JP5030044B2 - Crimpable re-peelable pressure-sensitive adhesive composition for bonding and use thereof - Google Patents

Crimpable re-peelable pressure-sensitive adhesive composition for bonding and use thereof Download PDF

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JP5030044B2
JP5030044B2 JP2004333966A JP2004333966A JP5030044B2 JP 5030044 B2 JP5030044 B2 JP 5030044B2 JP 2004333966 A JP2004333966 A JP 2004333966A JP 2004333966 A JP2004333966 A JP 2004333966A JP 5030044 B2 JP5030044 B2 JP 5030044B2
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清州 高嶋
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Soken Chemical and Engineering Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description

本発明は、貼合用の圧着性再剥離型粘着剤組成物に関し、より詳細には、隠蔽はがき、親展ハガキ、封書等の二つ折り又は三つ折り連続帳票用紙に設ける粘着剤層用として、圧着性で、再剥離のできる粘着剤組成物であって、このようなＺ折りの帳票用紙をシーラー装置に連続供給させて、その回転する圧着ローラを介して、圧着・貼合・搬送させながら貼合製品に加工させるに際して、シーラー装置の加工作業性に優れる圧着性再剥離型の貼合用粘着剤組成物及びその粘着剤組成物を用いる用途に関する。   The present invention relates to a pressure-sensitive adhesive releasable pressure-sensitive adhesive composition for bonding, and more specifically, as a pressure-sensitive adhesive layer provided on bi-fold or tri-fold continuous form paper such as concealment postcards, confidential postcards, sealed letters, etc. The adhesive composition can be re-peeled and can be re-peeled, and such Z-folded form paper is continuously supplied to the sealer device, and is applied while being pressed, bonded and conveyed via the rotating pressure roller. The present invention relates to a pressure-sensitive adhesive re-peeling pressure-sensitive adhesive composition for bonding, which is excellent in processing workability of a sealer device, and an application using the pressure-sensitive adhesive composition.

従来から多岐に及ぶ分野に、テープ状、フィルム状又はシート状の紙、有機樹脂材が貼り合わせ部材や、被覆部材として利用されている。このような素材を貼合部材又は被覆部材として加工時又は実使用時における取り扱い性、作業性等に優れることから、その片面又は両面に粘着剤が塗工された粘着テープ、粘着シート又は粘着フィルムとして広く用いられている。また、このような素材の仕様は、圧着性で、再剥離を可能にさせるものであって、粘着剤の機能として初期接着性を有し、貼り合させた後、適宜容易に再剥離させることができるものである。このように一時的に貼合接着させて再剥離させることから、各種の新規材料面の使用前までの表面保護・錆止め被覆材として、また、各種の表示用のレッテル材として用いられている。   Conventionally, in various fields, tape-like, film-like or sheet-like paper, and organic resin materials have been used as bonding members and covering members. Since such a material is used as a bonding member or a covering member and is excellent in handleability, workability, etc. at the time of processing or actual use, an adhesive tape, an adhesive sheet or an adhesive film coated with an adhesive on one or both sides thereof Is widely used. In addition, the specifications of such a material are pressure-bonding properties and enable re-peeling, and have initial adhesiveness as a function of the pressure-sensitive adhesive. It is something that can be done. Since it is temporarily bonded and adhered and re-peeled in this way, it is used as a surface protection / rust prevention coating material before use of various new material surfaces, and as a label material for various displays.

また、近年に至っては、このような圧着による一時貼り合わせで、適宜自在に再剥離ができる粘着剤機能を活かして、オフィス、学校、官公庁等におけるメール業務の多量化・多様化に対処すべく、請求書、通知書等の隠蔽・親展情報や、各種案内・通知情報を手早く、低料金で、しかも、一時的なプライバシー保護（又は秘密隠蔽）を可能にさせる目的から、隠蔽ハガキ、親展ハガキや、封書として隠蔽下に郵送され、再剥離させて特定情報を剥離・開封・確認することができる。   In recent years, in order to cope with the increasing and diversification of e-mail business in offices, schools, government offices, etc., by utilizing the adhesive function that can be re-separated as needed by temporary bonding by such crimping. Concealment / confidential information such as invoices, notices, etc. and various information / notification information for the purpose of enabling quick, low-cost, temporary privacy protection (or secret concealment) Or, it can be mailed in a concealed form as a sealed letter, and it can be peeled off again to peel off, open and confirm specific information.

このような隠蔽ハガキ、親展ハガキ、封書等を加工させるに際しては、連続帳票用紙の片面又は両面の所定の箇所に粘着剤組成物（以後、単に粘着剤と記すこともある）を塗工させた二つ折り又は三つ折りの連続帳票用紙を搬送させながら圧着貼合させて貼合製品とする。従って、このような一連の加工作業において、塗工済みの粘着剤は、粘着剤層の支持体であるカット用紙に対しては、初期粘着力を発揮させ且つ脱着することがなく、一方、その支持体に塗工されている粘着剤層は、対向貼合面の用紙被着体に対しては、圧着下に容易に貼合接着するが、再剥離時には粘着剤層が剥がれて転写することがなく、更には、一連の加工作業時においては、通常、圧着させながら搬送させる回転ロール型の部材面に、粘着力を発揮させないことが望まれる。   When processing such concealment postcards, confidential postcards, sealed letters, etc., an adhesive composition (hereinafter sometimes simply referred to as an adhesive) was applied to a predetermined part of one or both sides of a continuous form paper. Bonded products are made by pressure-bonding while conveying bi-fold or tri-fold continuous forms. Therefore, in such a series of processing operations, the coated adhesive does not exhibit and remove the initial adhesive force with respect to the cut paper that is the support of the adhesive layer. The pressure-sensitive adhesive layer coated on the support is easily bonded and bonded to the paper substrate on the opposite bonding surface under pressure, but the pressure-sensitive adhesive layer is peeled off when transferred again. Furthermore, during a series of processing operations, it is usually desirable not to exert adhesive force on the surface of a rotary roll type member that is conveyed while being crimped.

そこで、例えば、［特許文献１］には、支持体の紙、合成樹脂フィルムに粘着剤を塗工させ、貼り合わせ、再剥離が可能であるマスキングテープ及びシート、表示ラベル等として各種被着体に貼り付けるに最適な粘着剤が提案されている。このような仕様で用いられる粘着剤は、被着体に対して粘着力を発揮させ、しかも、適宜容易に剥離させることができる。また、剥離後に被着体には、粘着剤を残さず汚染させない粘着剤である。そのために、［特許文献１］には、主成分としてアルキル基の炭素数が４〜１２の（メタ）アクリル酸エステルと、（メタ）アクリル酸、酢酸ビニル、イタコン酸、無水マレイン酸等の共重合可能な不飽和単量体との混合モノマー１００重量部に、１〜１０重量部のリン酸エステル系界面活性剤を含有するアクリル系エマルジョン型の粘着剤が好適に用いられると記載されている。更には、エポキシ化合物、ポリイソシアネート化合物等を架橋剤として添加されることも記載されている。   Therefore, for example, in [Patent Document 1], various adherends such as masking tapes and sheets, display labels, and the like that can be bonded and re-peeled by applying an adhesive to paper or a synthetic resin film of a support. Adhesives that are optimal for pasting to the skin have been proposed. The pressure-sensitive adhesive used in such specifications can exert an adhesive force on the adherend and can be easily peeled off as appropriate. Moreover, it is an adhesive which does not leave the adhesive on the adherend after peeling and does not contaminate the adherend. Therefore, [Patent Document 1] includes co-polymers such as (meth) acrylic acid ester having 4 to 12 carbon atoms in the alkyl group as a main component, (meth) acrylic acid, vinyl acetate, itaconic acid, maleic anhydride and the like. It is described that an acrylic emulsion-type pressure-sensitive adhesive containing 1 to 10 parts by weight of a phosphate ester surfactant is suitably used for 100 parts by weight of a monomer mixed with a polymerizable unsaturated monomer. . Furthermore, it is described that an epoxy compound, a polyisocyanate compound, or the like is added as a crosslinking agent.

また、［特許文献２］には、アルキル基の炭素数が４〜１２のアクリル酸アルキルエステルと、（メタ）アクリロニトリルと、α，β−不飽和カルボン酸とを乳化重合させてなるアクリルエマルジョン及びリン酸エステル系乳化剤を含有する感圧性のアクリルエマルジョン型で、再剥離後に被着体に対する耐糊汚染性に優れる粘着剤が提案されている。特に、リン酸エステル系乳化剤の添加効果は、再剥離性に関連して粘着力の経時向上を抑制させる効果を発揮させて、被着体に対する保持力とバランスさせる成分であると記載されている。   [Patent Document 2] includes an acrylic emulsion obtained by emulsion polymerization of an alkyl acrylate having an alkyl group having 4 to 12 carbon atoms, (meth) acrylonitrile, and an α, β-unsaturated carboxylic acid, and A pressure-sensitive acrylic emulsion type containing a phosphate ester emulsifier has been proposed which is excellent in anti-glue resistance to an adherend after re-peeling. In particular, it is described that the addition effect of the phosphate ester emulsifier is a component that balances the retention strength against the adherend by exerting the effect of suppressing the improvement in adhesive strength over time in relation to the removability. .

また、［特許文献３］には、アルキル基の炭素数が４〜１４の（メタ）アクリル酸アルキルエステルの５０〜９９．９重量％と、支持体への密着性、被着体への初期接着性に係わって、（メタ）アクリル酸、イタコン酸、マレイン酸等のカルボキシル基含有モノマー５〜０．１重量％と、初期接着性に係わって、シクロヘキシル（メタ）アクリレート、イソボニル（メタ）アクリレート、（メタ）アクリル酸グリシジル、（メタ）アクリル酸２−ヒドロキシエチル、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド等の官能性モノマーの０〜４５重量％とを乳化重合させて得られる重合体ラテックス１００重量部に対して、再剥離性や再剥離後の被着体面に対する再接着性（表面保護フィルム、塗装用マスキングテープ、粘着メモ等に有用な再剥離型感圧接着シートを提供できる）のため、特定のリン酸エステル系界面活性剤の０．１〜３重量部とを含有する感圧性の再剥離型の粘着剤が記載されている。   [Patent Document 3] includes 50 to 99.9 wt% of (meth) acrylic acid alkyl ester having 4 to 14 carbon atoms in the alkyl group, adhesion to the support, and initial adhesion to the adherend. Involved in adhesion, 5 to 0.1% by weight of a carboxyl group-containing monomer such as (meth) acrylic acid, itaconic acid, maleic acid, and in relation to initial adhesion, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate Polymer latex 100 obtained by emulsion polymerization of 0 to 45% by weight of a functional monomer such as glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, etc. For parts by weight, re-peelability and re-adhesion to the adherend after re-peeling (re-peeling useful for surface protection film, coating masking tape, adhesive memo, etc. For possible to provide a pressure-sensitive adhesive sheet), removable pressure-sensitive adhesive of the pressure-sensitive containing a 0.1-3 parts by weight of a specific phosphoric ester surfactants have been described.

また、このような感圧接着性で再剥離型粘着剤を用いた用途として、例えば、［特許文献４］には、用紙支持体の両面に、感圧接着剤層を設けた三つ折り圧着ハガキが提案されている。その感圧粘着剤として、天然ゴム系の樹脂である生天然ゴムラテックス、加硫天然ゴムラテックス、また、ＭＭＡをグラフト重合させた天然ゴムラテクス１００重量部に、耐ブロッキング性、印刷インキ受容性に係わって炭カル、カオリン、シリカ、マイカー等の無機充填剤の９０〜４００重量部からなる粘着剤が開示されている。また、接着力の調節、耐ブロッキング性及び滑り性を向上させることから、有機充填剤として、セルロース粉末、各種の澱粉、メタクリル酸メチルビーズ等の粉末を添加させることが記載されている。   Further, as an application using such a pressure-sensitive adhesive and re-peelable pressure-sensitive adhesive, for example, [Patent Document 4] describes a tri-fold pressure-bonded postcard in which a pressure-sensitive adhesive layer is provided on both sides of a paper support. Has been proposed. As the pressure sensitive adhesive, natural rubber latex, vulcanized natural rubber latex, which is a natural rubber resin, and 100 parts by weight of natural rubber latex obtained by graft polymerization of MMA are involved in blocking resistance and printing ink acceptance. An adhesive comprising 90 to 400 parts by weight of an inorganic filler such as charcoal cal, kaolin, silica, or miker is disclosed. In addition, it is described that cellulose powder, various starches, methyl methacrylate beads and other powders are added as organic fillers in order to improve adhesive strength, blocking resistance and slipperiness.

また、［特許文献５］には、乳化重合法で得られる（メタ）アクリル酸エステル系重合体のラテックス１００重量部に、接着力を調整するため５０〜３００重量部の澱粉等の有機充填剤と合成シリカ、タルク、カオリン、マイカー等の無機充填剤とを組合わせ添加させてなる再剥離性接着剤組成物が提案されている。 In [Patent Document 5], an organic filler such as 50 to 300 parts by weight of starch or the like is added to 100 parts by weight of latex of a (meth) acrylic acid ester polymer obtained by an emulsion polymerization method in order to adjust the adhesive force. There has been proposed a releasable adhesive composition comprising a combination of an inorganic filler such as synthetic silica, talc, kaolin, and miker.

また、［特許文献６］には、接着剤樹脂として自己架橋型アクリル系エマルジョンの乾燥物１００重量部に、平均粒子径１〜２０μｍのシリカ、炭カル、カオリンクレー等の無機充填剤と澱粉等の有機充填剤との組合わせ添加量として５〜２５０重量部の充填剤を含有する再剥離性（疑似接着性）の接着剤組成物が提案されている。   [Patent Document 6] describes, as an adhesive resin, 100 parts by weight of a dried product of a self-crosslinking acrylic emulsion, an inorganic filler such as silica, charcoal cal, kaolin clay and starch having an average particle diameter of 1 to 20 μm, starch, and the like. A releasable (pseudoadhesive) adhesive composition containing 5 to 250 parts by weight of a filler as a combination addition amount of the organic filler has been proposed.

特開昭６０−０６７５７９JP 60-0675779 特開２００１−０４０３１３JP 2001-040313 A 特開平０９−３１６４０７JP 09-316407 特開平０８−２３８８７２Japanese Patent Application Laid-Open No. 08-238872 特開平０９−３１００５６JP 09-310056 A 特開平０９−２６３７４３JP 09-263743

以上のように、従来から、多くの分野で、粘着剤の初期接着性（又は一時貼合接着性）で、再剥離性である粘着特性を活かした粘着テープ、粘着フィルム及び粘着シートが、（１）ラベル、レッテル、ステッカ等の貼り合わせ表示部材として、（２）秘密漏洩防止被覆材として、（３）使用前の新規な各種材料面の耐擦傷被覆保護材として、（４）耐汚染、耐錆止め表面保護材としての仕様で、貼り合わせ被覆部材として広く用いられている。   As described above, in many fields, adhesive tapes, adhesive films, and adhesive sheets that take advantage of adhesive properties that are releasable in the initial adhesiveness (or temporary bonding adhesiveness) of adhesives have been ( 1) As a bonded display member for labels, labels, stickers, etc., (2) As a secret leakage prevention coating material, (3) As an anti-scratch coating protection material for various new materials before use, (4) Contamination resistance, It is a specification as a rust-proof surface protective material and is widely used as a bonded covering member.

