JPH0391586A - Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet - Google Patents
Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheetInfo
- Publication number
- JPH0391586A JPH0391586A JP22966889A JP22966889A JPH0391586A JP H0391586 A JPH0391586 A JP H0391586A JP 22966889 A JP22966889 A JP 22966889A JP 22966889 A JP22966889 A JP 22966889A JP H0391586 A JPH0391586 A JP H0391586A
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- heat
- pressure
- adhesive composition
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract 6
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000004014 plasticizer Substances 0.000 claims abstract description 12
- 230000001070 adhesive effect Effects 0.000 claims description 39
- 239000000853 adhesive Substances 0.000 claims description 38
- 239000004005 microsphere Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 claims 1
- 230000000903 blocking effect Effects 0.000 abstract description 16
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract description 7
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 abstract description 6
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002148 esters Chemical class 0.000 abstract description 4
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 abstract description 3
- 206010057040 Temperature intolerance Diseases 0.000 abstract description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001038 ethylene copolymer Polymers 0.000 abstract description 2
- 230000008543 heat sensitivity Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229920002261 Corn starch Polymers 0.000 description 3
- 239000008120 corn starch Substances 0.000 description 3
- 229940099112 cornstarch Drugs 0.000 description 3
- 238000012674 dispersion polymerization Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229920001353 Dextrin Polymers 0.000 description 2
- 239000004375 Dextrin Substances 0.000 description 2
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000019425 dextrin Nutrition 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- LVTPRIAGCBEGPW-UHFFFAOYSA-N (2-benzoyloxyphenyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1OC(=O)C1=CC=CC=C1 LVTPRIAGCBEGPW-UHFFFAOYSA-N 0.000 description 1
- XJSYXHKRYFDECG-UHFFFAOYSA-N 2-(benzenesulfonyloxy)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1OS(=O)(=O)C1=CC=CC=C1 XJSYXHKRYFDECG-UHFFFAOYSA-N 0.000 description 1
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- LIDDQKAMUXHIQD-UHFFFAOYSA-N phenyl 2-benzoyloxybenzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 LIDDQKAMUXHIQD-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008542 thermal sensitivity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
（Ａ）産業上の利用分野
本発明は、常温では粘着性が無く、加熱により活性化し
て粘着性（タック）が顕れ、しかも熱源から離れた後も
粘着性が長時間持続する感熱性粘着組成物、および、そ
れをシート状支持体上に塗設した感熱性粘着シートに関
する。DETAILED DESCRIPTION OF THE INVENTION (A) Industrial Application Field The present invention has no tackiness at room temperature, becomes tacky when activated by heating, and remains tacky for a long time even after being removed from the heat source. The present invention relates to a heat-sensitive adhesive composition that lasts for a long time, and a heat-sensitive adhesive sheet in which the same is coated on a sheet-like support.
（Ｂ）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、１３１頁（高分子刊行会発行、
昭和５５年）に記載されている。(B) Prior Art Heat-sensitive adhesive compositions are already known, for example, "Adhesive Handbook" 12th edition, p. 131 (published by Kobunshi Kankokai,
(1981).
すなわち、基本的に（ａ）高分子材料、（ｂ）粘着付与
剤、（ｃ）固体可塑剤の３者から成る組成物であって、
常温では粘着性がないが加熱によって粘着性がでて、そ
れが冷却後もかなりの期間持続するような接着剤をいう
。That is, it is a composition basically consisting of (a) a polymer material, (b) a tackifier, and (c) a solid plasticizer,
An adhesive that is not sticky at room temperature, but becomes sticky when heated and remains sticky for a considerable period of time even after cooling.
