) * | 2014-12-02 | 2016-06-20 | 住友精化株式会社 | ANIONIC AQUEOUS DISPERSION OF α-OLEFIN-VINYL ACETATE-BASED ELASTOMER PARTICLES, METHOD FOR PRODUCING THE SAME, MOLDED PRODUCT AND RESORCIN-FORMALIN-LATEX ADHESIVE AGENT |
| JP2018150444A (en) * | 2017-03-13 | 2018-09-27 | 東洋インキＳｃホールディングス株式会社 | Heat-melting composition and use of the same |
| CN112795336A (en) * | 2020-12-29 | 2021-05-14 | 德庆威斯达化工有限公司 | Water-based EVA hot melt adhesive, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3298599B2 (en) | 2002-07-02 |
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