このような部材を加工及び実使用するに際しては、粘着剤が、粘着剤層の支持体であるテープ状又はフィルム状又はシート状の紙体又は合成樹脂体に、初期粘着力を発揮させて、その支持体から脱着することがなく、一方、この支持体に塗工される粘着剤層は、実使用時の対向貼り合せる面の紙体、合成樹脂体、金属体、セラミック体等のその他の被着体に圧着下に貼合接着され、再剥離時には、その塗工粘着剤層が支持体から剥がれて被着体面に転写されることのない粘着剤であることが望まれる。   When processing and actually using such a member, the pressure-sensitive adhesive exhibits an initial adhesive force on a tape-like or film-like or sheet-like paper body or synthetic resin body that is a support for the pressure-sensitive adhesive layer, On the other hand, the pressure-sensitive adhesive layer applied to the support is not separated from the support, and the other side such as a paper body, a synthetic resin body, a metal body, and a ceramic body on the surface to be oppositely bonded in actual use. It is desirable that the pressure-sensitive adhesive is bonded to the adherend under pressure bonding and the adhesive layer is not peeled off from the support and transferred to the adherend surface at the time of re-peeling.

すなわち、従来から、このような一時貼合接着させた後、再剥離させる仕様で塗工される粘着剤層は、
（１）支持体面から脱着して剥がれずに、ガラス、金属、セラミックス、プラスチック、紙、木材等の平滑な被着体面には、
（２）圧着させることで適宜容易に初期接着性を発揮させ、また、圧着下の貼合接着後に、強制的に剥がさない限り、
（３）粘着剤層は相当する所定の剥離接着力を呈し、
（４）被着体面から適宜容易に再剥離させられる粘着剤特性で、しかも、剥離させるに当たっては、
（５）粘着剤層が支持体面から剥ぎ取られて対向貼り合わせ面である被着体面に転写されない。いわゆる、再剥離時に被着体面に剥ぎ取られて、被着体面を汚染させない粘着剤層であることが重要である。 That is, from the past, after such a temporary pasting adhesion, the adhesive layer applied with the specification to re-peel,
(1) On a smooth adherend surface such as glass, metal, ceramics, plastic, paper, and wood without being detached from the support surface,
(2) The initial adhesiveness can be easily and appropriately exerted by pressure bonding, and after bonding under pressure bonding, unless forcibly removed,
(3) The pressure-sensitive adhesive layer exhibits a corresponding predetermined peel adhesive strength,
(4) Adhesive properties that can be easily re-peeled from the adherend surface, and when peeling,
(5) The pressure-sensitive adhesive layer is peeled off from the support surface and is not transferred to the adherend surface, which is the opposite bonding surface. It is important that the pressure-sensitive adhesive layer is a so-called pressure-sensitive adhesive layer that is peeled off from the adherend surface during re-peeling and does not contaminate the adherend surface.

ところが、粘着剤や、支持体や、被着体等の種類にもよるが、このように、所定の圧着力下に一時貼合接着させて、適宜自在に再剥離ができる。しかも、粘着剤層の剥がれ、転写等による被着体への付着汚染のない耐汚染性等を可能にさせる仕様で、従来から種々提案されている感圧接着性（又は圧着性）の再剥離型粘着剤の粘着特性として、必ずしもその仕様を十分満足させるに至っていない傾向にある。   However, depending on the type of the pressure-sensitive adhesive, the support, the adherend, etc., it can be re-peeled as needed by temporarily bonding and bonding under a predetermined pressure. In addition, it has been proposed to allow various types of pressure-sensitive adhesive (or pressure-bonding) re-peeling, with specifications that enable anti-contamination without adhesion and contamination to the adherend due to peeling of the adhesive layer or transfer. There is a tendency that the specifications of the mold pressure-sensitive adhesive do not necessarily satisfy the specifications sufficiently.

そこで、このような圧着下に初期接着性（又は一時貼合接着性）で、再剥離性で、耐転写性（又は耐汚染性）である粘着特性を、作用効果として活かして、製品を加工させる加工作業時に適宜に反映させてなる粘着剤の用途として、既に上述した如く、近年、その用途動向として、急速に普及している隠蔽ハガキ、親展ハガキ、封書等を挙げることができる。   Therefore, the product is processed by making use of the adhesive properties that are initial adhesiveness (or temporary bonding adhesiveness), removability, and transfer resistance (or contamination resistance) as a working effect under such pressure bonding. As already described above, the application trends of the pressure-sensitive adhesive appropriately reflected at the time of the processing operation to be performed include concealment postcards, confidential postcards, sealed letters and the like that have been rapidly spreading in recent years.

すなわち、これらの貼合製品は、支持体に塗布される粘着剤の観点からは、粘着剤の支持体が帳票用紙であって、貼合させる対向面が被着体の帳票用紙であったり又はその対向面も、粘着剤層を設ける帳票用紙であったりする。しかも、この帳票用紙に塗工される貼合用の粘着剤層は、所定の圧着力下に一時貼合接着され、実使用の経時下に適宜自在に再剥離できる粘着特性が活かされている。
また、従来から、このような貼合製品は、通常、このような仕様を満足させる粘着剤層を設けた二つ折り又は三つ折りされた連続帳票用紙を、シーラーの回転するローラ部に連続供給させながらの圧着・貼合・搬送下に製品化されるのが一般的である。 That is, in these bonding products, from the viewpoint of the pressure-sensitive adhesive applied to the support, the pressure-sensitive adhesive support is a form paper, and the facing surface to be bonded is an adherend form paper or The opposite surface may also be a form paper provided with an adhesive layer. Moreover, the adhesive layer for bonding applied to the form paper is temporarily bonded and bonded under a predetermined pressing force, and the adhesive property that can be re-removed as needed during actual use is utilized. .
In addition, conventionally, such a bonded product usually continuously supplies bi-fold or tri-fold continuous form paper provided with an adhesive layer satisfying such specifications to a rotating roller portion of a sealer. In general, it is made into a product under pressure bonding / bonding / conveying.

従って、特に、このような製品の加工作業時においては、帳票用紙を圧着させながら搬送させるシーラーの回転型のローラ部材面に対して、この支持体用紙に塗工されている粘着剤層が、粘着力を発揮させてローラ面を付着汚染させたり、この粘着剤層が係わって、圧着・貼合・搬送させるシーラーの加工作業性を損ねさせてはならない。   Therefore, particularly when processing such products, the pressure-sensitive adhesive layer coated on the support sheet is applied to the rotating roller member surface of the sealer that conveys the form sheet while being crimped. Do not detract from the roller work surface by exerting adhesive force, or impair the workability of the sealer to be crimped / bonded / conveyed due to this adhesive layer.

しかるに、既に上記した［特許文献１］には、支持体の紙、合成紙、樹脂フィルムに粘着剤を塗工させ、貼り合わせ、再剥離が可能であるマスキングテープ、シート、ラベルとして、各種被着体に貼り付けるに最適な粘着剤が提案されている。このような仕様に用いる粘着剤は、被着体に対しては粘着力があって、容易に再剥離させることができ、しかも、剥離後の被着体には、粘着剤を残さず被着体を汚染させない粘着剤であると記載されている。   However, in the above-mentioned [Patent Document 1], as a masking tape, a sheet, and a label that can be bonded and re-peeled by applying an adhesive to the support paper, synthetic paper, and resin film, various coating materials can be used. The most suitable adhesive for sticking to a kimono has been proposed. The pressure-sensitive adhesive used for such specifications has an adhesive force to the adherend and can be easily removed again, and the adherend without peeling remains on the adherend after peeling. It is described as an adhesive that does not contaminate the body.

更には、［特許文献４］には、粘着剤の支持体であるカット用紙の紙体に、塗工された粘着剤層が、同じく紙体である被着体に感圧下に貼合圧着され、且つこの被着体である紙体から、粘着剤層を設ける支持体のカット用紙に、再剥離できる感圧接着剤層が設けられている三つ折り圧着はがきが開示されている。
その感圧接着性で再剥離型の粘着剤樹脂組成物として、
（１）天然ゴム系の樹脂である生天然ゴムラテックス、加硫天然ゴムラテックス、また、ＭＭＡをグラフト重合させた天然ゴムラテックスの１００重量部に、
（２）炭カル、カオリン、シリカ、マイカー等の無機充填剤の９０〜４００重量部を組合わせてなる粘着剤樹脂組成物で、
更には、接着力の調節、耐ブロッキング性及び滑り性を向上させるためから、
（３）有機充填剤として、セルロース粉末、澱粉、メタクリル酸メチルビーズ等を添加させることが記載されている。 Furthermore, in [Patent Document 4], a coated pressure-sensitive adhesive layer is bonded and pressure-bonded to an adherend, which is also a paper body, under pressure. Also disclosed is a tri-fold pressure-bonded postcard in which a pressure-sensitive adhesive layer that can be peeled again is provided on a cut sheet of a support on which an adhesive layer is provided from a paper body that is an adherend.
As a pressure-sensitive adhesive and re-peelable pressure-sensitive adhesive resin composition,
(1) 100 parts by weight of a natural rubber latex, a natural rubber latex, a vulcanized natural rubber latex, or a natural rubber latex obtained by graft polymerization of MMA,
(2) An adhesive resin composition comprising a combination of 90 to 400 parts by weight of an inorganic filler such as charcoal cal, kaolin, silica, or miker,
Furthermore, in order to improve adhesion control, blocking resistance and slipperiness,
(3) It is described that cellulose powder, starch, methyl methacrylate beads and the like are added as organic fillers.

従って、このように一時的に貼合接着させて、且つ適宜自在に再剥離を可能にさせる粘着剤層特性は、通常の再剥離型粘着剤にとって、従来から発揮されている周知の特性であるとも言える。   Therefore, the pressure-sensitive adhesive layer properties that are temporarily bonded and bonded as described above and can be re-removed as appropriate are well-known properties that have been conventionally demonstrated for ordinary re-peelable pressure-sensitive adhesives. It can also be said.

更には、既に上述する如く、再剥離型の粘着剤であって、シーラーの回転する圧着ローラに加工用紙を供給させながらの圧着・貼合・搬送下に、連続させて製品化される隠蔽ハガキ等の一連の加工作業には、従来から、下記（１）〜（３）の要件を満足する粘着剤であることも周知の事実であるとも言える。
（１）粘着剤層の支持体であるテープ状又はシート状の連続帳票用紙には、初期粘着力を発揮させて脱着することがなく、
（２）一方、その支持体に塗工された塗工粘着剤層は、対向貼り合わせ面の紙体用紙の被着体には貼合接着するが剥がれて転写することがなく、
（３）更には、一連の加工処理時おいては、圧着させながら搬送させる圧着搬送ロール部材面には、少なくとも、粘着力を及ぼすことがなく耐付着汚染性の粘着剤であることが重要である。 Furthermore, as already mentioned above, it is a re-peeling type adhesive, and it is a concealing postcard that is continuously produced under pressure bonding / bonding / conveying while supplying the processed paper to the rotating pressure roller of the sealer. It can also be said that it is a well-known fact that the adhesives satisfy the following requirements (1) to (3) for a series of processing operations such as:
(1) The tape-like or sheet-like continuous form paper that is the support of the pressure-sensitive adhesive layer does not desorb by exhibiting the initial adhesive force,
(2) On the other hand, the coating pressure-sensitive adhesive layer coated on the support does not peel off and transfer to the adherend of the paper sheet on the opposite lamination surface,
(3) Furthermore, at the time of a series of processing, it is important that the pressure-sensitive conveying roll member surface to be conveyed while being pressure-bonded is at least an adhesion-stain-resistant pressure-sensitive adhesive without exerting adhesive force. is there.

また、従来からエマルジョン型又はラテックス型の再剥離型粘着剤として提案されている［特許文献１］〜［特許文献６］の記載からも明らかなように、このような用途に用いる粘着剤の粘着特性として、確かに圧着下に初期接着性（又は一時貼合接着性）で、再剥離性の粘着特性を有する粘着剤であることが開示されている。しかしながら、その粘着特性に係わって、圧着・貼合・搬送下に貼合製品化させる加工作業性について言及すると、連続帳票用紙を、圧着・貼合・搬送させながら製品に加工させるシーラーの回転するローラに係わる加工作業性と、このような仕様を充分に満足させる粘着剤及びその粘着特性との係わりが、必ずしも明確にされていない。   Further, as is apparent from the description of [Patent Document 1] to [Patent Document 6], which has been conventionally proposed as an emulsion-type or latex-type re-peelable pressure-sensitive adhesive, the pressure-sensitive adhesive of the pressure-sensitive adhesive used for such applications is used. As a characteristic, it is disclosed that it is a pressure-sensitive adhesive having an initial adhesiveness (or temporary bonding adhesiveness) and a releasable adhesive property under pressure bonding. However, referring to the workability of making a bonded product under pressure bonding / bonding / conveying due to its adhesive properties, the sealer that turns the continuous form paper into a product while being crimped / bonded / conveyed rotates. The relationship between the workability related to the roller, the pressure-sensitive adhesive sufficiently satisfying such specifications, and the pressure-sensitive adhesive properties are not necessarily clarified.

すなわち、シーラーに連続供給させる二つ折り又は三つ折り等の帳票用紙の片面又は両面には粘着剤層が予め塗工されている。また、通常、隠蔽情報を含め所定の印刷事項がこの粘着剤層を含めて印刷されている。このような用紙を、回転するローラで搬送させながら貼合製品化させるシーラーの加工作業性に対して、この用紙に塗工されている粘着剤層面が、一連の圧着・貼合・搬送の加工作業において、圧着下に一時貼合接着性で、且つ適宜再剥離できる再剥離型である粘着特性とが係わり、加工作業をバランスさせていると理解される。従って、このような帳票用紙に設ける粘着剤層の粘着特性（以後、粘着剤層特性と称す）が、シーラーが果たす加工作業性にどのように係わり、且つどのような粘着剤であればこの加工作業性を満足させられるのか、従来の再剥離型粘着剤には、未だ十分に開示、評価されていないのが実状である。   That is, an adhesive layer is coated in advance on one side or both sides of a bi-fold or tri-fold form paper continuously supplied to the sealer. Further, usually, predetermined printing items including concealment information are printed including the adhesive layer. The adhesive layer coated on this paper has a series of crimping, bonding, and conveyance processes for the workability of the sealer, which makes such a sheet into a bonded product while being conveyed by a rotating roller. In the work, it is understood that the pressure-bonding adhesive property that is temporarily bonded under pressure and is a re-peelable type that can be re-peeled as appropriate, balances the work. Therefore, how the pressure-sensitive adhesive properties (hereinafter referred to as pressure-sensitive adhesive layer properties) of the pressure-sensitive adhesive layer provided on such form paper are related to the workability of the sealer and what pressure-sensitive adhesive is used. Whether the workability can be satisfied, the actual re-peeling adhesive has not yet been sufficiently disclosed and evaluated.

