JPH06313163A - Heat-and pressure-sensitive adhesive composition and heat-and pressure-sensitive adhesive sheet - Google Patents
Heat-and pressure-sensitive adhesive composition and heat-and pressure-sensitive adhesive sheetInfo
- Publication number
- JPH06313163A JPH06313163A JP15681793A JP15681793A JPH06313163A JP H06313163 A JPH06313163 A JP H06313163A JP 15681793 A JP15681793 A JP 15681793A JP 15681793 A JP15681793 A JP 15681793A JP H06313163 A JPH06313163 A JP H06313163A
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- Prior art keywords
- heat
- sensitive adhesive
- water
- sheet
- adhesive composition
- 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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- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は感熱性粘着組成物及び感
熱性粘着シートに関し、常温では粘着性が無く、加熱に
より活性化して熱源をとり去った後にも粘着性が暫時持
続する性質を備えた感熱性粘着組成物及び感熱性粘着シ
ートに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive adhesive composition and a heat-sensitive adhesive sheet, which has no adhesiveness at room temperature and has a property that the adhesiveness lasts for a while even after being activated by heating and removing the heat source. The present invention relates to a heat-sensitive adhesive composition and a heat-sensitive adhesive sheet.
【０００２】[0002]
【従来技術】感熱性粘着組成物については既に知られて
いて、例えば「接着便覧」第１２版第１３１頁（高分子
刊行会昭和５５年発行）に記載されている。すなわち、
基本的な組成は、高分子材料、粘着付与剤、固体可塑剤
から成り、常温では粘着性がないが加熱によって粘着性
が生じて、それが冷却後もかなりの期間持続するような
接着剤（粘着剤）をいう。通常、この粘着剤の乾燥塗膜
はタックがなく、剥離紙が不要である。2. Description of the Related Art Heat-sensitive adhesive compositions are already known and are described, for example, in "Adhesion Handbook", 12th edition, page 131 (published by Kobunshi Kobunkai, 1980). That is,
The basic composition consists of a polymeric material, a tackifier, and a solid plasticizer. An adhesive that is not tacky at room temperature but becomes tacky by heating, and that lasts for a considerable period after cooling ( Adhesive). Usually, the dry coating film of this pressure-sensitive adhesive is tack-free and does not require release paper.
【０００３】ここで前記高分子材料は、接着力を与える
成分であり、例えば、ポリ酢酸ビニル、コポリエチレン
−酢酸ビニル、ポリアクリル酸エステル系、ポリ塩化ビ
ニル系、天然ゴム、合成ゴム、コポリ酢酸ビニル−アク
リル酸エステル、ポリエステル系、ポリウレタン系の高
分子化合物類が使用される。Here, the polymer material is a component that gives an adhesive force, and is, for example, polyvinyl acetate, copolyethylene-vinyl acetate, polyacrylic acid ester type, polyvinyl chloride type, natural rubber, synthetic rubber, copolyacetic acid. Vinyl-acrylic acid ester, polyester-based and polyurethane-based polymer compounds are used.
【０００４】また、前記粘着付与剤は、加熱により活性
化された際に粘着性を増強するための成分であり、例え
ば、ロジン誘導体、テルペン樹脂系、石油樹脂系、フェ
ノール樹脂系、キシレン樹脂系等の樹脂類が使用され
る。The tackifier is a component for enhancing the tackiness when activated by heating, and is, for example, a rosin derivative, a terpene resin system, a petroleum resin system, a phenol resin system, a xylene resin system. Resins such as are used.
【０００５】また、前記固体可塑剤は、常温では固体で
あって、その融点以上に加熱されると溶融し、前記高分
子材料や粘着付与剤を膨潤・溶解して、粘・接着性を発
現させる。そして、一旦溶融した後はなかなか結晶化し
ないので、熱活性化後の粘着保持時間を長くとることが
でき、例えば、フタル酸ジフェニル、フタル酸ジヘキシ
ル、フタル酸ジシクロヘキシル、フタル酸ジヒドロアビ
エチル、イソフタル酸ジメチル、安息香酸スクロース、
ジ安息香酸エチレングリコール、トリ安息香酸トリメチ
ロールエタン、トリ安息香酸グリセリド、テトラ安息香
酸ペンタエリエット、オクタ酢酸スクロース、クエン酸
トリシクロヘキシルＮ−シクロヘキシル−Ｐ−トルエン
スルホンアミド等の常温で固体の有機化合物が使用され
ている。The solid plasticizer is solid at room temperature and melts when heated above its melting point, swells and dissolves the polymer material and the tackifier, and develops viscosity and adhesiveness. Let And, since it does not crystallize easily after being melted once, it is possible to take a long time for holding the adhesive after the heat activation. Dimethyl, sucrose benzoate,
Organic compounds that are solid at room temperature, such as ethylene glycol dibenzoate, trimethylolethane tribenzoate, tribenzoic acid glyceride, pentaerythrate tetrabenzoate, sucrose octaacetate, and tricyclohexyl N-cyclohexyl-P-toluenesulfonamide citrate, It is used.