（ａ）高分子材料としては、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、コポリビニルピロリドン
−スチレン、コポリスチレン−ブタジェン、コポリスチ
レン−アクリル酸エステル、ポリエステル系、ポリウレ
タン系等の高分子化合物類、（ｂ）粘着付与剤としては
、ロジン誘導体（ロジン、重合ロジン、水素添加ロジン
、それらのグリセリン、ペンタエリスリトール等とのエ
ステル、樹脂酸ダイマー等）、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、
（ｃ）固体可塑剤としては、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、カテコー
ルジベンゾエート、２−ベンゾイルオキシ安息香酸フェ
ニル、２−フェニルスルホニルオキシ安息香酸フェニル
、Ｎ−シクロヘキシル−ｐ−）ルエンスルホンアミド、
ｐ−ヒドロキシ安息香酸ベンジル等の常温で固体の有機
化合物が使用される。(a) Examples of polymeric materials include polyvinyl acetate, copolyethylene-vinyl acetate, polyacrylic ester, polyvinyl chloride, natural rubber, synthetic rubber, copolyvinyl acetate-acrylic ester, and copolyvinylpyrrolidone-styrene. , copolystyrene-butadiene, copolystyrene-acrylic acid ester, polyester type, polyurethane type, etc. (b) As the tackifier, rosin derivatives (rosin, polymerized rosin, hydrogenated rosin, their glycerin, esters with pentaerythritol, resin acid dimers, etc.), resins such as terpene resins, petroleum resins, phenolic resins, xylene resins, etc.
(c) Solid plasticizers include diphenyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, dihydroabiethyl phthalate, dimethyl isophthalate, catechol dibenzoate, phenyl 2-benzoyloxybenzoate, and 2-phenylsulfonyloxybenzoic acid. phenyl, N-cyclohexyl-p-)luenesulfonamide,
Organic compounds that are solid at room temperature, such as benzyl p-hydroxybenzoate, are used.
ここで（ａ）高分子材料は接着力を与える成分であり、
（ｂ）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る。Here (a) the polymeric material is a component that provides adhesive strength,
(b) The tackifier is a component for increasing tackiness when activated by heating.
（ｃ）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、近傍の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
、−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る。(c) A solid plasticizer is solid at room temperature, melts when heated above its melting point, swells and dissolves nearby polymeric materials and tackifiers, and develops tackiness and adhesive properties. Moreover, since it does not crystallize easily after being melted, the adhesion can be maintained for a long time after being thermally activated.
かかる感熱性粘着組成物は、好ましくは、基本成分のそ
れぞれを□、水性懸濁液の形に調製し、適正な比率で混
合することによって得られる。Such a heat-sensitive adhesive composition is preferably obtained by preparing each of the basic components in the form of an aqueous suspension and mixing them in appropriate proportions.
こうして得た水性混合懸濁液を、紙やフィルムのような
シートの上へ塗布し、乾燥すれば、能率良く感熱性粘着
シートを製造することができる。By applying the thus obtained aqueous mixed suspension onto a sheet such as paper or film and drying it, a heat-sensitive adhesive sheet can be efficiently produced.
（ｃ）発明が解決しようとする課題
感熱性粘着組成物の実際の使用形態は種々あるが、シー
ト上に塗設して感熱性粘着シートの形で用いられること
が最も多く、かかる塗設シートは当然、巻き取られたり
重ねられたりして、保管される。保管場所も、極く低温
のところもあれば、可成り高温の場合もある。特に高温
寄りの環境に置かれたときは、塗設シート同士がくっつ
きあう、いわゆるブロッキングという望ましくない現象
に見舞われる。(c) Problems to be Solved by the Invention Although there are various forms of actual use of heat-sensitive adhesive compositions, they are most often used in the form of heat-sensitive adhesive sheets by coating them on sheets, and such coated sheets Naturally, they are rolled up or stacked on top of each other for storage. Some storage locations are extremely cold, while others are quite high. Particularly when placed in a high-temperature environment, coated sheets tend to stick together, an undesirable phenomenon known as blocking.
実用上は、粘着発現温度すなわち活性化温度は極力低く
、保管可能温度は成るべく高くという、完全に矛盾した
ことが要求される。従って、従来技術の範囲では、かか
る要求に十分応えられる状況には至っていす、ブロッキ
ング・トラブルに、しばしば悩まされてきた。In practical terms, the adhesion development temperature, that is, the activation temperature, is required to be as low as possible, and the storage temperature is as high as possible, which are completely contradictory requirements. Therefore, within the scope of the prior art, the situation has not yet reached a point where such requirements can be fully met, but blocking troubles have often occurred.