そこで、本発明の目的は、隠蔽ハガキ、親展ハガキ、又は封書の如く支持体の紙体に感圧接着性（又は圧着性）で、再剥離型の粘着剤層を設けるに際して、本発明に用いる貼合・粘着剤層用の粘着剤主成分は、その製法が著しく簡便で、コスト的にも低廉で、支持体に粘着剤用として加工させる又は実使用時のハンドリング及び作業性に優れ、しかも、その粘着剤層には所定の印刷及び印字を可能にさせる（メタ）アクリル酸エステル系エマルジョンを粘着剤主成分とする圧着性再剥離型の粘着剤組成物を提供させることである。   Therefore, an object of the present invention is to use in the present invention when a re-peelable pressure-sensitive adhesive layer is provided on a paper body of a support such as a concealment postcard, a confidential postcard, or a sealed letter. The main component of the adhesive for the adhesive / adhesive layer is extremely simple in its production method, low in cost, processed into a support for adhesive, or excellent in handling and workability in actual use. The pressure-sensitive adhesive layer is to provide a pressure-sensitive adhesive re-peelable pressure-sensitive adhesive composition having a (meth) acrylic acid ester emulsion as a main component of the pressure-sensitive adhesive that enables predetermined printing and printing.

すなわち、このような用途に適材として提供させる本発明による圧着性再剥離型の貼合用粘着剤組成物にとって、従来から一層改善すべき重要課題としては、その貼合製品加工性に係わって、圧着・貼合・搬送させるシーラーの回転型ローラに係わって、粘着剤層を設ける二つ折り又は三折り状態の連続帳票である加工用紙を連続させて圧着・貼合・搬送させながら隠蔽ハガキ、親展ハガキ、封書等に製品加工させる加工作業性に優れる粘着剤組成物を提供させることである。   That is, for the pressure-sensitive adhesive peelable adhesive composition according to the present invention to be provided as a suitable material for such applications, as an important issue to be further improved from the past, in connection with the processability of the bonded product, Concealed postcards and confidential documents that are related to the rotating roller of the sealer that is crimped, bonded, and transported, and is processed continuously as a bi-fold or tri-fold continuous form with an adhesive layer, while being crimped, bonded, and transported. It is to provide a pressure-sensitive adhesive composition excellent in processing workability for processing a product on a postcard, a sealed letter or the like.

また、本発明の他の目的は、このようにシーラーの加工作業性を阻害させない粘着剤層で、印刷層として設けている隠蔽ハガキ、親展ハガキ、封書等を提供させることである。   Another object of the present invention is to provide a concealing postcard, confidential postcard, sealed letter, etc. provided as a printing layer with an adhesive layer that does not impair the workability of the sealer.

そこで、本発明者は、これらの課題を鋭意検討した結果、このような加工作業を行う回転型圧着搬送ローラなるシーラーを介して、例えば、連続させて親展三つ折りハガキや、三つ折り封書を貼合加工させるに際しては、単に、この圧着搬送させるシーラーの回転ローラによる圧着貼合性、また、ローラ部での回転搬送性を評価するにとどまらない。   Therefore, as a result of earnest examination of these problems, the present inventor, for example, continuously puts a confidential three-fold postcard or a three-fold sealed letter through a sealer that is a rotary pressure-conveying and carrying roller that performs such a processing operation. When performing the combined processing, it is not only to evaluate the pressure bonding property by the rotating roller of the sealer to be conveyed by pressure bonding and the rotation conveying property at the roller portion.

すなわち、連続的に供給・搬送される帳票用紙面には、粘着剤層特性として圧着下に貼合接着性で、再剥離性である粘着剤層が塗工されている。そこで、本発明者は、その粘着剤層特性を、シーラーの回転する圧着ローラ面に対しては、耐付着汚染性で、耐粘着性であるようにバランスさせることに着目させて、帳票用紙を連続供給させて、しかも、連続させて効果的に貼り合わせ搬送させるシーラーの加工作業性を、著しく左右させることを見出して、ハガキや、封書としての印刷適性を有し、ハガキや、封書として貼合製品化時又は実使用時のハンドリング性に優れる圧着再剥離型粘着剤層用に所望する粘着剤組成物を発明するに至った。   That is, the surface of the form paper that is continuously supplied / conveyed is coated with a pressure-sensitive adhesive layer that is adhesively bonded and removable under pressure bonding. Therefore, the present inventor made the form sheet suitable for balancing the adhesive layer characteristics with the adhesion roller resistance and the adhesion resistance against the rotating pressure roller surface where the sealer rotates. We found that the workability of the sealer, which is continuously supplied and continuously and effectively bonded and transported, greatly affects the workability of the sealer, and has printability as a postcard and sealed letter, and is pasted as a postcard and sealed letter. The inventors have invented a desired pressure-sensitive adhesive composition for a pressure-removable pressure-sensitive adhesive layer that is excellent in handling properties at the time of commercialization or actual use.

本発明によれば、片面又は両面に、印刷適性を有し、取り扱いハンドリング性を損ねない粘着剤層を設ける二つ折り又は三つ折り連続帳票用紙を搬送させながら貼合加工させて、隠蔽ハガキ、親展ハガキ、封書等の製品に加工させるに際して、シーラーに連続して加工用紙を供給させて製品に貼合加工させるシーラーの圧着・貼合・搬送なる加工作業性を損ねることなく、連続させて効果的に貼合製品化される「シーラー加工性」に優れることを特徴とする貼合用圧着性再剥離型の粘着剤組成物を提供する。   According to the present invention, a half-fold or three-fold continuous form sheet that is provided with an adhesive layer that has printability on one side or both sides and that does not impair handling handling properties is bonded while carrying a concealment postcard, confidential When processing into products such as postcards, sealed letters, etc., it is effective to continuously supply the processing paper to the sealer and bond it to the product without damaging the workability of the sealer's crimping, bonding, and conveyance. The present invention provides a pressure-bonding re-peelable pressure-sensitive adhesive composition for bonding, which is excellent in “sealer processability” which is made into a bonded product.

すなわち、本発明によって提供する粘着剤組成物は、
（１）アルキル基の炭素数が１〜１２の（メタ）アクリル酸アルキルエステル（ａ）の９０〜９８．９５重量部と、
（２）カルボキシル基含有モノマー（ｂ）の１〜５重量部と、
（３）エポキシ基、水酸基、シラノール基及びメチロール基から選ばれる何れかの官能基を有するモノマー（ｃ）の０．０５〜５重量部とを用いて乳化重合させた（メタ）アクリル酸エステル系エマルジョンで、そのゲル分率が６０％以上８５％以下の範囲にあって粘着剤主成分（Ａ）として、その乾燥物基準の１００重量部当たり、リン酸エステル系界面活性剤（Ｂ）の０．５〜５重量部と、有機系及び無機系微細粉末とを組合わせた充填剤（Ｃ）の４０〜３００重量部とを含有している圧着性の再剥離型粘着剤組成物である。 That is, the pressure-sensitive adhesive composition provided by the present invention is:
(1) 90 to 98.95 parts by weight of an alkyl group (meth) acrylic acid alkyl ester (a) having 1 to 12 carbon atoms;
(2) 1 to 5 parts by weight of the carboxyl group-containing monomer (b);
(3) (meth) acrylic acid ester system emulsion-polymerized with 0.05 to 5 parts by weight of monomer (c) having any functional group selected from epoxy group, hydroxyl group, silanol group and methylol group In the emulsion, the gel fraction is in the range of 60 % or more and 85% or less , and 0 % of the phosphate ester surfactant (B) per 100 parts by weight of the dry matter basis as the adhesive main component (A). It is a pressure-removable pressure-sensitive adhesive composition containing 5 to 5 parts by weight and 40 to 300 parts by weight of a filler (C) obtained by combining organic and inorganic fine powders.

また、本発明によれば、このような本発明による圧着性の再剥離型粘着剤組成物を、二つ折り又は三つ折り連続帳票用紙の片面又は両面に粘着剤層で印刷層として、塗工膜厚１〜５０μmの範囲で設けていることを特徴する隠蔽ハガキ又は封書を提供する。   Further, according to the present invention, the pressure-removable pressure-sensitive adhesive composition according to the present invention is applied as a printing layer with a pressure-sensitive adhesive layer on one or both sides of a bi-fold or tri-fold continuous form paper. Provided is a concealment postcard or a sealed letter characterized by being provided in a thickness range of 1 to 50 μm.

以上から、このように提供する本発明による圧着性再剥離型の粘着剤組成物は、所定の圧着力下に、一時的に貼合接着させることができ、且つ適宜自在に再剥離できる粘着剤である。しかも、貼合接着時の被着体に対しては、耐付着汚染性である粘着剤機能を必要とする貼合用の粘着剤としての用途に最適な圧着性再剥離型の粘着剤である。このような仕様を必要条件とする粘着剤の用途として、本発明の圧着性再剥離型の粘着剤組成物は、例えば、隠蔽ハガキや、親展ハガキや、封書の貼合用の粘着剤層に好適に用いることができる。   As described above, the pressure-sensitive adhesive re-peelable pressure-sensitive adhesive composition according to the present invention thus provided can be temporarily bonded and bonded under a predetermined pressure and can be re-peeled as appropriate. It is. Moreover, it is a pressure-sensitive adhesive re-peelable pressure-sensitive adhesive that is optimal for use as a pressure-sensitive adhesive for bonding, which requires a pressure-sensitive adhesive function that is resistant to adhesion and contamination. . As an application of the pressure-sensitive adhesive having such a specification as a necessary condition, the pressure-sensitive adhesive re-peelable pressure-sensitive adhesive composition of the present invention can be used, for example, as a concealing postcard, a confidential postcard, or a pressure-sensitive adhesive layer for sealing a sealed letter. It can be used suitably.

しかも、本発明による圧着性再剥離型の粘着剤組成物は、このような貼合製品に用いる粘着剤として、貼合加工させて製品化させるに際しては、シーラーの回転型ローラを介して、粘着剤層を設ける二つ折り又は三つ折り状態の連続帳票用紙を、圧着下に搬送させながら製品化させる加工作業性を全く阻害させないことから、効率よく貼合製品化させることができる。   Moreover, the pressure-sensitive adhesive re-peelable pressure-sensitive adhesive composition according to the present invention is used as a pressure-sensitive adhesive for such a bonded product, and is bonded through a sealer rotary roller when commercialized by bonding. Since the bi-fold or tri-fold continuous form paper provided with the agent layer is not disturbed at all by the processing workability to be commercialized while being conveyed under pressure bonding, it can be efficiently made into a bonded product.

更には、この用紙に設ける本発明による粘着剤層面には、例えば、インクジェット・プリンターや、通常の印刷法で良好な印字、印刷を形成させることから、隠蔽ハガキ、親展ハガキ、封書として設ける粘着剤層には、宛名情報や、隠蔽面の隠蔽情報を記載する印刷層としての印刷適性を有する粘着剤層を設けることができる。   Furthermore, the pressure-sensitive adhesive layer according to the present invention provided on the paper is provided with, for example, an ink jet printer or a normal printing method so that good printing and printing can be performed. The layer can be provided with a pressure-sensitive adhesive layer having printability as a print layer for describing address information and concealment surface concealment information.

このような仕様、機能を果たす本発明が提供する圧着性で、再剥離性である粘着剤組成物中の粘着剤主成分（Ａ）は、（メタ）アクリル酸エステル系エマルジョンで、且つゲル分率が６０〜９０％の範囲にある樹脂質成分を、粘着剤層の主粘着剤成分としている。更に、リン酸エステル系界面活性剤と、澱粉等の有機系微粉末と吸油性のある多孔質シリカ粉末等の無機系微粉末を組合わせた充填剤を含有しているものである。特に、実使用時に支持体面に設けた粘着剤層面同士を、貼合させても、再剥離時には、互いの再剥離性を阻害させない耐ブロッキング適性を発揮させることが特徴である。また、この耐ブロッキング適性に係わって、本発明による粘着剤層は、圧着下に貼合接着し、且つ再剥離されるに伴い、この耐ブロッキング適性に係わって、シーラーの回転ローラ面に対しては、耐付着汚染性を発揮させる。   The pressure-sensitive adhesive and re-peelable pressure-sensitive adhesive composition (A) provided by the present invention that fulfills such specifications and functions is a (meth) acrylate emulsion and has a gel content. The resinous component having a rate in the range of 60 to 90% is used as the main adhesive component of the adhesive layer. Furthermore, it contains a filler in which a phosphate ester-based surfactant, an organic fine powder such as starch, and an inorganic fine powder such as an oil-absorbing porous silica powder are combined. In particular, even if the pressure-sensitive adhesive layer surfaces provided on the support surface during actual use are bonded to each other, the anti-blocking property that does not impair each other's re-peelability is exhibited at the time of re-peeling. Also, in connection with this blocking resistance, the pressure-sensitive adhesive layer according to the present invention is bonded and bonded under pressure bonding, and re-peeled. Exhibits anti-fouling resistance.

本発明においては、このような組成からなる粘着剤を片面又は両面に塗布加工させた二つ折り又は三つ折り状態の連続帳票用紙を、シーラーの回転するローラに連続供給させて、回転ロール間で圧着・貼合させながら連続帳票用紙を搬送させる一連の圧着・貼合・搬送の加工作業性を阻害させることなく、著しく効率よく貼合製品として搬出させる。   In the present invention, a bi-fold or tri-fold continuous form sheet obtained by applying an adhesive having such a composition on one or both sides is continuously supplied to a rotating roller of a sealer, and is pressed between rotating rolls. -A series of crimping / bonding / conveying processes that convey continuous form paper while bonding are carried out as a bonded product extremely efficiently without impeding the workability of the process.