【０００６】このような、上記高分子材料、粘着付与
剤、固体可塑剤を基本成分とする樹脂水性分散体よりな
る感熱性粘着剤を紙やフィルム等の基材に、少なくとも
片面に塗布、乾燥することにより感熱性粘着シートを製
造することができる。A heat-sensitive adhesive composed of an aqueous resin dispersion containing the above polymeric material, tackifier, and solid plasticizer as basic components is applied to at least one side of a substrate such as paper or film and dried. By doing so, a heat-sensitive adhesive sheet can be manufactured.
【０００７】高分子材料、粘着付与剤及び固体可塑剤を
混合した感熱性粘着剤を、紙やフィルム等の基材の少な
くとも片面に塗布、乾燥して得られた上記感熱性接着シ
ートは、熱活性後、各種被着体に貼着される。The heat-sensitive adhesive sheet obtained by applying a heat-sensitive adhesive obtained by mixing a polymer material, a tackifier and a solid plasticizer on at least one side of a substrate such as paper or film and drying it is After activation, it is attached to various adherends.
【０００８】[0008]
【発明が解決しようとする課題】上記の感熱性粘着シー
トは、例えば、ガラス板、ステンレス板、ポリエチレン
板、ポリエステルフィルム等、あるいはガラス瓶、プラ
スチックボトル等の各種容器等にラベルやシール等とし
て貼着して利用されるものであるが、一旦貼着された感
熱性粘着シートを、これら被着体から剥離するような場
合には、その被着体によって接着強度（貼着強度）に格
差はあるものの、粘着剤が被着体側にしっかり転着して
残ってしまってきれいに剥離されず、被着体に残存した
粘着剤を除去するのに多大の労力を要したり、あるいは
基材シートの破断等を生じて容易に剥離することが困難
であった。また、貼着物を熱溶媒中（例えば、水やアル
コール、ＮａＯＨ水溶液等）に浸漬しても、容易に自己
剥離（外力なしでシート自身が剥離）せず、従来の感熱
性粘着シートはそのような自己剥離機能を備えていなか
った。The above heat-sensitive adhesive sheet is attached as a label, a seal or the like to, for example, a glass plate, a stainless plate, a polyethylene plate, a polyester film, or various containers such as a glass bottle and a plastic bottle. However, when the heat-sensitive adhesive sheet that has been once adhered is peeled from these adherends, there is a difference in adhesive strength (sticking strength) depending on the adherends. However, the adhesive does not peel off cleanly because it remains firmly adhered to the adherend, and it takes a great deal of effort to remove the adhesive remaining on the adherend, or the base sheet breaks. It was difficult to peel easily due to such problems. In addition, even when the adhered material is immersed in a hot solvent (for example, water, alcohol, aqueous NaOH solution, etc.), it does not easily peel off itself (the sheet itself peels off without external force), and the conventional heat-sensitive adhesive sheet is It did not have a self-peeling function.
【０００９】本発明はこの様な問題点に着目してなされ
たものであって、その課題とするところは、感熱性粘着
シートの貼着された貼着物を、熱溶媒中（例えば、水，
アルコール，ＮａＯＨ水溶液等）に浸漬することによ
り、容易に粘着剤を溶解させることにあり、その目的と
するところは、熱溶媒中に浸漬することにより、被着体
から基材シートを容易に自己剥離（外力なしでシート自
身で剥離）できるようにするとともに、粘着シートの自
己剥離時における被着体への粘着剤の転着をできるかぎ
り少なくすることにある。The present invention has been made by paying attention to such a problem, and the problem is that an adhesive product having a heat-sensitive adhesive sheet attached is placed in a hot solvent (for example, water,
The purpose is to easily dissolve the pressure-sensitive adhesive by immersing it in alcohol, NaOH aqueous solution, etc., and the purpose is to soak the base material sheet from the adherend easily by immersing it in a hot solvent. The purpose is to enable peeling (peeling by itself without external force), and to minimize transfer of the pressure-sensitive adhesive to the adherend during self-peeling of the pressure-sensitive adhesive sheet.