すなわち、本発明が解決すべき課題は、感熱性粘着組成
物塗設シートを、巻き取ったり重ねたりして保管した場
合にもブロッキングの恐れがなく、しかも活性化温度が
極力低い、言替えれば感熱感度が十分に高い、感熱性粘
着組成物および感熱性粘着シートを実現することである
。In other words, the problem to be solved by the present invention is to create a heat-sensitive adhesive composition-coated sheet that is free from blocking even when stored rolled up or stacked, and that has an activation temperature as low as possible. The object of the present invention is to realize a heat-sensitive adhesive composition and a heat-sensitive adhesive sheet having sufficiently high heat sensitivity.
（Ｄ）課題を解決するための手段
かかる課題は、上記組成物中に更に、（ｄ）高分子ミク
ロスフェアを添加することによって、解決することがで
きた。(D) Means for Solving the Problems This problem could be solved by further adding (d) polymer microspheres to the above composition.
高分子ミクロスフェアとは、スチレン、アクリル酸エス
テル、メタクリル酸エステル等の広義のオレフィン系モ
ノマーを懸濁重合法もしくは分散重合法等で重合して得
た、平均粒径がミクロン（μｍ）オーダー以上の高分子
微粒体のことである。特に、近年技術進歩の著しい分散
重合法による高分子ミクロスフェア（文献例、ザ・ブリ
ティシュ・ポリマー・ジャーナル、ＰＰ１３３〜１３６
．１９８２年刊；材料技術、ＰＰ１５１〜１６３．１９
８９年刊）は、粒子径の単分散性が優れているので、本
発明において最も好適である。Polymer microspheres are obtained by polymerizing broadly defined olefin monomers such as styrene, acrylic esters, methacrylic esters, etc. by suspension polymerization or dispersion polymerization, and have an average particle size of the order of microns (μm) or more. This refers to fine polymer particles. In particular, polymer microspheres produced by the dispersion polymerization method, which has undergone remarkable technological progress in recent years (Reference example, The British Polymer Journal, PP133-136)
．． Published in 1982; Materials Technology, PP151-163.19
(published in 1989) is most suitable in the present invention because it has excellent monodispersity in particle size.
本発明の感熱性粘着剤とは異なるが、再湿接着剤という
ものがある。これは通常は乾燥していて接着力はないが
、水を与えると活性化して接着力が生じる。このものも
、乾燥状態で保管中にブロッキングを起こす恐れがある
ので、デキストリンとかコーンスターチのような粒子を
添加することがよく行われている。Although different from the heat-sensitive adhesive of the present invention, there is also a rewetting adhesive. This is normally dry and non-adhesive, but when water is applied it becomes activated and becomes adhesive. This product also has the risk of causing blocking during storage in a dry state, so particles such as dextrin or cornstarch are often added.
感熱性粘着組成物へデキストリンやコーンスターチのよ
うな粒子を添加しても、確かにプロッキングは改善され
るが、それに伴って肝心の接着能力が大幅に悪化してし
まって、実用にならないことを本発明者は見出したので
ある。Adding particles such as dextrin or corn starch to a heat-sensitive adhesive composition certainly improves blocking, but the essential adhesive ability deteriorates significantly, making it impractical. This is what the inventor discovered.
かかる経過から接着能力を後退させずにブロッキングを
防ぐに有効な方法を探索し、ここに高分子ミクロスフェ
アが要望に答え得るものであることを見出した。Based on this process, we searched for an effective method to prevent blocking without reducing adhesive ability, and found that polymer microspheres could meet our needs.
本発明で好適に用い得る高分子ミクロスフェアは、熱可
塑性高分子から成り、しかも未架橋のものが最も良い。The polymer microspheres that can be suitably used in the present invention are best made of thermoplastic polymers and uncrosslinked.
平均粒径は１〜１００μｍの範囲が好ましく、特に５〜
３０μｍの範囲が適している。本発明の感熱性粘着組成
物においては、（ａ）高分子材料、（ｂ）粘着付与剤お
よび（ｃ）固体可塑剤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１０〜１５０重量
部、固体可塑剤が３０〜３００重量部である。The average particle size is preferably in the range of 1 to 100 μm, particularly in the range of 5 to 100 μm.