従って、このような連続帳票用紙に粘着剤層として設ける本発明による再剥離型粘着剤組成物は、シーラーの圧着・貼合・搬送させる一連の加工作業性を阻害させず、貼合製品化効率を著しく向上させることから、本発明においては、この用紙に設ける粘着剤層の粘着特性に起因して、シーラーが果たすべき加工作業性を左右させている事実から、このような用途に設けた貼合用の粘着剤層は、後述する実施例において定義した「シーラー加工性」を充分に発揮させると評価できる。   Therefore, the re-peelable pressure-sensitive adhesive composition according to the present invention provided as an adhesive layer on such continuous form paper does not hinder a series of work workability for pressure bonding / bonding / conveying of the sealer, and the efficiency of bonding product production Therefore, in the present invention, due to the adhesive property of the adhesive layer provided on the paper, the workability that the sealer should perform is influenced. It can be evaluated that the combined pressure-sensitive adhesive layer sufficiently exhibits “sealer processability” defined in Examples described later.

すなわち、本発明による優れた「シーラー加工性」を有する圧着性の再剥離型粘着剤組成物は、少なくとも、この連続帳票用紙の片面又は両面に粘着剤層として設けた加工支持体用紙を、シーラーに連続供給させて圧着・貼合・搬送させながら、高効率で貼合製品化させる粘着剤層として用いられる。   That is, the pressure-removable pressure-sensitive adhesive composition having excellent “sealer processability” according to the present invention comprises at least a processing support sheet provided as an adhesive layer on one side or both sides of the continuous form sheet. It is used as a pressure-sensitive adhesive layer that is made into a bonded product with high efficiency while being continuously supplied to and bonded and transported.

以下に、本発明による二つ折り又は三つ折り連続帳票用紙を貼合搬送させるに用いられる印刷適性を有し、「シーラー加工性」に優れる圧着性の再剥離型の粘着剤組成物を実施する最良の形態について更に説明する。   Below, it is the best to implement a pressure-removable pressure-sensitive adhesive composition having printability and excellent “sealer processability” used for laminating and conveying a bi-fold or tri-fold continuous form paper according to the present invention. The embodiment will be further described.

既に上述する如く、本発明による圧着性再剥離型の粘着剤組成物は、片面又は両面に粘着剤層として設ける二つ折り又は三つ折り連続帳票用紙を連続して搬送貼り合わせさせて、隠蔽ハガキ又は封書に製品加工させるに際して、搬送貼合なる加工作業を実施させる回転型ローラであるシーラーが係わる加工作業性を、低下させず効果的に実施させることを特徴とする粘着剤組成物である。すなわち、このような粘着剤層を設ける連続帳票用紙を、回転型ローラのシーラー部に連続供給させて、このシーラーで圧着搬送させながら貼合製品化させるに際して、効果的な加工作業性を発揮させるいわゆる「シーラー加工性」に優れる圧着性再剥離型の粘着剤組成物を提供することができた。   As already mentioned above, the pressure-sensitive adhesive re-peelable pressure-sensitive adhesive composition according to the present invention is a concealed postcard or a double-fold or tri-fold continuous form sheet provided as a pressure-sensitive adhesive layer on one or both sides. A pressure-sensitive adhesive composition characterized in that when a sealed letter is processed into a product, the workability related to a sealer, which is a rotary roller for carrying out a work process of conveying and bonding, is effectively carried out without deteriorating. That is, when a continuous form paper provided with such an adhesive layer is continuously supplied to a sealer part of a rotary roller and is made to a bonded product while being pressure-bonded and conveyed by this sealer, an effective workability is exhibited. It was possible to provide a pressure-sensitive adhesive re-peelable pressure-sensitive adhesive composition excellent in so-called “sealer processability”.

そこで、既に上述した本発明による「シーラー加工性」に優れる圧着性再剥離型の粘着剤組成物は、以下の組成で構成されている。   Therefore, the pressure-bonding / removable pressure-sensitive adhesive composition having excellent “sealer processability” according to the present invention described above has the following composition.

その粘着剤主成分（Ａ）の構成及び特性は、如何なる温度及び湿度の自然環境下においても容易に剥離される観点から、ゲル分率が６０〜９０％の範囲にあることが重要で、好ましくは、このゲル分率が７０％以上である（メタ）アクリル酸エステル系エマルジョンであることが適宜好適に使用することができる。   The composition and characteristics of the main component (A) of the pressure sensitive adhesive are important in that the gel fraction is in the range of 60 to 90% from the viewpoint of easy peeling under a natural environment of any temperature and humidity. Can be suitably used preferably as a (meth) acrylic acid ester emulsion having a gel fraction of 70% or more.

本発明において、このようなゲル分率特性を有する粘着剤主成分は、以下に記載する（１）アルキル基の炭素数が１〜１２の（メタ）アクリル酸アルキルエステルであり、好ましくはアルキル基の炭素数が１〜４の（メタ）アクリル酸アルキルエステル（ａ）と、（２）カルボキシル基含有モノマー（ｂ）と、（３）エポキシ基、水酸基、シラノール基及びメチロール基から選ばれる何れかの官能基を有するモノマー（ｃ）とを用いて、従来から公知である通常の乳化重合法によって調製されたアクリル系エマルジョンを適宜好適に用いられる。   In the present invention, the main component of the pressure-sensitive adhesive having such a gel fraction characteristic is (1) (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms in the alkyl group described below, preferably an alkyl group. (Meth) acrylic acid alkyl ester (a) having 1 to 4 carbon atoms, (2) a carboxyl group-containing monomer (b), and (3) any one selected from an epoxy group, a hydroxyl group, a silanol group, and a methylol group An acrylic emulsion prepared by a conventional emulsion polymerization method conventionally known using the monomer (c) having the above functional group is suitably used.

本発明に用いる（１）の（メタ）アクリル酸アルキルエステル（ａ）としては、例えば、（メタ）アクリル酸メチル，（メタ）アクリル酸エチル，（メタ）アクリル酸プロピル，（メタ）アクリル酸イソプロピル，（メタ）アクリル酸ブチル，（メタ）アクリル酸イソブチル，（メタ）アクリル酸ペンチル，（メタ）アクリル酸ヘキシル，（メタ）アクリル酸２−エチルヘキシル，（メタ）アクリル酸オクチル，（メタ）アクリル酸ラウリル，（メタ）アクリル酸ノニル，（メタ）アクリル酸デシル，（メタ）アクリル酸ドデシル，
また、上記する炭素数とは、メチル基、エチル基、プロピル基、ブチル基、イソブチル基、イソアミル基、ヘキシル基、ヘプチル基、イソオクチル基、イソノニル基、イソデシル基等のアルキル基の炭素数である。 Examples of (1) (meth) acrylic acid alkyl ester (a) used in the present invention include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate. , Butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid Lauryl, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate,
The carbon number is the carbon number of an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, an isoamyl group, a hexyl group, a heptyl group, an isooctyl group, an isononyl group, or an isodecyl group. .

本発明においては、これらの単独又は２種以上の（メタ）アクリル酸アルキルエステル（ａ）を適宜用いられる。その中でも必ずしも限定する必要性はないが、本発明においては、例えば、初期接着性及び再剥離性の観点から、好ましくは、アルキル基の炭素数が４以下の（メタ）アクリル酸アルキルエステル（ａ）であって、特に好ましくは、ＢＡを主成分に、ＥＡ及び／又はＭＭＡの副成分を混合成分とすることがより好適である。また、これらの（メタ）アクリル酸エステル（ａ）は、９０〜９８．９５重量部の範囲で使用され、この範囲外の使用量では乳化重合で得られる（メタ）クリル酸エステル系エマルジョンは、粘着性に係わって、初期接着性が不足ぎみになる傾向で、特に、高湿度環境下に接着性が不良となって好ましくない。   In this invention, these single or 2 or more types of (meth) acrylic-acid alkylester (a) is used suitably. Among them, although it is not necessarily limited, in the present invention, for example, from the viewpoint of initial adhesiveness and removability, an alkyl group (meth) acrylic acid alkyl ester having a carbon number of 4 or less (a) In particular, it is more preferable that BA is a main component and EA and / or MMA subcomponents are mixed components. Further, these (meth) acrylic acid esters (a) are used in the range of 90 to 98.95 parts by weight, and (meth) acrylic acid ester emulsions obtained by emulsion polymerization when used outside this range, The initial adhesiveness tends to be insufficient due to the tackiness, and the adhesiveness becomes poor particularly in a high humidity environment, which is not preferable.

本発明に用いる（２）のカルボキシル基含有モノマー（ｂ）としては、例えば、（メタ）アクリル酸、テトラヒドロフタル酸、イタコン酸、シトラコン酸、クロトン酸、イソクロトン酸、マレイン酸、フマル酸、ノルボルネンジカルボン酸及びこれらの誘導体としての無水マレイン酸、無水イタコン酸、無水シトラコン酸、テトラヒドロ無水フタル酸、メタクリル酸アミノエチル、メタクリル酸アミノプロピル等を挙げることができる。これらのカルボキシル基含有モノマー（ｂ）は、１〜５重量部の範囲で適宜好適に使用される。この範囲外の使用量では乳化重合で得られるアクリル酸エステル系エマルジョン型樹脂は、粘着性が不良となって好ましくない。   Examples of the carboxyl group-containing monomer (b) used in the present invention (2) include (meth) acrylic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, norbornene dicarboxylic acid. Mention may be made of maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, aminoethyl methacrylate, aminopropyl methacrylate and the like as acids and derivatives thereof. These carboxyl group-containing monomers (b) are suitably used suitably in the range of 1 to 5 parts by weight. If the amount is outside this range, the acrylate emulsion type resin obtained by emulsion polymerization is not preferred because of poor adhesion.

また、本発明に用いる（３）のエポキシ基、水酸基、シラノール基及びメチロール基から選ばれる何れかの官能基を有するモノマー（ｃ）の内、エポキシ基含有モノマーとしては、例えば、グリシジル（メタ）アクリレート、３，４−エポキシ−１−ブテン、３，４−エポキシ−３−メチル−１−ブテン、３，４−エポキシ−１−ペンテン、３，４−エポキシ−３−メチル−１−ペンテン、５，６−エポキシ−１−ヘキセン、ビニルシクロヘキセンモノオキシド等のエポキシ基含有モノマーを挙げることができる。   Among the monomers (c) having any functional group selected from the epoxy group, hydroxyl group, silanol group and methylol group (3) used in the present invention, examples of the epoxy group-containing monomer include glycidyl (meth). Acrylate, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, Mention may be made of epoxy group-containing monomers such as 5,6-epoxy-1-hexene and vinylcyclohexene monoxide.

また、水酸基含有モノマーとしては、例えば、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸４−ヒドロキシブチル、クロロ−２−ヒドロキシプロピルアクリレート、ジエチレングリコールモノ（メタ）アクリレート、1,1,1-トリヒドロキシメチルエタントリアクリレート，1,1,1-トリスヒドロキシメチルメチルエタントリアクリレート，1,1,1-トリスヒドロキシメチルプロパントリアクリレート、ヒドロキシビニルエーテル，ヒドロキシプロピルビニルエーテル，ヒドロキシブチルビニルエーテル等のヒドロキシアルキルビニルエーテル等を挙げることができる。   Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, chloro-2-hydroxypropyl acrylate, and diethylene glycol mono (Meth) acrylate, 1,1,1-trihydroxymethylethane triacrylate, 1,1,1-trishydroxymethylmethylethane triacrylate, 1,1,1-trishydroxymethylpropane triacrylate, hydroxy vinyl ether, hydroxypropyl Examples thereof include hydroxyalkyl vinyl ethers such as vinyl ether and hydroxybutyl vinyl ether.

また、シラノール基含有モノマーとして、例えば、アルコキシシラン、アシロキシシラン、シランカップリング剤、シリル化剤等のシラン化合物が挙げられる。アルコキシシランとしては、Ｓｉ(ＯＭｅ)4 ，ＭｅＳｉ(ＯＭｅ)3 ，Ｍｅ２Ｓｉ(ＯＭｅ)２，Ｍｅ３Ｓｉ(ＯＭｅ) ，Ｃ２Ｈ５Ｓｉ(ＯＭｅ)3 ，ｎ−Ｃ3Ｈ7Ｓｉ(ＯＭｅ)3 ，ｎ−Ｃ6Ｈ13Ｓｉ(ＯＭｅ)3 ，ｎ−Ｃ10Ｈ21Ｓｉ(ＯＭｅ)3 ，ＣＨ２=ＣＨＳｉ(ＯＭｅ)3 ，Ｃ6Ｈ5Ｓｉ(ＯＭｅ)3 ，(Ｃ6Ｈ5)２Ｓｉ(ＯＭｅ)２ 、また、シランカップリング剤としては、ＮＨ２ＣＨ２ＣＨ２ＮＨＣＨ２ＣＨ２ＣＨ２ＭｅＳｉ(ＯＭｅ)3 ，ＮＨ２ＣＨ２ＣＨ２ＮＨＣＨ２ＣＨ２ＣＨ２ＳｉＭｅ(ＯＭｅ)２，ＨＳＣＨ２ＣＨ２ＣＨ２Ｓｉ(ＯＭｅ)3 ，Ｃ６Ｈ５ＮＨＣＨ２ＣＨ２ＣＨ２Ｓｉ(ＯＭｅ)3 ，ＣＨ２＝(ＣＨ３)ＣＣＯＯＣＨ２ＣＨ２ＣＨ２Ｓｉ(ＯＭｅ)3 、また、Ｓｉ(ＯＥｔ)4 ，ＭｅＳｉ(ＯＥｔ)3 ，Ｍｅ２Ｓｉ(ＯＥｔ)２ ，Ｍｅ３ＳｉＯＥｔ等が挙げられ、また、アシロキシシランとしては、ＭｅＳｉ(ＯＣＯＣＨ３)３，Ｃ２Ｈ５Ｓｉ(ＯＭｅ) ３，ＣＨ２=ＣＨＳｉ(ＯＣＯＣＨ３)３ 等が挙げられる。
更に、メチロール基含有モノマーとして、例えば、Ｎ−メチロールアクリドアミド、Ｎ−メチロールメタクリルアミド等を挙げることができる。 Examples of the silanol group-containing monomer include silane compounds such as alkoxysilane, acyloxysilane, silane coupling agent, and silylating agent. Alkoxysilanes include Si (OMe) 4 , MeSi (OMe) 3 , Me 2 Si (OMe) 2 , Me 3 Si (OMe), C 2 H 5 Si (OMe) 3 , n-C 3 H 7 Si ( OMe) 3, n-C 6 H 13 Si (OMe) 3, n-C 10 H 21 Si (OMe) 3, CH 2 = CHSi (OMe) 3, C 6 H 5 Si (OMe) 3, (C 6 H 5 ) 2 Si (OMe) 2 , and silane coupling agents include NH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 MeSi (OMe) 3 , NH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 SiMe (OMe) 2 , HSCH 2 CH 2 CH 2 Si (OMe) 3 , C 6 H 5 NHCH 2 CH 2 CH 2 Si (OMe) 3 , CH 2 = (CH 3 ) CCOOCH 2 CH 2 CH 2 Si (OMe) 3, also, Si (OEt) 4, MeSi (OEt) 3, e 2 Si (OEt) 2, Me 3 SiOEt and the like, As the acyloxysilane, MeSi (OCOCH 3) 3, C 2 H 5 Si (OMe) 3, CH 2 = CHSi (OCOCH 3) 3 Etc.
Furthermore, examples of the methylol group-containing monomer include N-methylol acrylamide and N-methylol methacrylamide.