【００１０】[0010]
【課題を解決するための手段】本発明の第１の発明は、
高分子材料と粘着付与剤と固体可塑剤とからなる基本成
分中に、熱膨張性マイクロカプセルと水溶性高分子と適
宜溶媒とを含有し、樹脂水性分散体を呈していることを
特徴とする感熱性粘着組成物である。The first invention of the present invention is as follows:
In a basic component consisting of a polymeric material, a tackifier and a solid plasticizer, a heat-expandable microcapsule, a water-soluble polymer and an appropriate solvent are contained, and a resin aqueous dispersion is presented. It is a heat-sensitive adhesive composition.
【００１１】[0011]
【実施例】感熱性粘着組成物の基本成分である高分子材
料は、接着力を与える成分であって、例えばポリ酢酸ビ
ニル、コポリエチレン−酢酸ビニル、ポリアクリル酸エ
ステル系、ポリ塩化ビニル系、天然ゴム、合成ゴム、コ
ポリ酢酸ビニル−アクリル酸エステル、ポリエステル
系、ポリウレタン系の高分子化合物類が使用される。EXAMPLE A polymeric material, which is a basic component of a heat-sensitive adhesive composition, is a component that gives an adhesive force, and includes, for example, polyvinyl acetate, copolyethylene-vinyl acetate, polyacrylic acid ester-based, polyvinyl chloride-based, Natural rubber, synthetic rubber, copolyvinyl acetate-acrylic acid ester, polyester-based and polyurethane-based polymer compounds are used.
【００１２】また、感熱性粘着組成物の基本成分である
粘着付与剤は、加熱により活性化された際に粘着性を増
強するための成分であり、例えば、ロジン誘導体、テル
ペン樹脂系、石油樹脂系、フェノール樹脂系、キシレン
樹脂系等の樹脂類が使用される。The tackifier, which is the basic component of the heat-sensitive adhesive composition, is a component for enhancing the adhesiveness when activated by heating, and is, for example, a rosin derivative, a terpene resin system, a petroleum resin. Resins such as resin, phenol resin, xylene resin, etc. are used.
【００１３】また、感熱性粘着組成物の基本成分である
固体可塑剤は、常温では固体であって、その融点以上に
加熱されると溶融し、前記高分子材料や粘着付与剤を膨
潤・溶解して、粘・接着性を発現させる。そして、一旦
溶融した後はなかなか結晶化しないので、熱活性化後の
粘着保持時間を長くとることができ、例えば、フタル酸
ジフェニル、フタル酸ジヘキシル、フタル酸ジシクロヘ
キシル、フタル酸ジヒドロアビエチル、イソフタル酸ジ
メチル、安息香酸スクロース、ジ安息香酸エチレングリ
コール、トリ安息香酸トリメチロールエタン、トリ安息
香酸グリセリド、テトラ安息香酸ペンタエリエット、オ
クタ酢酸スクロース、クエン酸トリシクロヘキシルＮ−
シクロヘキシル−Ｐ−トルエンスルホンアミド等の常温
で固体の有機化合物が使用されている。The solid plasticizer, which is the basic component of the heat-sensitive adhesive composition, is solid at room temperature and melts when heated above its melting point to swell and dissolve the polymer material and tackifier. Then, it develops stickiness and adhesiveness. And, since it does not crystallize easily after being melted once, it is possible to take a long time for holding the adhesive after the heat activation. Dimethyl, sucrose benzoate, ethylene glycol dibenzoate, trimethylolethane tribenzoate, glyceride tribenzoate, pentaerythra tetrabenzoate, sucrose octaacetate, tricyclohexyl citrate N-
Organic compounds that are solid at room temperature such as cyclohexyl-P-toluenesulfonamide are used.
【００１４】上記第１の発明の感熱性粘着組成物は、上
記のような高分子材料と粘着付与剤と固体可塑剤とから
なる基本成分中に、熱膨張性マイクロカプセルと、水溶
性高分子と、適宜溶媒とを含有するものであって、組成
物全体として樹脂水性分散体を呈しているものである。The heat-sensitive adhesive composition of the first invention comprises a heat-expandable microcapsule and a water-soluble polymer in the basic component consisting of the above-mentioned polymer material, tackifier and solid plasticizer. And an appropriate solvent, and the composition as a whole exhibits a resin aqueous dispersion.
【００１５】熱膨張性マイクロカプセルとは、芯物質を
外殻物質のポリマーが封じ込んだもので、温度を上げる
と内包された芯物質がガス化し、マイクロカプセル自身
が風船玉のごとく膨れ上がるものである。The heat-expandable microcapsules are those in which a core substance is encapsulated by a polymer of an outer shell substance, and when the temperature is raised, the encapsulated core substance is gasified and the microcapsules themselves swell like balloons. Is.