A range of 30 μm is suitable. In the heat-sensitive adhesive composition of the present invention, the preferred blending ratio of (a) polymer material, (b) tackifier, and (c) solid plasticizer is that the tackifier is added to 100 parts by weight of the polymer material. is 10 to 150 parts by weight, and the solid plasticizer is 30 to 300 parts by weight.
（ｄ）高分子ミクロスフェアは、（ａ）＋ （ｂ）＋
（ｃ）＝１００重量部に対して、１〜１００重量部が好
ましく、更に好ましくは５〜５０重量部である。高分子
ミクロスフェアの量が少なすぎるとブロッキング防止効
果は小さくなり、多すぎると感熱感度が低下してしまう
。(d) Polymer microspheres are (a) + (b) +
For (c) = 100 parts by weight, the amount is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight. If the amount of polymeric microspheres is too small, the blocking prevention effect will be small, and if it is too large, the thermal sensitivity will be reduced.
（Ｅ）作用
接着剤中に粒子を混入すれば、ブロッキングは改善され
るが、接着能力は低下してしまう。(E) Working If particles are mixed into the adhesive, blocking will be improved, but the adhesion ability will be reduced.
本発明の感熱性粘着組成物においても、加熱活性時、不
融不溶の粒子が存在すると接着能力は低下する。高分子
ミクロスフェア、殊に熱可塑性高分子からなる未架橋の
高分子ミクロスフェアは、固体可塑剤の融点以下ではあ
るが、高温寄りの保管条件下で、高分子ミクロスフェア
が存在しなければ感熱性粘着シートがブロッキングを起
してしまうような時に、ブロッキングを防止する。そし
て、活性化温度以上に加熱した時は、走査型電子顕微鏡
で観察しても、最早粒子（通常、球形）の姿は認められ
ず、組成物全体が一様に溶融していることが分った。Also in the heat-sensitive adhesive composition of the present invention, the presence of infusible and insoluble particles during heat activation lowers the adhesion ability. Polymeric microspheres, especially uncrosslinked polymeric microspheres made of thermoplastic polymers, are thermosensitive under storage conditions that are below the melting point of solid plasticizers, but in the absence of polymeric microspheres. To prevent blocking when a sticky adhesive sheet causes blocking. When heated above the activation temperature, even when observed with a scanning electron microscope, the appearance of particles (usually spherical) is no longer observed, indicating that the entire composition is uniformly melted. It was.
このことが、本発明において高分子ミクロスフェアが有
用°な作用を示す原因と考えられる。This is considered to be the reason why the polymer microspheres exhibit useful effects in the present invention.
とりわけ、（メタ）アクリル酸エステル系を重合して得
た高分子ミクロスフェアを含有させた時は、加熱活性化
時の接着能力の低下が微少となる。In particular, when polymer microspheres obtained by polymerizing a (meth)acrylic ester type are contained, the adhesive ability upon heat activation is minimally reduced.
これは高分子ミクロスフェア自身も、融解した可塑剤に
溶解して接着力を発揮する為と考えられる。This is thought to be because the polymer microspheres themselves also dissolve in the melted plasticizer and exhibit adhesive strength.
高分子ミクロスフェアが、懸濁重合法で作ったものであ
る場合は、ブロッキング防止のための添加量（重量部）
が多い目になるのに対して、分散重合法で作ったものの
場合は、もつとも少ない量（重量部）で有効に働く。If the polymer microspheres are made by suspension polymerization, the amount added (parts by weight) to prevent blocking.
However, in the case of products made by dispersion polymerization, a small amount (parts by weight) is required to work effectively.
これは、後者の高分子ミクロスフェアが単分散であるた
めに、効果の劣る小粒径粒子を含んでいないことによる
ものと考えられる。このことは実用上、品質的にも経済
的にも大きなメリットである。This is thought to be because the latter polymer microspheres are monodisperse and do not contain small-sized particles, which are less effective. This is a great advantage in terms of practicality, quality, and economy.
（Ｆ）実施例
本実施例においては「部」は断りのない限り「重量部」
を表わす。(F) Example In this example, "parts" are "parts by weight" unless otherwise specified.
represents.