また、上記（１）〜（３）のモノマー１００重量部に対して、その他のモノマー０〜１０重量部程度を共重合させても良い。その他のモノマーとして、（メタ）アクリル酸フェニル，（メタ）アクリル酸メトキシエチル，（メタ）アクリル酸エトキシエチル，（メタ）アクリル酸プロポキシエチル，（メタ）アクリル酸ブトキシエチル，（メタ）アクリル酸エトキシプロピル等の（メタ）アクリル酸アルコキシエステル；ジエチルアミノエチル（メタ）アクリレート等のジアルキルアミノアルキル（メタ）アクリレート；（メタ）アクリルアミド；Ｎ−メチロール（メタ）アクリルアミド及びジアセトンアクリルアミド等の（メタ）アクリルアミド類；エチレングリコールのジアクリル酸エステル、ジエチルグリコールのジアクリル酸エステル、トリエチレングリコールのジアクリル酸エステル、ポリエチレングリコールのジアクリル酸エステル、ジプロピレングリコールのジアクリル酸エステル、トリプロピレングリコールのジアクリル酸エステル等の（ポリ）アルキレングリコールのジアクリル酸エステル類等を挙げることができる。   Further, about 0 to 10 parts by weight of other monomers may be copolymerized with respect to 100 parts by weight of the monomers (1) to (3). Other monomers include phenyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxy (meth) acrylate (Meth) acrylic acid alkoxyesters such as propyl; dialkylaminoalkyl (meth) acrylates such as diethylaminoethyl (meth) acrylate; (meth) acrylamides; (meth) acrylamides such as N-methylol (meth) acrylamide and diacetone acrylamide Ethylene glycol diacrylate, diethyl glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol It can be mentioned diacrylate esters Lumpur, such as diacrylate esters of tripropylene glycol (poly) diacrylate esters of alkylene glycols, and the like.

そこで、本発明においては、これら（３）のエポキシ基、水酸基、シラノール基及びメチロール基から選ばれる何れかの官能基を有するモノマー（ｃ）は、０．０５〜５重量部の範囲で適宜好適に用いて乳化重合させることができる。また、これらの共重合可能なモノマー（ｃ）は、従来からアクリル系粘着剤が、通常、凝集性に欠ける傾向にあり、本発明においては、粘着剤主成分である乳化重合で得られる（メタ）アクリル酸エステル系エマルジョンの架橋度を調整させて凝集力を増大させる効果を発揮させて凝集力をバランスさせる作用を発揮させることから、添加量が、０．０５〜５重量部の範囲外の使用量では、架橋度を充分に調整させて凝集力を向上、バランスさせる観点において好ましくない。   Therefore, in the present invention, the monomer (c) having any functional group selected from the epoxy group, hydroxyl group, silanol group and methylol group of (3) is suitably suitable in the range of 0.05 to 5 parts by weight. Can be used for emulsion polymerization. In addition, these copolymerizable monomers (c) are conventionally obtained by emulsion polymerization, which is the main component of the pressure-sensitive adhesive, in the present invention. ) Since the effect of increasing the cohesive force by adjusting the degree of crosslinking of the acrylate emulsion and exerting the effect of balancing the cohesive force, the addition amount is outside the range of 0.05 to 5 parts by weight. The amount used is not preferable from the viewpoint of sufficiently adjusting the degree of crosslinking to improve and balance the cohesive force.

以上から、本発明においては、このように調製した（メタ）アクリル酸エステル系エマルジョンを粘着剤主成分（Ａ）として用いることで、本発明が提供する「シーラー加工性」に優れる圧着性の再剥離型粘着剤組成物は、既に上述する如く、ゲル分率が６０〜９０％の範囲にある粘着剤主成分（Ａ）の１００重量部当たり、リン酸エステル系界面活性剤（Ｂ）が０．５〜５重量部の範囲で、好ましくは、１〜２重量部を適宜含有させる。   From the above, in the present invention, by using the (meth) acrylic ester emulsion prepared in this way as the main component of the pressure-sensitive adhesive (A), it is possible to restore the pressure-bonding property excellent in “sealer processability” provided by the present invention. As already described above, the release-type pressure-sensitive adhesive composition has 0 phosphoric ester surfactant (B) per 100 parts by weight of the pressure-sensitive adhesive main component (A) having a gel fraction in the range of 60 to 90%. In the range of 5 to 5 parts by weight, preferably 1 to 2 parts by weight is appropriately contained.

リン酸エステル系界面活性剤（Ｂ）としては、例えば、アルキルポリオキシエチレンリン酸アルキルフェノールポリオコシエチレンリン酸、アルキルポリオキシエチレンリン酸塩、アルキルフェノールポリオキシエチレンリン酸塩等が挙げられ、それぞれ単独又は２種以上を混合させて用いることができる。本発明においては、下限値０．５未満では、粘着剤層として接着力の経時的な上昇性が大きくなり、再剥離性を阻害させる。また上限値５を超えると接着性を低下阻害させる傾向にある。また、再剥離後の被着体表面を汚染させる傾向にあって、何れも好ましくない。   Examples of the phosphate ester-based surfactant (B) include alkyl polyoxyethylene phosphate alkylphenol polyoxyethylene phosphate, alkyl polyoxyethylene phosphate, alkylphenol polyoxyethylene phosphate, and the like. Or 2 or more types can be mixed and used. In the present invention, if the lower limit value is less than 0.5, the adhesive force increases with time as the pressure-sensitive adhesive layer, and re-peelability is inhibited. On the other hand, when the upper limit value of 5 is exceeded, the adhesiveness tends to be lowered and inhibited. Further, it tends to contaminate the adherend surface after re-peeling, and neither is preferable.

更に、本発明による圧着性の再剥離型粘着剤組成物は、貼合加工させる用途にもよるが、有機系及び無機系微粉末とを組合わせた充填剤（Ｃ）が４０〜３００重量部の範囲で、好ましくは、７０〜２５０重量部で、更に好ましくは１００〜２００重量部を含有させた粘着剤組成物である。   Furthermore, the pressure-removable pressure-sensitive adhesive composition according to the present invention has 40 to 300 parts by weight of a filler (C) combined with organic and inorganic fine powders, depending on the purpose of bonding. The pressure-sensitive adhesive composition preferably contains 70 to 250 parts by weight, more preferably 100 to 200 parts by weight.

この粘着剤組成物による塗工粘着剤層中で非接着成分である有機系及び無機系微粉末の組み合わせ充填剤（Ｃ）は、有機系及び無機系微粉末の組み合わせ充填剤（Ｃ）として添加されている。本発明において、有機系微粉末としては、接着力の調節、耐ブロッキング性を向上させる等の観点から、比較的に粒子形状が不揃いで、粒子表面が凹凸で、平均粒子径が５〜４０μｍの範囲にある有形系充填剤を用いられる。例えば、スチレン系樹脂粉末、アクリル系樹脂粉末、セルロース粉末、サツマイモ、馬鈴薯、小麦、トウモロコシ、米、タピオカ等の澱粉粉末を挙げることができる。中でも本発明においては、粘着剤層の粘着剤主成分が、乳化重合による水性エマルジョンとの親和性や、低廉であることから澱粉粉末を適宜好適に用いることができる。   The combined filler (C) of organic and inorganic fine powder which is a non-adhesive component in the coating adhesive layer by this adhesive composition is added as a combined filler (C) of organic and inorganic fine powder. Has been. In the present invention, the organic fine powder has a relatively irregular particle shape, irregular particle surface, and an average particle diameter of 5 to 40 μm from the viewpoint of adjusting adhesive force and improving blocking resistance. Tangible fillers in the range are used. Examples thereof include starch powders such as styrene resin powder, acrylic resin powder, cellulose powder, sweet potato, potato, wheat, corn, rice and tapioca. Among them, in the present invention, since the main component of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer is compatible with an aqueous emulsion by emulsion polymerization and is inexpensive, starch powder can be suitably used as appropriate.

また、本発明の粘着剤組成物層は、印刷面として印字面感圧接着層でもあることから、本発明においては、特に、耐ブロッキング性、印刷インキ受容性、印刷適性等をバランス又は向上させる観点から、ＪＩＳＫ５１０１の煮アマニ油法に準拠させて測定された吸油量が、１００ｍｌ／１００ｇ以上で、好ましくは、１５０ｍｌ／１００ｇ以上の吸油量を有する無機系微粉末を適宜好適に用いられる。例えば、炭カル、炭マグ、硫酸バリウム、サチンホワイト、合成ケイ酸カルシウム、合成ケイ酸マグネシウム、合成スメクタイト、シリカ、水酸化アルミニウム、合成雲母、合成マイカー、オラストナイト、ネフェリンサイト、タルク、カオリン、珪藻土等が挙げられる。本発明においては、吸油性で、多孔質非晶質シリカで、平均粒子径１〜２０μｍで、好ましくは３〜１０μｍのシリカ粉末を適宜好適に用いられるが、耐ブロッキング性のバランスや、印刷適性を向上させ、且つ印字面に平滑性を付与させる観点から、必要に応じて、シリカ粉末に、タルク、カオリン、炭カル、ネフェリンサイト、サチンホワイト、合成スメクタイト等の１種又は２種以上の混合無機微粉末を適宜用いることができる。   Further, since the pressure-sensitive adhesive composition layer of the present invention is also a printing surface pressure-sensitive adhesive layer as a printing surface, in the present invention, in particular, the anti-blocking property, printing ink acceptability, printability, etc. are balanced or improved. From the viewpoint, an inorganic fine powder having an oil absorption measured according to the boiled linseed oil method of JISK5101 is preferably 100 ml / 100 g or more, and preferably 150 ml / 100 g or more. For example, charcoal cal, charcoal mug, barium sulfate, satin white, synthetic calcium silicate, synthetic magnesium silicate, synthetic smectite, silica, aluminum hydroxide, synthetic mica, synthetic mica, orastite, nepheline site, talc, kaolin, Examples include diatomaceous earth. In the present invention, an oil-absorbing, porous amorphous silica having an average particle diameter of 1 to 20 μm, preferably 3 to 10 μm, is suitably used as appropriate, but the balance of blocking resistance and printability are suitable. From the viewpoint of improving the printing surface and imparting smoothness to the printed surface, if necessary, the silica powder is mixed with one or more of talc, kaolin, charcoal cal, nepheline site, satin white, synthetic smectite, etc. Inorganic fine powders can be used as appropriate.

本発明においては、有機系及び無機系微粉末の組み合わせ充填剤（Ｃ）において、上記に説明する理由から、特に、その組み合わせ粉末種によって必ずしも限定されないが、例えば、澱粉とシリカ粉末との組み合わせ充填剤（Ｃ）のうちで、重量％で表してシリカ粉末が１０〜９０％であることが好適である。   In the present invention, the combination filler (C) of organic and inorganic fine powders is not necessarily limited by the type of the combination powder, particularly for the reasons described above. For example, the combination filler of starch and silica powder is used. Among the agents (C), it is preferable that the silica powder is 10 to 90% in terms of% by weight.

また、必要に応じて、本発明による粘着剤組成物は、本発明の粘着剤特性としての効果を損ねない範囲で、それ自体公知の配合剤、例えば、可塑剤、滑剤、被膜形成助剤、消泡剤、増粘剤、帯電防止剤、紫外線吸収剤、抗菌・防カビ剤、染料、顔料等を適宜配合させることができる。これらの添加剤をそれぞれ個々に配合してもよく、２種以上を組合わせて混合配合させてもよい。その添加量は添加剤種にもよるが、通常、粘着剤組成物１００重量部当たり、０．０１〜４０重量部、好ましくは、２０重量部以下、更に好ましくは、１０重量部以下で適宜好適に添加させることができる。   Further, if necessary, the pressure-sensitive adhesive composition according to the present invention is a compounding agent known per se, for example, a plasticizer, a lubricant, a film-forming aid, within a range that does not impair the effect as the pressure-sensitive adhesive property of the present invention. An antifoaming agent, a thickener, an antistatic agent, an ultraviolet absorber, an antibacterial / antifungal agent, a dye, a pigment, and the like can be appropriately blended. These additives may be blended individually, or two or more may be combined and blended. The amount added depends on the type of additive, but is usually suitably 0.01 to 40 parts by weight, preferably 20 parts by weight or less, more preferably 10 parts by weight or less per 100 parts by weight of the pressure-sensitive adhesive composition. Can be added.

このように調製される本発明による圧着性再剥離型粘着剤組成物は、各種の被着体に対して、５〜２０ｋｇ／ｃｍ２圧着力での貼り合わせ後にテンシロン型引張試験機で引張速度１００ｍｍ／分におけるＴ型剥離速度が１０〜６０ｇ／２５ｍｍの初期接着力（又は一時貼合接着力）の圧着性を有している。また、貼合圧着後、適宜自在に再剥離されて、特に、長期の経時下においても接着力はほぼ不変で、再剥離力が６０ｇ／２５ｍｍ以下、好ましくは、４０ｇ／２５ｍｍ以下で、良好な再剥離性を有している。また、本発明において適宜好適に使用される紙支持体として、例えば、合成紙、コート紙、ラミネート紙、上質紙、金属蒸着紙、印刷用塗工紙、記録用塗工紙等を挙げることができる。 The pressure-removable pressure-sensitive adhesive composition according to the present invention prepared in this way is applied to various adherends at a tensile speed of 10-20 kg / cm 2 after bonding with a tensilon-type tensile tester. The T-type peeling speed at 100 mm / min has a pressure-bonding property with an initial adhesive strength (or temporary bonding adhesive strength) of 10 to 60 g / 25 mm. In addition, it can be re-peeled as appropriate after bonding and bonding, and the adhesive strength is almost unchanged even over a long period of time, and the re-peeling force is 60 g / 25 mm or less, preferably 40 g / 25 mm or less. Has removability. Examples of the paper support suitably used in the present invention include, for example, synthetic paper, coated paper, laminated paper, high-quality paper, metallized paper, coated paper for printing, coated paper for recording, and the like. it can.