【００１６】外殻物質としては、無機系と有機系とに区
分され、その代表的なものは、ガラス、シリカ、シラ
ス、カーボン、フェノール、塩化ビニリデン、塩化ビニ
リデン・アクリロニトリルコポリマー、アルミナ、ジリ
コニアなどがある。The shell material is classified into an inorganic type and an organic type, and typical examples thereof include glass, silica, silas, carbon, phenol, vinylidene chloride, vinylidene chloride / acrylonitrile copolymer, alumina and zirconia. is there.
【００１７】内包された芯物質としては、例えば、イソ
ブタン、プロパン等の炭化水素があり、また、重炭酸ソ
ーダ、アゾビスイソブチロニトリル、炭酸アンモニウム
等の発泡剤を使用しても良い。Examples of the encapsulated core substance include hydrocarbons such as isobutane and propane, and a foaming agent such as sodium bicarbonate, azobisisobutyronitrile and ammonium carbonate may be used.
【００１８】膨張開始温度については、外殻物質と芯物
質の組合せを変えることによりできる。これらの熱膨張
性マイクロカプセルの粒径は１〜１００μｍの範囲が好
ましく、特に１０〜３０μｍの範囲が適している。ま
た、膨張開始温度は６０℃〜１２０℃の範囲が好まし
く、特に８０℃〜１００℃の範囲が適している。The expansion start temperature can be changed by changing the combination of the outer shell material and the core material. The particle size of these heat-expandable microcapsules is preferably in the range of 1 to 100 μm, and particularly preferably in the range of 10 to 30 μm. The expansion start temperature is preferably in the range of 60 ° C to 120 ° C, and particularly preferably in the range of 80 ° C to 100 ° C.
【００１９】水溶性高分子とは、天然高分子、半合成品
および合成品に大別され、高分子が水に溶解するもので
ある。天然高分子には澱粉質（甘藷澱粉、馬鈴薯澱粉、
タピオカ澱粉、小麦澱粉、コーンスターチ）、マンナン
（蒟蒻）、海藻類（ふのり、寒天、アルギン酸ナトリウ
ム）、植物粘質物（トロロアオイ、トラガントゴム、ア
ラビアゴム）、蛋白質（にかわ、ゼラチン、カゼイン、
コラーゲン）がある。The water-soluble polymer is roughly classified into a natural polymer, a semi-synthetic product and a synthetic product, and the polymer is soluble in water. Natural polymers include starchy substances (sweet potato starch, potato starch,
Tapioca starch, wheat starch, corn starch), mannan (konjac), seaweed (funnel, agar, sodium alginate), plant mucilage (troloois, tragacanth gum, acacia gum), protein (a glue, gelatin, casein,
Collagen).
【００２０】半合成品にはセルロース系（ビスコース、
メチルセルロース、エチルセルロース、ヒドロキシエチ
ルセルロース、カルボキシメチルセルロース、澱粉系
（可溶性澱粉、カルボキシメチル澱粉、ジアルデヒド澱
粉）がある。更に、合成品としては、ポリビニルアルコ
ール、ポリアクリル酸塩、ポリエチレンオキシド、ロジ
ン塩、マレイン化ロジン塩、ポリイソブチレン／無水マ
レイン酸共重合物等がある。Semi-synthetic products include cellulosics (viscose,
There are methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and starch type (soluble starch, carboxymethyl starch, dialdehyde starch). Further, as synthetic products, there are polyvinyl alcohol, polyacrylic acid salt, polyethylene oxide, rosin salt, maleated rosin salt, polyisobutylene / maleic anhydride copolymer and the like.
【００２１】上記第１の発明の感熱性粘着組成物におい
て、高分子材料、粘着付与剤、固体可塑剤、熱膨張性マ
イクロカプセル、水溶性高分子の好ましい配合比は、高
分子材料１００重量部に対して、粘着付与剤が２０〜１
５０重量部、固体可塑剤が３０〜３００重量部、熱膨張
性マイクロカプセルが０．１〜５０重量部、水溶性高分
子が１〜１００重量部である。In the heat-sensitive adhesive composition of the first invention, the preferable mixing ratio of the polymer material, tackifier, solid plasticizer, heat-expandable microcapsule and water-soluble polymer is 100 parts by weight of polymer material. In contrast, the tackifier is 20 to 1
50 parts by weight, 30 to 300 parts by weight of solid plasticizer, 0.1 to 50 parts by weight of heat-expandable microcapsules, and 1 to 100 parts by weight of water-soluble polymer.