実施例１
（ａ）高分子材料として、
酢酸ビニル−エチレンコポリマー（酢酸ビニル含有ｆｆ
１７０重量％）の水性エマルジョン（固形分）１００部
（ｂ）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１００℃） （固形分）１００部（ｃ）固
体可塑剤として、
フタル酸ジシクロヘキシル水性分散物
（融点 ６２℃） （固形分）１００部（ｄ）高
分子ミクロスフェアとして、
分散重合法によるポリスチレンミクロスフェア（粒径８
〜１０μｍの球体）（ドライ）３０部これらを混合して
水性塗工液（固形分濃度５０％）を調製し、坪量８０ｇ
／ｒｄの両面アート紙の片面へ乾燥塗布量１５ ｇ／ｎ
ｆとなるように塗布し、５０℃で２分間乾燥し、非粘着
性の塗被紙を得た。Example 1 (a) Vinyl acetate-ethylene copolymer (vinyl acetate-containing ff
170% by weight) aqueous emulsion (solid content) 100 parts (b) As a tackifier, an aqueous emulsion of rosin ester (softening point 100°C) (solid content) 100 parts (c) As a solid plasticizer, dicyclohexyl phthalate aqueous Dispersion (melting point 62°C) (solid content) 100 parts (d) As polymer microspheres, polystyrene microspheres (particle size 8
~10 μm spheres) (dry) 30 parts These were mixed to prepare an aqueous coating liquid (solid content concentration 50%), and the basis weight was 80 g.
Dry coating amount 15 g/n on one side of /rd double-sided art paper
f and dried at 50° C. for 2 minutes to obtain a non-tacky coated paper.
比較例１
実施例１における（ｄ）高分子ミクロスフェアを加えな
い試料紙片を作製した。Comparative Example 1 A sample paper piece in which (d) polymer microspheres in Example 1 was not added was prepared.
比較例２
実施例１における（ｄ）高分子ミクロスフエアの代りに
コーンスターチ（ドライ）３０部を加えた試料紙片を作
製した。Comparative Example 2 A sample paper piece was prepared in which 30 parts of cornstarch (dry) was added instead of the polymer microspheres (d) in Example 1.
実施例２
実施例１における（ｄ）高分子ミクロスフェアであるポ
リスチレンミクロスフェアの代りに、分散重合法による
ポリメタクリル酸メチルミクロスフェア（粒径８〜１０
μｍの球体）（ドライ）３０部を用いた試料紙片を作製
した。Example 2 Polymethyl methacrylate microspheres (particle size 8 to 10
A sample paper piece was prepared using 30 parts of µm spheres (dry).
実施例３（傾斜式ポールタック法による粘接着能力の評
価）
実施例１、比較例１、比較例２および実施例２で作製し
た塗被紙片（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熱活性化させ、直ち
にタックの程度を傾斜式ポールタック測定法によって測
定（環境温度２０℃、傾斜角度３０度）した。タックす
なわち粘接着強度の程度は最大ポール番号で示した（数
字大はど粘接着強度大である）。Example 3 (Evaluation of adhesive ability by inclined pole tack method) The coated paper pieces (heat-sensitive adhesive sheets) prepared in Example 1, Comparative Example 1, Comparative Example 2, and Example 2 were heated at 120°C, respectively.
The tack was thermally activated by heating for 20 seconds, and the degree of tack was immediately measured by an inclined pole tack measurement method (ambient temperature: 20° C., inclination angle: 30°). The degree of tack, that is, adhesive strength, is indicated by the maximum pole number (the larger the number, the greater the adhesive strength).
測定結果は表１に示す。The measurement results are shown in Table 1.
実施例４
実施例１、比較例１、比較例２および実施例２で作製し
た塗被紙片（感熱性粘着シート）のブロッキング特性を
調べるために、各塗被紙片試料を表面と裏面が相対する
ように重ねて、１ｋｇ／ａＩとなるように錘（おもり）
を載せて、環境温度５０℃にて３０分間放置した。引続
いてブロッキングの有無を紙片同士を手で剥すことによ
り感覚テスト（剥し易さ、剥すときの音、表面のむけ等
を総合評価）によって調べた。Example 4 In order to investigate the blocking properties of the coated paper strips (heat-sensitive adhesive sheets) produced in Example 1, Comparative Example 1, Comparative Example 2, and Example 2, the front and back sides of each coated paper strip sample were placed opposite each other. Stack the weights so that the weight is 1kg/aI.
was placed and left for 30 minutes at an environmental temperature of 50°C. Subsequently, the presence or absence of blocking was examined by a sensory test (comprehensive evaluation of ease of peeling, sound when peeling, peeling of the surface, etc.) by peeling the pieces of paper together by hand.