本発明による圧着性再剥離型粘着剤組成物の塗付量は、通常、３〜４０ｇ／ｍ２（乾燥物重量）の坪量で、下限値３未満では、接着性が十分に発揮されず、上限値４０を超えると、接着力が高すぎて再剥離が困難になって支持体である連続帳票用紙破れを起こす。また、紙支持体に対する粘着剤組成物の塗工は、例えば、エアナイフコーター、ブレードコーター、バーコーター、スクリーン印刷、フレキソ印刷、グラビア印刷機等の従来から公知の塗布機又は印刷機を用いて粘着剤層として塗布することができる。 The application amount of the pressure-sensitive adhesive re-peelable pressure-sensitive adhesive composition according to the present invention is usually a basis weight of 3 to 40 g / m 2 (dry matter weight), and if the lower limit value is less than 3, the adhesiveness is not sufficiently exhibited. If the upper limit value 40 is exceeded, the adhesive force is too high and re-peeling becomes difficult, and the continuous form paper as the support is torn. In addition, the application of the pressure-sensitive adhesive composition to the paper support is performed by using a conventionally known coating machine or printing machine such as an air knife coater, a blade coater, a bar coater, screen printing, flexographic printing, or a gravure printing machine. It can apply | coat as an agent layer.

また、本発明による圧着性再剥離型粘着剤組成物は、二つ折り又は三つ折りの連続帳票用紙に貼合用隠蔽ハガキや、親展ハガキや、封書に粘着剤層として適宜好適に設けることができるが、このような用途に設ける粘着剤層は、既に上述する如く、二つ折り又は三つ折り連続帳票用紙に設ける貼合接着層であって、同時にこの粘着剤層は、宛名印刷層、隠蔽情報印刷層であることから、本発明においては、隠蔽ハガキや、親展ハガキや、封書として、この圧着性再剥離型粘着剤組成物を、塗工膜厚が１〜５０μｍの範囲になるように、好ましくは、１〜１０μｍの範囲で適宜に塗工することができる。本発明において、下限値１μｍ未満では、良好な印刷適性を粘着剤層に付与させ難く、上限値５０μｍを超えると貼合接着面として、耐ブロッキング性を低下させ、また、印刷面としての表面平滑性を低下させる傾向にある。   In addition, the pressure-removable pressure-sensitive adhesive composition according to the present invention can be suitably provided as a pressure-sensitive adhesive layer for concealment postcards, confidential postcards, and sealed letters on bi-fold or tri-fold continuous forms. However, as already described above, the pressure-sensitive adhesive layer provided for such use is a bonding adhesive layer provided on a bi-fold or tri-fold continuous form paper, and at the same time, this pressure-sensitive adhesive layer is used for address printing layer, concealment information printing. Since it is a layer, in the present invention, as a concealing postcard, a confidential postcard, or a sealed letter, this pressure-removable pressure-sensitive adhesive composition is preferably used so that the coating film thickness is in the range of 1 to 50 μm. Can be appropriately applied in the range of 1 to 10 μm. In the present invention, when the lower limit value is less than 1 μm, it is difficult to impart good printability to the pressure-sensitive adhesive layer, and when the upper limit value exceeds 50 μm, the anti-blocking property is lowered as a bonding adhesive surface, and the surface smoothness as a printing surface It tends to decrease the sex.

以下に、本発明を実施例により更に説明するが、本発明は、これらの実施例にいささかも限定されるものではない。   EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

（実施例）
本発明において、以下のように定義した「シーラー加工性」の評価法を用いて、（イ）５〜２０ｋｇ／ｃｍ２圧着後の接着性が、テンシロン型引張試験機で引張速度１００ｍｍ／分におけるＴ型剥離力において０〜６０ｇ／２５ｍｍの初期接着力（又は一時貼合接着力）の圧着性を有し、（ロ）貼合圧着後、長期の経時下においても接着力はほぼ不変で、再剥離力が６０ｇ／２５ｍｍ以下である本発明による圧着性再剥離型粘着剤組成物（再剥離性粘着剤−１〜再剥離性粘着剤−９）が果たす「シーラー加工性」について評価した。
上質紙の紙支持体の片面（一部につき両面）に、コンマコーターを用いて、以下に調製した９種の本発明による圧着性再剥離型粘着剤組成物（以後、単に再剥離性粘着剤と記す）を、乾燥後の塗工量が６．２、６．３、６．５（ｇ／ｍ２）坪量である塗工紙に加工した。 (Example)
In the present invention, using the evaluation method of “sealer workability” defined as follows, (b) the adhesiveness after 5-20 kg / cm 2 pressure bonding was measured at a tensile speed of 100 mm / min with a Tensilon type tensile tester. It has a pressure-bonding property with an initial adhesive force (or temporary bonding adhesive force) of 0 to 60 g / 25 mm in T-type peeling force, and (b) the adhesive force is almost unchanged even after a long period of time after the bonding pressure bonding, The “sealer processability” performed by the pressure-removable pressure-sensitive adhesive composition (removable pressure-sensitive adhesive-1 to re-peelable pressure-sensitive adhesive-9) according to the present invention having a re-peeling force of 60 g / 25 mm or less was evaluated.
Nine types of pressure-sensitive releasable pressure-sensitive adhesive compositions according to the present invention (hereinafter simply referred to as re-peelable pressure-sensitive adhesives) prepared as follows using a comma coater on one side (both sides of a part) of a high-quality paper support. Are coated into coated paper having a coating weight of 6.2, 6.3, 6.5 (g / m 2 ) basis weight after drying.

（イ）＜初期接着力＞
評価用紙支持体の粘着剤塗布面同士を合わせ、ステンレス−ステンレス・ロールニップ間で線圧５００ｋｇ／ｃｍを掛けて圧着し、これを幅２５ｍｍ、長さ１７０ｍｍに裁断し２０℃、ＲＨ６５％の雰囲気下にテンシロン型引張試験機で引張速度１００ｍｍ／分におけるＴ型剥離速度を測定した。
（ロ）＜剥離感＞
評価用紙支持体を（イ）に準拠させて接着させた後、手で剥離させた感触で以下のように評価した。◎印：滑らかに剥離する。△印：若干滑らかさに欠ける。×印：滑らかさがない。
（ハ）＜耐ブロッキング性＞
粘着剤を塗工した面同士を重ね合わせ、５００ｇ／ｃｍ２の圧力を加え、相対湿度８５％、５０℃×１ｈｒ放置後、引き剥がした面の状態を目視観察して評価した。その結果、引き剥がしがすんなり抵抗感がなく、紙支持体の表面が傷んでないものをブロッキングの問題なしと◎印とし、表面が傷んでパルプ繊維が毛羽立っているものをブロッキングするとして×印とした。
（ニ）＜「シーラー加工性」の評価＞
本発明による再剥離型粘着剤組成物を用いて、隠蔽ハガキ、親展ハガキ等の二つ折り又は三つ折りの連続帳票用紙である紙支持体の片面又は両面に設けた粘着剤層は、（イ）の初期接着力、（ロ）の剥離感及び（ハ）の耐ブロッキング性なる「粘着剤層特性」を満たすことによって、このような用途に供するに際しては、シーラーの回転ローラによる圧着・貼合・搬送なる一連の加工作業性である貼合製品化効率を低下（又は阻害）させない。
従って、このような用途における紙支持体に設けた粘着剤層は、上記（イ）〜（ハ）なる「粘着剤層特性」に起因して、シーラーが果たすべき圧着・貼合・搬送なる加工作業性を左右させている。これらを実施した事実から、本発明においては、このような印刷・印字性を有し、圧着性で、再剥離性である貼合粘着剤層は、圧着・貼合・搬送に係わる回転ローラの「シーラー加工性」を発揮させていると評価できる。 (I) <Initial adhesive strength>
The adhesive-coated surfaces of the evaluation paper support are aligned and bonded by applying a linear pressure of 500 kg / cm between a stainless steel and a stainless steel roll nip, and this is cut to a width of 25 mm and a length of 170 mm, and in an atmosphere of 20 ° C. and RH 65%. The T-type peel rate at a tensile rate of 100 mm / min was measured with a Tensilon type tensile tester.
(B) <Peeling feeling>
After the evaluation paper support was bonded in accordance with (A), it was evaluated as follows with the touch peeled by hand. ◎: Peel off smoothly. Δ: Slightly lacking in smoothness X mark: There is no smoothness.
(C) <Blocking resistance>
The surfaces coated with the pressure-sensitive adhesive were overlapped, and a pressure of 500 g / cm 2 was applied. After leaving at a relative humidity of 85% and 50 ° C. × 1 hr, the state of the peeled surface was visually observed and evaluated. As a result, peeling was not easily felt, and the paper support surface was not damaged and marked as ◎ without blocking, and the surface was scratched and fluffy pulp fibers were marked as x .
(D) <Evaluation of “sealerability”
Using the re-peelable pressure-sensitive adhesive composition according to the present invention, a pressure-sensitive adhesive layer provided on one or both sides of a paper support, which is a bi-fold or tri-fold continuous form paper such as a concealment postcard or a confidential postcard, By satisfying the “adhesive layer characteristics” of (ii) initial peel strength, (ii) feeling of peeling, and (iii) anti-blocking properties, when used in such applications, pressure-bonding / bonding with a rotating roller of a sealer It does not reduce (or inhibit) the bonding product efficiency, which is a series of processing workability to be conveyed.
Accordingly, the pressure-sensitive adhesive layer provided on the paper support in such applications is processed by pressure bonding / bonding / conveyance to be achieved by the sealer due to the “pressure-sensitive adhesive layer characteristics” (i) to (c) above. Workability is affected. From the fact that these were carried out, in the present invention, the bonding adhesive layer having such printing / printing property, pressure bonding property, and removability is the rotation roller for pressure bonding / bonding / conveyance. It can be evaluated that “sealer workability” is exhibited.

以上から、本発明による圧着性再剥離型粘着剤組成物は、シーラーの回転ローラが果たす連続帳票用紙の「圧着・貼合・搬送」の加工作業に対して「シーラー加工性」を損ねる（又は低下させる）少なくとも下記（ａ）〜（ｃ）なる要因をクリヤしていることが重要である。
（ａ）（イ）なる初期接着力を発揮させる本発明による紙支持体に設ける粘着剤層は、シーラーによる加工工程である圧着接触時にシーラーの回転ローラー面に対しては、全く密着感及び／又は付着汚染を及ぼさず、しかも、紙支持体の回転ローラによる搬送性を低下させない。
（ｂ） （イ）なる初期接着力は、シーラーの回転ローラー間の線圧５００ｋｇ／ｃｍ圧着下に発現され、且つ（ロ）なる剥離感を達成させる。
（ｃ）シーラーの回転ローラー間での線圧５００ｋｇ／ｃｍ圧着下に発現される（イ）及び（ロ）を満たす塗布粘着剤層は、（ハ）なる耐ブロッキング性を達成させる。 From the above, the pressure-removable pressure-sensitive adhesive composition according to the present invention impairs “sealer processability” with respect to the processing operation of “crimping / bonding / conveying” of continuous form paper performed by the rotating roller of the sealer (or It is important to clear at least the following factors (a) to (c).
(A) (a) The pressure-sensitive adhesive layer provided on the paper support according to the present invention that exhibits the initial adhesive force is completely adhered to the rotating roller surface of the sealer at the time of pressure contact, which is a processing step by the sealer. Or, it does not cause adhesion contamination, and does not deteriorate the transportability of the paper support by the rotating roller.
(B) The initial adhesive force (a) is expressed under the pressure of 500 kg / cm of linear pressure between the rotating rollers of the sealer and achieves the peeling feeling (b).
(C) The coating pressure-sensitive adhesive layer satisfying (a) and (b) expressed under a pressure of 500 kg / cm between the rotating rollers of the sealer achieves the blocking resistance (c).

本発明が提供した圧着性で、再剥離性である粘着剤組成物中の粘着剤主成分は、（メタ）アクリル酸エステル系エマルジョンで、且つゲル分率が６０〜９０％の範囲にある樹脂質成分と、リン酸エステル系界面活性剤と、澱粉等の有機系微粉末と吸油性のある多孔質シリカ粉末等の無機系微粉末を組み合わせた充填剤を含有している。
＜再剥離性粘着剤−１＞
主成分ＢＡの７４．５重量部と、副成分ＥＡの２０重量部とのアルキル基の炭素数が１
〜４の（メタ）アクリル酸エステル（ａ）の９４．５重量部と、アクリル酸のカルボキシル基含有モノマー（ｂ）の３重量部と、官能基がエポキシ基であるＧＭＡなる官能基モノマー（ｃ）の２．５重量部とを用いて乳化重合させて、ゲル分率が８３％である（メタ）アクリル酸エステル系エマルジョンを調製して、これを粘着剤主成分（Ａ）とした。
次いで、この粘着剤主成分（Ａ）の１００重量部当たり、ポリオキシエチレンアルキルリン酸エステル（以後、ＰＯＥＡＰＥと略記する）のリン酸エステル系界面活性剤（Ｂ）の２重量部と、更に、澱粉の１００重量部とＪＩＳＫ５１０１の煮アマニ油法に準拠させて得られた吸油量２３０（ｍｌ／１００ｇ）のシリカ粉末の１００重量部との組合わせ充填剤（Ｃ）の２００重量部とからなる本発明による圧着性再剥離型粘着剤組成物を調製した。この再剥離性粘着剤−１を上質紙の片面に塗工量が６．２（ｇ／ｍ２）坪量で、塗膜３μｍで塗工させた。 The pressure-sensitive adhesive and re-peelable pressure-sensitive adhesive composition provided by the present invention has a (meth) acrylic ester emulsion as the main component of the pressure-sensitive adhesive and a gel fraction in the range of 60 to 90%. And a filler comprising a combination of an organic fine powder such as starch and an inorganic fine powder such as an oil-absorbing porous silica powder.
<Removable adhesive-1>
The carbon number of the alkyl group of 74.5 parts by weight of the main component BA and 20 parts by weight of the subcomponent EA is 1
94.5 parts by weight of -4 (meth) acrylic acid ester (a), 3 parts by weight of carboxyl group-containing monomer (b) of acrylic acid, and a functional group monomer (c) whose functional group is an epoxy group ) Was subjected to emulsion polymerization to prepare a (meth) acrylic acid ester emulsion having a gel fraction of 83%, and this was used as the pressure-sensitive adhesive main component (A).
Next, 2 parts by weight of a polyoxyethylene alkyl phosphate ester (hereinafter abbreviated as POEAPE) phosphate ester-based surfactant (B) per 100 parts by weight of the adhesive main component (A), Composed of 200 parts by weight of filler (C) in combination with 100 parts by weight of starch and 100 parts by weight of silica powder having an oil absorption of 230 (ml / 100 g) obtained in accordance with the boiled linseed oil method of JISK5101 A pressure-sensitive re-peelable pressure-sensitive adhesive composition according to the present invention was prepared. This re-peelable pressure-sensitive adhesive-1 was applied to one surface of a high-quality paper with a coating amount of 6.2 (g / m 2 ) basis weight with a coating film of 3 μm.