【００２２】本発明の第２の発明は、高分子材料と粘着
付与剤と固体可塑剤とからなる基本成分中に熱膨張性マ
イクロカプセルと水溶性高分子と適宜溶媒とを含有し、
樹脂水性分散体を呈している感熱性粘着組成物が、シー
ト基材の少なくとも片面に塗布されていることを特徴と
する感熱性粘着シートである。上記感熱性粘着シート
は、図１に示すように、紙、プラスチックフィルム等、
あるいはそれらの複合材からなるシート材、テープ材等
のシート基材１を用い、該シート基材１の表面には印刷
等によって適宜絵柄、文字、記号等による表示層２を施
し、そのシート基材１の少なくとも裏面に、前述した第
１の発明による熱膨張性マイクロカプセル４と水溶性高
分子とを含有する感熱性粘着組成物を塗工することによ
って、感熱性粘着剤層３を設けて感熱性粘着シートとし
たものであり、適宜商品等の物品（被着体）に貼着して
使用する感熱性粘着ラベル、感熱性粘着シール、感熱性
粘着テープ等の感熱性粘着シートとして使用されるもの
である。The second invention of the present invention comprises heat-expandable microcapsules, a water-soluble polymer and an appropriate solvent in a basic component consisting of a polymer material, a tackifier and a solid plasticizer,
A heat-sensitive adhesive sheet characterized in that a heat-sensitive adhesive composition presenting an aqueous resin dispersion is applied to at least one surface of a sheet base material. The heat-sensitive adhesive sheet, as shown in FIG. 1, paper, plastic film,
Alternatively, a sheet base material 1 such as a sheet material or a tape material made of a composite material thereof is used, and the surface of the sheet base material 1 is appropriately provided with a display layer 2 with a picture, characters, symbols, etc. by printing or the like, and the sheet base material is used. The heat-sensitive adhesive layer 3 is provided by applying the heat-sensitive adhesive composition containing the heat-expandable microcapsules 4 according to the first invention and the water-soluble polymer on at least the back surface of the material 1. It is a heat-sensitive adhesive sheet, and is used as a heat-sensitive adhesive sheet such as a heat-sensitive adhesive label, a heat-sensitive adhesive sticker, a heat-sensitive adhesive tape, etc., which is appropriately attached to an article (adherent) such as a product. It is something.
【００２３】[0023]
【作用】本発明による感熱性粘着組成物、又は感熱性粘
着シートは、高分子材料、粘着付与剤、固体可塑剤を基
本成分とする感熱性粘着組成物、又は基材１の少なくと
も片面に該感熱性粘着組成物を塗工して形成される感熱
性粘着剤層３に、熱膨張性マイクロカプセル４と水溶性
高分子を含有しており、固体可塑剤を加熱溶融活性化し
て粘着性を付与するために十分な熱量、例えば１２０℃
〜１５０℃、数秒〜３０秒間程度の加熱処理を行なった
際においては、その加熱処理によって該組成物（又は粘
着剤層）中の熱膨張性マイクロカプセル４は、不完全な
状態で僅かに熱膨張するものであり、該マイクロカプセ
ル４を含む粘着組成物（又は粘着剤層３）は僅かに膨張
した状態で粘着性が付与され、前記感熱性粘着組成物に
よる感熱性粘着剤層３を備えた感熱性粘着シートは、被
着体に対して実質的にその粘着接触面積が僅かに少なく
なった状態で貼着される。The heat-sensitive adhesive composition or the heat-sensitive adhesive sheet according to the present invention comprises a heat-sensitive adhesive composition containing a polymer material, a tackifier, and a solid plasticizer as a basic component, or the substrate 1 on at least one surface thereof. The heat-sensitive adhesive layer 3 formed by applying the heat-sensitive adhesive composition contains the heat-expandable microcapsules 4 and the water-soluble polymer, and heat-melts and activates the solid plasticizer to increase the adhesiveness. A sufficient amount of heat to apply, for example 120 ° C
When the heat treatment is carried out at ˜150 ° C. for several seconds to 30 seconds, the heat-expandable microcapsules 4 in the composition (or the pressure-sensitive adhesive layer) are slightly heated by the heat treatment in an incomplete state. The pressure-sensitive adhesive composition (or pressure-sensitive adhesive layer 3) containing the microcapsules 4 is provided with tackiness in a slightly expanded state, and includes the heat-sensitive pressure-sensitive adhesive layer 3 formed of the heat-sensitive pressure-sensitive adhesive composition. The heat-sensitive adhesive sheet is attached to an adherend with the adhesive contact area thereof being slightly reduced.