結果を表１に示すが、ブロッキングの程度をＡｌＢ、Ｃ
，ＤＳＥの５段階で表現してあり、ＡＳＢおよびＣは実
用上差し支えなく、ＤおよびＥは実用上問題ありとの意
である。The results are shown in Table 1, and the degree of blocking was determined by AlB, C
, DSE, with ASB and C meaning that there is no problem in practical use, and D and E meaning that there is a problem in practical use.
（以下余白）
表
（Ｇ）発明の効果
感熱性粘着組成物から成る層を紙のようなシート状支持
体上へ塗設した場合の、シート同士のくっつき、即ち、
ブロッキングを防ぎ、かつ粘接着能力を高い水準に保つ
には、上述の通り、合成高分子からなるミクロスフェア
の実質量を添加するのが極めて有効であることが判明し
た。(Margins below) Table (G) Effects of the Invention When a layer made of a heat-sensitive adhesive composition is coated on a sheet-like support such as paper, sticking of the sheets to each other, i.e.,
In order to prevent blocking and maintain the adhesive ability at a high level, it has been found that it is extremely effective to add a substantial amount of microspheres made of synthetic polymers, as described above.
Claims (4)
体可塑剤の３者を基本成分として含有して成る感熱性粘
着組成物において、更に、（ｄ）高分子ミクロスフェア
を含有することを特徴とする感熱性粘着組成物。(1) A heat-sensitive adhesive composition comprising three basic components: (a) a polymeric material, (b) a tackifier, and (c) a solid plasticizer, further comprising (d) polymeric microspheres. A heat-sensitive adhesive composition comprising:
性高分子から成るミクロスフェアである、請求項１記載
の感熱性粘着組成物。(2) The heat-sensitive adhesive composition according to claim 1, wherein the polymer microspheres (d) are microspheres made of an uncrosslinked thermoplastic polymer.
体可塑剤の３者を基本成分として含有する感熱性粘着組
成物から成る層を、シート状支持体の少なくも片面へ塗
設して成る感熱性粘着シートにおいて、該塗設層が更に
、（ｄ）高分子ミクロスフェアを含有することを特徴と
する感熱性粘着シート。(3) A layer consisting of a heat-sensitive adhesive composition containing as basic components (a) a polymeric material, (b) a tackifier, and (c) a solid plasticizer is applied to at least one side of a sheet-like support. A heat-sensitive pressure-sensitive adhesive sheet formed by applying a coating to a heat-sensitive pressure-sensitive adhesive sheet, wherein the coating layer further contains (d) polymer microspheres.
性高分子から成るミクロスフェアである、請求項３記載
の感熱性粘着シート。(4) The heat-sensitive adhesive sheet according to claim 3, wherein the polymer microspheres (d) are microspheres made of an uncrosslinked thermoplastic polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22966889A JPH0391586A (en) | 1989-09-05 | 1989-09-05 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22966889A JPH0391586A (en) | 1989-09-05 | 1989-09-05 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0391586A true JPH0391586A (en) | 1991-04-17 |
Family
ID=16895805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22966889A Pending JPH0391586A (en) | 1989-09-05 | 1989-09-05 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0391586A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002003817A (en) * | 2000-06-23 | 2002-01-09 | Dainippon Ink & Chem Inc | Delayed tack pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| US6396528B1 (en) | 1997-07-22 | 2002-05-28 | Ricoh Company, Ltd. | Image forming system, intermediate transfer medium and method with temporary attachment features |
-
1989
- 1989-09-05 JP JP22966889A patent/JPH0391586A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6396528B1 (en) | 1997-07-22 | 2002-05-28 | Ricoh Company, Ltd. | Image forming system, intermediate transfer medium and method with temporary attachment features |
| JP2002003817A (en) * | 2000-06-23 | 2002-01-09 | Dainippon Ink & Chem Inc | Delayed tack pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
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