次いで、調製した片面に粘着剤層を設けた２０ｃｍ×４５ｃｍの塗工紙について、フォーム印刷機で粘着剤塗布面にオフセットで印刷をし、次いで市販のキャノン社製のＢＪインクジェットプリンターで、印字を行った結果、ドット濃度が高く、色味が鮮明で、ブディングやフェザリング等のインク滲みがなく、印字品質が良好で、紙支持体の印字走行性もスムーズで良好であった。また、この塗工紙の粘着剤層特性である圧着下の貼合接着性も良好で、剥離感も◎印で、また、◎印の耐ブロッキング性を発揮させて、その結果、再剥離性粘着剤−１によって、良好な「シーラー加工性」を発揮させることができた。   Next, about 20cm x 45cm coated paper provided with a pressure-sensitive adhesive layer on one side, it was printed on the pressure-sensitive adhesive coated surface with a foam printer, and then printed with a commercially available BJ inkjet printer manufactured by Canon. As a result, the dot density was high, the color was vivid, there was no ink bleeding such as bubbling or feathering, the printing quality was good, and the printing support of the paper support was smooth and good. Also, the adhesive property of this coated paper is good adhesion under pressure bonding, the peel feeling is also marked with ◎, and the blocking resistance of ◎ is demonstrated, as a result, re-peelability Adhesive-1 was able to exhibit good “sealer processability”.

＜再剥離性粘着剤−２＞
主成分ＢＡの７４重量部と、副成分ＥＡの２０重量部とのアルキル基の炭素数が１〜４の（メタ）アクリル酸エステル（ａ）の９４重量部と、アクリル酸のカルボキシル基含有モノマー（ｂ）の４．５重量部と、官能基がメチロール基であるＮ−メチロールアクリドアミドなる官能基モノマー（ｃ）の１．５重量部とを用いて乳化重合させて、ゲル分率が８０％である（メタ）アクリル酸エステル系エマルジョンを調製して、これを粘着剤主成分（Ａ）とした。次いで、この粘着剤主成分（Ａ）の１００重量部当たり、ＰＯＥＡＰＥのリン酸エステル系界面活性剤（Ｂ）の４重量部と、更に、澱粉の１００重量部と吸油量２３０（ｍｌ／１００ｇ）のシリカ粉末の５０重量部とタルクの５０重量部との有機系及び無機系微細粉末とを組合わせ充填剤（Ｃ）の２００重量部とからなる本発明による圧着性再剥離型粘着剤組成物を調製した。この再剥離性粘着剤−２を上質紙の片面に塗工量が６．２（ｇ／ｍ２）坪量で、塗膜２μｍで塗工させた。
次いで、調製した片面に粘着剤層を設けた２０ｃｍ×４５ｃｍの塗工紙について、再剥離性粘着剤−１と同様にして、良好な印刷及び印字性を発揮し、インク滲みがなく、印字品質が良好であった。また、この塗工紙の粘着剤層特性である圧着下の貼合接着性も良好で、剥離感も◎印で、また、◎印の耐ブロッキング性を発揮させて、その結果、再剥離性粘着剤−２によって、良好な「シーラー加工性」を発揮させることができた。 <Removable adhesive-2>
74 parts by weight of the main component BA and 20 parts by weight of the subcomponent EA, 94 parts by weight of the (meth) acrylic acid ester (a) having 1 to 4 carbon atoms, and a carboxyl group-containing monomer of acrylic acid Emulsion polymerization is carried out using 4.5 parts by weight of (b) and 1.5 parts by weight of the functional group monomer (c) N-methylolacylamide whose functional group is a methylol group, and the gel fraction is An 80% (meth) acrylic acid ester emulsion was prepared and used as the pressure-sensitive adhesive main component (A). Next, 4 parts by weight of POEAPE phosphate ester surfactant (B), 100 parts by weight of starch, and oil absorption 230 (ml / 100 g) per 100 parts by weight of this adhesive main component (A) A pressure-sensitive adhesive releasable pressure-sensitive adhesive composition according to the present invention comprising 200 parts by weight of a filler (C) in which 50 parts by weight of silica powder and 50 parts by weight of talc are combined with organic and inorganic fine powders. Was prepared. This re-peelable pressure-sensitive adhesive-2 was applied to one surface of a high-quality paper with a coating weight of 6.2 (g / m 2 ) basis weight and a coating film of 2 μm.
Next, the coated paper of 20 cm × 45 cm provided with a pressure-sensitive adhesive layer on one side was prepared in the same manner as the releasable pressure-sensitive adhesive-1, and exhibited good printing and printability, no ink bleeding, and print quality. Was good. Also, the adhesive property of this coated paper is good adhesion under pressure bonding, the peel feeling is also marked with ◎, and the blocking resistance of ◎ is demonstrated, as a result, re-peelability Adhesive-2 was able to exhibit good “sealer processability”.

＜再剥離性粘着剤−３＞
主成分ＢＡの７６．５重量部と、副成分ＥＡの１５重量部と、ＭＭＡの５重量部とからなるアルキル基の炭素数が１〜４の（メタ）アクリル酸エステル（ａ）の９６．５重量部と、アクリル酸のカルボキシル基含有モノマー（ｂ）の３．０重量部と、官能基がシラノール基であるγメタクリロキシプロピルトリメトキシシランの官能基モノマー（ｃ）の０．５重量部とを用いて乳化重合させて、ゲル分率が８５である（メタ）アクリル酸エステル系エマルジョンを調製して、これを粘着剤主成分（Ａ）とした。次いで、この粘着剤主成分（Ａ）の１００重量部当たり、ＰＯＥＡＰＥなるリン酸エステル系界面活性剤（Ｂ）の４重量部と、更に、澱粉の１００重量部と吸油量１８０（ｍｌ／１００ｇ）のシリカ粉末５０重量部とタルクの１０重量部とを組合わせた充填剤（Ｃ）の１６０重量部とからなる本発明による圧着性再剥離型粘着剤組成物を調製した。この再剥離性粘着剤−３を上質紙の片面に塗工量が６．２（ｇ／ｍ２）坪量で、塗膜２μｍで塗工させた。
次いで、調製した片面又部分的には両面に粘着剤層を設けた２０ｃｍ×４５ｃｍの塗工紙について、再剥離性粘着剤−１と同様にして、良好な印刷及び印字性を発揮し、インク滲みがなく、印字品質が良好であった。また、この塗工紙の粘着剤層特性である圧着下の貼合接着性も良好で、特に両面塗工面を併せたものについても、剥離感も◎印で、また、◎印の耐ブロッキング性を発揮させた。その結果、再剥離性粘着剤−３によって、良好な「シーラー加工性」を発揮させることができた。 <Removable adhesive-3>
The alkyl group consisting of 76.5 parts by weight of the main component BA, 15 parts by weight of the sub-component EA, and 5 parts by weight of MMA has an alkyl group of 1 to 4 carbon atoms of (meth) acrylic acid ester (a) of 96. 5 parts by weight, 3.0 parts by weight of a carboxyl group-containing monomer (b) of acrylic acid, and 0.5 parts by weight of a functional group monomer (c) of γ-methacryloxypropyltrimethoxysilane whose functional group is a silanol group And (meth) acrylic acid ester emulsion having a gel fraction of 85 was prepared, and this was used as the main component of the pressure-sensitive adhesive (A). Next, 4 parts by weight of POEAPE phosphate ester surfactant (B), 100 parts by weight of starch and oil absorption 180 (ml / 100 g) per 100 parts by weight of the main component of the adhesive (A) A pressure-bondable re-peelable pressure-sensitive adhesive composition according to the present invention comprising 160 parts by weight of filler (C) in which 50 parts by weight of silica powder and 10 parts by weight of talc were combined was prepared. This re-peelable pressure-sensitive adhesive-3 was applied to one surface of a high-quality paper with a coating weight of 6.2 (g / m 2 ) basis weight and a coating film of 2 μm.
Next, the coated paper of 20 cm × 45 cm provided with an adhesive layer on one side or partially on both sides was prepared in the same manner as the releasable adhesive-1, and exhibited good printing and printability. There was no bleeding and the print quality was good. In addition, the adhesive property of this coated paper under pressure bonding, which is a characteristic of the adhesive layer, is also good, especially when both sides are coated, the feeling of peeling is also marked with ◎, and the blocking resistance of ◎ marks Was demonstrated. As a result, the re-peelable pressure-sensitive adhesive-3 was able to exhibit good “sealer processability”.

＜再剥離性粘着剤−４＞
主成分ＢＡの７６．９重量部と、副成分ＥＡの１５重量部と、ＭＭＡの５重量部とからなるアルキル基の炭素数が１〜４の（メタ）アクリル酸エステル（ａ）の９７重量部と、アクリル酸のカルボキシル基含有モノマー（ｂ）の３．０重量部と、官能基がエポキシ基であるＧＭＡなる官能基モノマー（ｃ）の０．１重量部とを用いて乳化重合させて、ゲル分率が７５％である（メタ）アクリル酸エステル系エマルジョンを調製して、これを粘着剤主成分（Ａ）とした。次いで、この粘着剤主成分（Ａ）の１００重量部当たり、ＰＯＥＡＰＥなるリン酸エステル系界面活性剤（Ｂ）の１．６重量部と、更に、澱粉５０重量部と吸油量１８０（ｍｌ／１００ｇ）のシリカ粉末５０重量部とタルクの１０重量部とを組合わせた充填剤（Ｃ）の１１０重量部とからなる本発明による圧着性再剥離型粘着剤組成物を調製した。この再剥離性粘着剤−４を上質紙の片面に塗工量が６．３（ｇ／ｍ２）坪量で、塗膜２μｍで塗工させた。
次いで、調製した片面に粘着剤層を設けた２０ｃｍ×４５ｃｍの塗工紙について、再剥離性粘着剤−１と同様に、良好な印刷及び印字性を発揮し、インク滲みがなく、印字品質が良好であった。また、この塗工紙の粘着剤層特性である圧着下の貼合接着性も良好で、剥離感も◎印で、また、◎印の耐ブロッキング性を発揮させた。その結果、再剥離性粘着剤−４によって、良好な「シーラー加工性」を発揮させることができた。 <Removable adhesive-4>
97 weight parts of (meth) acrylic acid ester (a) having 1 to 4 carbon atoms in the alkyl group consisting of 76.9 parts by weight of main component BA, 15 parts by weight of subcomponent EA, and 5 parts by weight of MMA Part, 3.0 parts by weight of the carboxyl group-containing monomer (b) of acrylic acid, and 0.1 parts by weight of the functional group monomer (c) GMA whose functional group is an epoxy group. A (meth) acrylic acid ester emulsion having a gel fraction of 75% was prepared and used as the main component of the pressure-sensitive adhesive (A). Then, per 100 parts by weight of the main component of the pressure-sensitive adhesive (A), 1.6 parts by weight of POEAPE phosphate ester surfactant (B), 50 parts by weight of starch, and oil absorption 180 (ml / 100 g) The pressure-bondable re-peelable pressure-sensitive adhesive composition according to the present invention was prepared, comprising 110 parts by weight of filler (C) in which 50 parts by weight of silica powder and 10 parts by weight of talc were combined. This re-peelable pressure-sensitive adhesive-4 was applied to one surface of a high-quality paper with a coating weight of 6.3 (g / m 2 ) and a coating film of 2 μm.
Next, the coated paper of 20 cm × 45 cm provided with a pressure-sensitive adhesive layer on one side exhibits good printing and printability as in the case of the releasable pressure-sensitive adhesive-1, and there is no ink bleeding and print quality. It was good. Further, the adhesive property of this coated paper under pressure bonding, which is a pressure-sensitive adhesive layer property, was good, the feeling of peeling was marked with ◎, and the blocking resistance of ◎ was exhibited. As a result, the re-peelable pressure-sensitive adhesive-4 was able to exhibit good “sealer processability”.

＜再剥離性粘着剤−５＞
主成分ＢＡの８６重量部と、副成分ＭＭＡの１０重量部とからなるアルキル基の炭素数が２又は４の（メタ）アクリル酸エステル（ａ）の９６重量部と、アクリル酸のカルボキシル基含有モノマー（ｂ）の３．０重量部と、官能基が水酸基である２−ヒドロキシエチルメタアクリレートなる官能基モノマー（ｃ）の０．５重量部と、官能基がメチロール基であるＮ−ＭＡＭなる官能基モノマー（ｃ）の０．５重量部とを用いて乳化重合させて、ゲル分率が６２％である（メタ）アクリル酸エステル系エマルジョンを調製して、これを粘着剤主成分（Ａ）とした。次いで、この粘着剤主成分（Ａ）の１００重量部当たり、ＰＯＥＡＰＥなるリン酸エステル系界面活性剤（Ｂ）の１重量部と、更に、澱粉１００重量部と吸油量１８０（ｍｌ／１００ｇ）のシリカ粉末１００重量部とタルクの３０重量部とを組合わせた充填剤（Ｃ）の２３０重量部とからなる本発明による圧着性再剥離型粘着剤組成物を調製した。この再剥離性粘着剤−５を上質紙の片面に塗工量が６．３（ｇ／ｍ２）坪量で、塗膜２μｍで塗工させた。
次いで、調製した片面に粘着剤層を設けた２０ｃｍ×４５ｃｍの塗工紙について、再剥離性粘着剤−１と同様に、良好な印刷及び印字性を発揮し、インク滲みがなく、印字品質が良好であった。また、この塗工紙の粘着剤層特性である圧着下の貼合接着性も良好で、剥離感も◎印で、また、◎印の耐ブロッキング性を発揮させた。その結果、再剥離性粘着剤−５によって、良好な「シーラー加工性」を発揮させることができた。 <Removable adhesive-5>
96 parts by weight of (meth) acrylic acid ester (a) having 2 or 4 carbon atoms in the alkyl group consisting of 86 parts by weight of main component BA and 10 parts by weight of subcomponent MMA, and carboxyl group of acrylic acid 3.0 parts by weight of the monomer (b), 0.5 parts by weight of the functional group monomer (c) composed of 2-hydroxyethyl methacrylate whose functional group is a hydroxyl group, and N-MAM whose functional group is a methylol group Emulsion polymerization is performed using 0.5 part by weight of the functional group monomer (c) to prepare a (meth) acrylic acid ester emulsion having a gel fraction of 62%. ). Next, per 100 parts by weight of the pressure-sensitive adhesive main component (A), 1 part by weight of POEAPE phosphate surfactant (B), 100 parts by weight of starch, and oil absorption 180 (ml / 100 g) A pressure-bondable re-peelable pressure-sensitive adhesive composition according to the present invention comprising 230 parts by weight of a filler (C) obtained by combining 100 parts by weight of silica powder and 30 parts by weight of talc was prepared. This re-peelable pressure-sensitive adhesive-5 was applied to one surface of a high-quality paper with a coating weight of 6.3 (g / m 2 ) and a coating film of 2 μm.
Next, the coated paper of 20 cm × 45 cm provided with a pressure-sensitive adhesive layer on one side exhibits good printing and printability as in the case of the releasable pressure-sensitive adhesive-1, and there is no ink bleeding and print quality. It was good. Further, the adhesive property of this coated paper under pressure bonding, which is a pressure-sensitive adhesive layer property, was good, the feeling of peeling was marked with ◎, and the blocking resistance of ◎ was exhibited. As a result, the re-peelable pressure-sensitive adhesive-5 was able to exhibit good “sealer processability”.