【００２４】また、感熱性粘着組成物及び感熱性粘着シ
ートは、感熱性粘着組成物中に水溶性高分子を添加して
あるため水性の加熱溶媒に対する溶解度があり、その結
果、該組成物を、例えば、５０℃若しくは６０℃以上の
水性の加熱溶媒中に１分〜数分間浸漬した際において
は、不完全な状態で膨張を停止している該組成物中の熱
膨張性マイクロカプセル４は一層膨張して、被着体に対
する該組成物の自己剥離を促進して、自己剥離の促進に
より被着体への粘着剤の残留による汚染性を従来よりも
改善することができる。Further, since the heat-sensitive adhesive composition and the heat-sensitive adhesive sheet have a water-soluble polymer added to the heat-sensitive adhesive composition, they have a solubility in an aqueous heating solvent, and as a result, the composition is For example, when immersed in an aqueous heating solvent at 50 ° C. or 60 ° C. or higher for 1 minute to several minutes, the thermally expandable microcapsules 4 in the composition whose expansion is stopped in an incomplete state are The composition is further expanded to promote self-peeling of the composition from the adherend, and by promoting self-peeling, stain resistance due to residual adhesive on the adherend can be improved more than before.
【００２５】また、本発明の上記感熱性粘着組成物を介
して被着体に貼着される感熱性粘着シートは、５０℃若
しくは６０℃以上の水性の加熱溶媒中に１分〜数分間浸
漬した際において、熱膨張する熱膨張性マイクロカプセ
ル４は、基材シート１の自己剥離を促進して、基材シー
ト１は被着体に対して例えば外側にカールしながら自己
剥離するものである。The heat-sensitive adhesive sheet to be adhered to the adherend via the above-mentioned heat-sensitive adhesive composition of the present invention is dipped in an aqueous heating solvent at 50 ° C. or 60 ° C. or higher for 1 minute to several minutes. In doing so, the thermally expandable microcapsules 4 that thermally expand promote the self-peeling of the base material sheet 1, and the base material sheet 1 is self-peeling while curling outwardly to the adherend, for example. .
【００２６】以下に、本発明の感熱性粘着組成物及び感
熱性粘着シートの具体的実施例を示す。Specific examples of the heat-sensitive adhesive composition and the heat-sensitive adhesive sheet of the present invention are shown below.
【００２７】＜実施例１＞ 高分子材料として アクリル酸エステル共重合物の水性エマルジョン （固形分）１００重量部 粘着付与剤として ロジンエステルの水性エマルジョン（軟化点８４℃）（固形分）１００重量部 固体可塑剤として フタル酸ジシクロヘキシル水性分散体（融点６４℃）（固形分）１００重量部 熱膨張性マイクロカプセル（粒径１０〜２０μｍ、膨張開始温度８０℃）として 外殻物質；塩化ビニリデン・アクリロニトリルコポリマー 芯物質；イソブタン を用いた熱膨張性マイクロカプセル （固形分） １０重量部 水溶性高分子として ポリアクリル酸ソーダ （固形分） １０重量部Example 1 Aqueous emulsion of acrylic acid ester copolymer as polymer material (solid content) 100 parts by weight Aqueous emulsion of rosin ester as tackifier (softening point 84 ° C.) (solid content) 100 parts by weight As a solid plasticizer Dicyclohexyl phthalate aqueous dispersion (melting point 64 ° C.) (solid content) 100 parts by weight As thermally expandable microcapsules (particle size 10 to 20 μm, expansion starting temperature 80 ° C.) outer shell material; vinylidene chloride / acrylonitrile copolymer Core substance; heat-expandable microcapsule using isobutane (solid content) 10 parts by weight Sodium polyacrylate as water-soluble polymer (solid content) 10 parts by weight
【００２８】これらを固形分濃度５０％の低級アルコー
ル溶媒を用いて混合して、水性樹脂分散体（エマルジョ
ン）を呈する感熱性粘着組成物を調製した。These were mixed using a lower alcohol solvent having a solid content concentration of 50% to prepare a heat-sensitive adhesive composition exhibiting an aqueous resin dispersion (emulsion).
【００２９】その後、上記感熱性粘着組成物を、２５μ
ｍのポリエステルフィルムの基材シート片面に塗工して
４５℃で２分間乾燥させ、該基材シート片面に１８μｍ
膜厚の感熱粘着層を有する感熱性粘着シートを作製し
た。Then, the above heat-sensitive adhesive composition was added to 25 μm.
m polyester film on one side of the base sheet and dried at 45 ° C. for 2 minutes to give 18 μm on one side of the base sheet.
A heat-sensitive adhesive sheet having a heat-sensitive adhesive layer having a film thickness was produced.
【００３０】＜実施例２＞上記実施例１における熱膨張
性マイクロカプセルの添加量を、１０重量部から２０重
量部に変更した以外は、実施例１と同様にして感熱性粘
着シートを作製した。Example 2 A heat-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the amount of the heat-expandable microcapsules added in Example 1 was changed from 10 parts by weight to 20 parts by weight. .
【００３１】＜実施例３＞上記実施例１における水溶性
高分子（ポリアクリル酸ソーダ）をマレイン化ロジンの
Ｎａ塩水溶液に変更した以外は、実施例１と同様にして
感熱性粘着シートを作製した。<Example 3> A heat-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the water-soluble polymer (sodium polyacrylate) in Example 1 was changed to an aqueous sodium salt solution of maleated rosin. did.
【００３２】＜比較例１＞上記実施例１における水溶性
高分子を加えない以外は、実施例１と同様にして感熱性
粘着シートを作製した。<Comparative Example 1> A heat-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the water-soluble polymer in Example 1 was not added.
【００３３】＜比較例２＞上記実施例１における熱膨張
性マイクロカプセルを加えない以外は、実施例１と同様
にして感熱性粘着シートを作製した。Comparative Example 2 A heat-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the heat-expandable microcapsules in Example 1 were not added.
【００３４】次に、これらの感熱性粘着シートの特性を
チェックするため以下の項目について確認試験を行い下
記の表１に示すような結果を得た。Next, in order to check the characteristics of these heat-sensitive adhesive sheets, confirmation tests were conducted on the following items, and the results shown in Table 1 below were obtained.
【００３５】感熱性粘着シートの確認試験は、８０ｍｍ
×１３０ｍｍに裁断された感熱性粘着シートをそれぞれ
１２０℃にて２０秒間加熱することによって、感熱性粘
着組成物中の固体可塑剤を熱活性化して粘着性を付与
し、被着体（ガラス板）に貼り合わせて貼着物を得、該
貼着物を各種水性の熱溶媒中に浸漬させて、基材シート
の自己剥離性（剥がれ状態）、剥離時間、汚染性を観察
するものである。なお、自己剥離性とは、外力なしでシ
ート自身で剥離することを示し、剥離時間とは、自己剥
離するまでの時間を示し、汚染性とは自己剥離後の被着
体表面での粘着剤の残留付着具合いを示すものである。The confirmation test of the heat-sensitive adhesive sheet is 80 mm.
Each of the heat-sensitive adhesive sheets cut to have a size of 130 mm is heated at 120 ° C. for 20 seconds to heat-activate the solid plasticizer in the heat-sensitive adhesive composition to impart tackiness to the adherend (glass plate). ) Is adhered to obtain an adhered product, and the adhered product is immersed in various aqueous hot solvents to observe the self-peeling property (peeling state), the peeling time, and the staining property of the base sheet. The self-peeling property means that the sheet is peeled by itself without external force, the peeling time means the time until self-peeling, and the stain property is the pressure-sensitive adhesive on the adherend surface after self-peeling. It shows the residual adhesion condition of.
【００３６】[0036]
【表１】 [Table 1]
【００３７】[0037]
【発明の効果】本発明の感熱性粘着組成物及び感熱性粘
着シートは、熱膨張性マイクロカプセル及び水溶性高分
子を含有することを特徴とする樹脂水性分散体（エマル
ジョンタイプ）の感熱性粘着組成物及び該組成物を基材
シートに塗工した感熱性粘着シートであり、該感熱性粘
着シートを熱活性化して被着体（例えば、ガラス板，ス
テンレス板，ポリエチレン板，ポリエステルフィルム
等）に貼着した貼着物は、６０℃以上の熱溶媒中（例え
ば、水，アルコール，ＮａＯＨ水溶液等）に浸漬するこ
によって基材シートが容易に自己剥離でき、粘着剤の被
着体に対する転着残りが減少する等の効果がある。The heat-sensitive adhesive composition and heat-sensitive adhesive sheet of the present invention contain heat-expandable microcapsules and a water-soluble polymer, which is a heat-sensitive adhesive of an aqueous resin dispersion (emulsion type). A composition and a heat-sensitive adhesive sheet obtained by applying the composition to a substrate sheet, the heat-sensitive adhesive sheet being heat-activated to be an adherend (eg, glass plate, stainless plate, polyethylene plate, polyester film, etc.) The base material sheet can be easily peeled off by immersing the adherend adhered to the substrate in a hot solvent (for example, water, alcohol, NaOH aqueous solution, etc.) at 60 ° C or higher, and transfer of the adhesive to the adherend. It has the effect of reducing the rest.
【図１】本発明の第２の発明における感熱性粘着シート
の概要側断面図である。FIG. 1 is a schematic side sectional view of a heat-sensitive adhesive sheet according to a second invention of the present invention.
１…基材 ２…表示層 ３…感熱性粘着剤層 ４…熱膨
張性マイクロカプセルDESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Display layer 3 ... Thermosensitive adhesive layer 4 ... Thermally expandable microcapsule
───────────────────────────────────────────────────── フロントページの続き (72)発明者 堀井 信明 東京都台東区台東一丁目５番１号 凸版印 刷株式会社内 (72)発明者 今井 ゆか 東京都台東区台東一丁目５番１号 凸版印 刷株式会社内 (72)発明者 黒田 健二郎 東京都台東区台東一丁目５番１号 凸版印 刷株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Nobuaki Horii, No. 1-5-1, Taito, Taito-ku, Tokyo, Toppan Printing Co., Ltd. (72) Yuka Imai, No. 1-5, Taito, Taito-ku, Tokyo Toppan In Printing Co., Ltd. (72) Kenjiro Kuroda Inventor Kenjiro Kuroda 1-5-1 Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd.
Claims (4)
らなる基本成分中に、熱膨張性マイクロカプセルと水溶
性高分子と適宜溶媒とを含有し、樹脂水性分散体を呈し
ていることを特徴とする感熱性粘着組成物。1. A resin aqueous dispersion containing a thermally expansive microcapsule, a water-soluble polymer, and an appropriate solvent in a basic component consisting of a polymer material, a tackifier, and a solid plasticizer. A heat-sensitive adhesive composition characterized by the above.
以上で熱膨張を開始する１種類の熱膨張性マイクロカプ
セル、又は熱膨張開始温度の異なる２種類以上の熱膨張
性マイクロカプセルを混合したものである請求項１に記
載の感熱性粘着組成物。2. The heat-expandable microcapsules have a temperature of 60 ° C.
The heat-sensitive adhesive composition according to claim 1, which is one kind of heat-expandable microcapsules that starts thermal expansion as described above, or a mixture of two or more kinds of heat-expandable microcapsules having different heat expansion start temperatures.
１種類の水溶性高分子、又は組成の異なる２種類以上の
水性高分子を混合したものである請求項１に記載の感熱
性粘着組成物。3. The heat-sensitive polymer according to claim 1, wherein the water-soluble polymer is one water-soluble polymer soluble in water or a mixture of two or more water-soluble polymers having different compositions. Adhesive composition.
らなる基本成分中に熱膨張性マイクロカプセルと水溶性
高分子と適宜溶媒とを含有し、樹脂水性分散体を呈して
いる感熱性粘着組成物が、シート基材の少なくとも片面
に塗布されていることを特徴とする感熱性粘着シート。4. A heat-sensitive resin, which comprises a resin aqueous dispersion containing heat-expandable microcapsules, a water-soluble polymer and an appropriate solvent in a basic component consisting of a polymer material, a tackifier and a solid plasticizer. A heat-sensitive adhesive sheet, wherein the heat-sensitive adhesive composition is applied to at least one surface of a sheet base material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5156817A JP3026700B2 (en) | 1993-03-05 | 1993-06-28 | Heat-sensitive adhesive composition and heat-sensitive adhesive sheet |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4490093 | 1993-03-05 | ||
| JP5-44900 | 1993-03-05 | ||
| JP5156817A JP3026700B2 (en) | 1993-03-05 | 1993-06-28 | Heat-sensitive adhesive composition and heat-sensitive adhesive sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06313163A true JPH06313163A (en) | 1994-11-08 |
| JP3026700B2 JP3026700B2 (en) | 2000-03-27 |
Family
ID=26384875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5156817A Expired - Fee Related JP3026700B2 (en) | 1993-03-05 | 1993-06-28 | Heat-sensitive adhesive composition and heat-sensitive adhesive sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3026700B2 (en) |
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| JP2007077369A (en) * | 2005-09-16 | 2007-03-29 | Ricoh Co Ltd | Thermosensitive adhesive and thermosensitive adhesive material |
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|---|---|---|---|---|
| SG120911A1 (en) | 2002-02-25 | 2006-04-26 | Nitto Denko Corp | Aqueous dispersion type pressure-sensitive adhesive composition and pressure-sensisive adhesive product |
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1993
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| US9849655B2 (en) | 2013-11-27 | 2017-12-26 | Henkel IP & Holding GmbH | Adhesive for insulative articles |
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| Publication number | Publication date |
|---|---|
| JP3026700B2 (en) | 2000-03-27 |
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