＜再剥離性粘着剤−６＞
主成分ＢＡの８１．９重量部と、副成分ＥＡの１５重量部とからなるアルキル基の炭素数が２又は４の（メタ）アクリル酸エステル（ａ）の９７重量部と、アクリル酸のカルボキシル基含有モノマー（ｂ）の３．０重量部と、官能基がシラノール基であるトリメトキシシリルアクリレートなる官能基モノマー（ｃ）の０．１重量部とを用いて乳化重合させて、ゲル分率が７５％である（メタ）アクリル酸エステル系エマルジョンを調製して、これを粘着剤主成分（Ａ）とした。次いで、この粘着剤主成分（Ａ）の１００重量部当たり、ＰＯＥＡＰＥなるリン酸エステル系界面活性剤（Ｂ）の１．２重量部と、更に、澱粉５０重量部と吸油量１８０（ｍｌ／１００ｇ）のシリカ粉末５０重量部とを組合わせた充填剤（Ｃ）の１００重量部とからなる本発明による圧着性再剥離型粘着剤組成物を調製した。この再剥離性粘着剤−６を上質紙の片面に塗工量が６．５（ｇ／ｍ２）坪量で、塗膜２μｍで塗工させた。
次いで、調製した片面に粘着剤層を設けた２０ｃｍ×４５ｃｍの塗工紙について、再剥離性粘着剤−１と同様に、良好な印刷及び印字性を発揮し、インク滲みがなく、印字品質が良好であった。また、この塗工紙の粘着剤層特性である圧着下の貼合接着性も良好で、剥離感も◎印で、また、◎印の耐ブロッキング性を発揮させた。その結果、再剥離性粘着剤−６によって、良好な「シーラー加工性」を発揮させることができた。 <Removable adhesive-6>
97 parts by weight of (meth) acrylic acid ester (a) having 2 or 4 carbon atoms in the alkyl group, consisting of 81.9 parts by weight of main component BA and 15 parts by weight of subcomponent EA, and carboxyl of acrylic acid The gel fraction is obtained by emulsion polymerization using 3.0 parts by weight of the group-containing monomer (b) and 0.1 parts by weight of the functional monomer (c) composed of trimethoxysilyl acrylate whose functional group is a silanol group. A (meth) acrylic acid ester emulsion having a ratio of 75% was prepared and used as the main component (A) of the pressure-sensitive adhesive. Next, per 100 parts by weight of the pressure-sensitive adhesive main component (A), 1.2 parts by weight of POEAPE phosphate ester surfactant (B), 50 parts by weight of starch, and oil absorption 180 (ml / 100 g) The pressure-removable pressure-sensitive adhesive composition according to the present invention comprising 100 parts by weight of the filler (C) in combination with 50 parts by weight of silica powder was prepared. This re-peelable pressure-sensitive adhesive-6 was applied to one surface of a high-quality paper with a coating weight of 6.5 (g / m 2 ) and a coating film of 2 μm.
Next, the coated paper of 20 cm × 45 cm provided with a pressure-sensitive adhesive layer on one side exhibits good printing and printability as in the case of the releasable pressure-sensitive adhesive-1, and there is no ink bleeding and print quality. It was good. Further, the adhesive property of this coated paper under pressure bonding, which is a pressure-sensitive adhesive layer property, was good, the feeling of peeling was marked with ◎, and the blocking resistance of ◎ was exhibited. As a result, the re-peelable pressure-sensitive adhesive-6 was able to exhibit good “sealer processability”.

＜再剥離性粘着剤−７＞
主成分ＢＡの７８．９重量部と、ＥＡの１５重量部と、アルキル基の炭素数が１２のラウリルメタアクリレートの３重量部との（メタ）アクリル酸エステル（ａ）の９７重量部と、アクリル酸のカルボキシル基含有モノマー（ｂ）の３．０重量部と、官能基がエポキシ基であるＧＭＡの官能基モノマー（ｃ）の０．１重量部とを用いて乳化重合させて、ゲル分率が７０％である（メタ）アクリル酸エステル系エマルジョンを調製して、これを粘着剤主成分（Ａ）とした。次いで、この粘着剤主成分（Ａ）の１００重量部当たり、ＰＯＥＡＰＥなるリン酸エステル系界面活性剤（Ｂ）の１．２重量部と、更に、澱粉１００重量部と吸油量２３０（ｍｌ／１００ｇ）のシリカ粉末１００重量部とを組合わせた充填剤（Ｃ）の２００重量部とからなる本発明による圧着性再剥離型粘着剤組成物を調製した。この再剥離性粘着剤−７を上質紙の片面に塗工量が６．５（ｇ／ｍ２）坪量で、塗膜２μｍで塗工させた。
次いで、調製した片面に粘着剤層を設けた２０ｃｍ×４５ｃｍの塗工紙について、再剥離性粘着剤−１と同様に、良好な印刷及び印字性を発揮し、インク滲みがなく、印字品質が良好であった。また、この塗工紙の粘着剤層特性である圧着下の貼合接着性も良好で、剥離感も◎印で、また、◎印の耐ブロッキング性を発揮させた。その結果、再剥離性粘着剤−７によって、良好な「シーラー加工性」を発揮させることができた。 <Removable adhesive-7>
97 parts by weight of (meth) acrylic acid ester (a) of 78.9 parts by weight of the main component BA, 15 parts by weight of EA, and 3 parts by weight of lauryl methacrylate having 12 alkyl groups, Using 3.0 parts by weight of the carboxyl group-containing monomer (b) of acrylic acid and 0.1 parts by weight of the functional group monomer (c) of GMA whose functional group is an epoxy group, emulsion polymerization is performed to obtain a gel fraction. A (meth) acrylic acid ester emulsion having a rate of 70% was prepared and used as the pressure-sensitive adhesive main component (A). Next, per 100 parts by weight of the main component of the pressure-sensitive adhesive (A), 1.2 parts by weight of the phosphoric ester surfactant (B) as POEAPE, 100 parts by weight of starch, and an oil absorption of 230 (ml / 100 g) The pressure-bondable re-peelable pressure-sensitive adhesive composition according to the present invention comprising 200 parts by weight of filler (C) in combination with 100 parts by weight of silica powder was prepared. This re-peelable pressure-sensitive adhesive-7 was applied to one surface of a high-quality paper with a coating weight of 6.5 (g / m 2 ) and a coating film of 2 μm.
Next, the coated paper of 20 cm × 45 cm provided with a pressure-sensitive adhesive layer on one side exhibits good printing and printability as in the case of the releasable pressure-sensitive adhesive-1, and there is no ink bleeding and print quality. It was good. Further, the adhesive property of this coated paper under pressure bonding, which is a pressure-sensitive adhesive layer property, was good, the feeling of peeling was marked with ◎, and the blocking resistance of ◎ was exhibited. As a result, the re-peelable pressure-sensitive adhesive-7 was able to exhibit good “sealer processability”.

＜再剥離性粘着剤−８＞
主成分ＢＡの７９．９重量部と、ＥＡの１４重量部と、アルキル基の炭素数が１２のラウリルメタアクリレートの３重量部とからの（メタ）アクリル酸エステル（ａ）の９６．９重量部と、アクリル酸のカルボキシル基含有モノマー（ｂ）の３重量部と、官能基がシラノール基であるトリメトキシシリルアクリレートなる官能基モノマー（ｃ）の０．１重量部とを用いて乳化重合させて、ゲル分率が７２％である（メタ）アクリル酸エステル系エマルジョンを調製し、これを粘着剤主成分（Ａ）とした。次いで、この粘着剤主成分（Ａ）の１００重量部当たり、ＰＯＥＡＰＥなるリン酸エステル系界面活性剤（Ｂ）の１重量部と、更に、澱粉１００重量部と吸油量２３０（ｍｌ／１００ｇ）のシリカ粉末１００重量部とを組合わせた充填剤（Ｃ）の２００重量部とからなる本発明による圧着性再剥離型粘着剤組成物を調製した。この再剥離性粘着剤−８を上質紙の片面に塗工量が６．３（ｇ／ｍ２）坪量で、塗膜２μｍで塗工させた。
次いで、調製した片面に粘着剤層を設けた２０ｃｍ×４５ｃｍの塗工紙について、再剥離性粘着剤−１と同様に、良好な印刷及び印字性を発揮し、インク滲みがなく、印字品質が良好であった。また、この塗工紙の粘着剤層特性である圧着下の貼合接着性も良好で、剥離感も◎印で、また、◎印の耐ブロッキング性を発揮させた。その結果、再剥離性粘着剤−８によって、良好な「シーラー加工性」を発揮させることができた。 <Removable adhesive-8>
96.9 parts by weight of (meth) acrylic acid ester (a) from 79.9 parts by weight of the main component BA, 14 parts by weight of EA and 3 parts by weight of lauryl methacrylate having 12 alkyl groups 1 part by weight, 3 parts by weight of a carboxyl group-containing monomer (b) of acrylic acid, and 0.1 part by weight of a functional group monomer (c) made of trimethoxysilyl acrylate whose functional group is a silanol group Then, a (meth) acrylic acid ester emulsion having a gel fraction of 72% was prepared and used as the pressure-sensitive adhesive main component (A). Next, per 100 parts by weight of this adhesive main component (A), 1 part by weight of POEAPE phosphate ester surfactant (B), 100 parts by weight of starch, and oil absorption 230 (ml / 100 g) A pressure-bonding removable adhesive composition according to the present invention comprising 200 parts by weight of a filler (C) combined with 100 parts by weight of silica powder was prepared. This releasable pressure-sensitive adhesive-8 was applied to one surface of a high-quality paper with a coating weight of 6.3 (g / m 2 ) basis weight and a coating film of 2 μm.
Next, the coated paper of 20 cm × 45 cm provided with a pressure-sensitive adhesive layer on one side exhibits good printing and printability as in the case of the releasable pressure-sensitive adhesive-1, and there is no ink bleeding and print quality. It was good. Further, the adhesive property of this coated paper under pressure bonding, which is a pressure-sensitive adhesive layer property, was good, the feeling of peeling was marked with ◎, and the blocking resistance of ◎ was exhibited. As a result, the re-peelable pressure-sensitive adhesive-8 was able to exhibit good “sealer processability”.

＜再剥離性粘着剤−９＞
主成分ＢＡの７２重量部と、ＥＡの１５重量部と、アルキル基の炭素数が８の２エチルヘキシルアクリレートの１０重量部との（メタ）アクリル酸エステル（ａ）の９７重量部と、アクリル酸のカルボキシル基含有モノマー（ｂ）の２．９重量部と、官能基がエポキシ基であるＧＭＡなる官能基モノマー（ｃ）の０．１重量部とを用いて乳化重合させて、ゲル分率が８０％である（メタ）アクリル酸エステル系エマルジョンを調製し、これを粘着剤主成分（Ａ）とした。次いで、この粘着剤主成分（Ａ）の１００重量部当たり、ＰＯＥＡＰＥなるリン酸エステル系界面活性剤（Ｂ）の１重量部と、更に、澱粉８０重量部と吸油量２３０（ｍｌ／１００ｇ）のシリカ粉末６０重量部とタルクの１０重量部とを組合わせた充填剤（Ｃ）の１５０重量部とからなる本発明による圧着性再剥離型粘着剤組成物を調製した。この再剥離性粘着剤−９を上質紙の片面に塗工量が６．２（ｇ／ｍ２）坪量で、塗膜２μｍで塗工させた。
次いで、調製した片面に粘着剤層を設けた２０ｃｍ×４５ｃｍの塗工紙について、再剥離性粘着剤−１と同様に、良好な印刷及び印字性を発揮し、インク滲みがなく、印字品質が良好であった。また、この塗工紙の粘着剤層特性である圧着下の貼合接着性も良好で、剥離感も◎印で、また、◎印の耐ブロッキング性を発揮させた。その結果、再剥離性粘着剤−９によって、良好な「シーラー加工性」を発揮させることができた。 <Removable adhesive-9>
97 parts by weight of (meth) acrylic acid ester (a), 72 parts by weight of main component BA, 15 parts by weight of EA, 10 parts by weight of 2-ethylhexyl acrylate having an alkyl group of 8 carbon atoms, acrylic acid And 2.9 parts by weight of the carboxyl group-containing monomer (b) and 0.1 part by weight of the functional group monomer (c) GMA whose functional group is an epoxy group, and the gel fraction is A 80% (meth) acrylic acid ester emulsion was prepared and used as the main component of the pressure-sensitive adhesive (A). Next, 1 part by weight of POEAPE phosphate ester surfactant (B), 100 parts by weight of starch, and 230 parts by weight of oil absorption (100 ml / 100 g) per 100 parts by weight of the adhesive main component (A). A pressure-bondable re-peelable pressure-sensitive adhesive composition according to the present invention comprising 150 parts by weight of a filler (C) obtained by combining 60 parts by weight of silica powder and 10 parts by weight of talc was prepared. The releasable pressure-sensitive adhesive-9 was applied to one surface of a high-quality paper with a coating weight of 6.2 (g / m 2 ) basis weight and a coating film of 2 μm.
Next, the coated paper of 20 cm × 45 cm provided with a pressure-sensitive adhesive layer on one side exhibits good printing and printability as in the case of the releasable pressure-sensitive adhesive-1, and there is no ink bleeding and print quality. It was good. Further, the adhesive property of this coated paper under pressure bonding, which is a pressure-sensitive adhesive layer property, was good, the feeling of peeling was marked with ◎, and the blocking resistance of ◎ was exhibited. As a result, the re-peelable pressure-sensitive adhesive-9 was able to exhibit good “sealer processability”.

（比較例）
本発明による再剥離性粘着剤の「シーラー加工性」との係わりを明確にするため、その粘着剤主成分である（メタ）アクリル酸エステル系エマルジョンのゲル分率が６０〜９０％範囲から外れる樹脂質成分からなる再剥離性粘着剤−比１及び再剥離性粘着剤−比２を比較例として調製して、その「シーラー加工性」との係わりを評価した。
＜再剥離性粘着剤−比１＞
主成分ＢＡの７４．５重量部と、副成分ＥＡの２０重量部とのアルキル基の炭素数が２又は４の（メタ）アクリル酸エステル（ａ）の９４．５重量部と、アクリル酸のカルボキシル基含有モノマー（ｂ）の４重量部と、官能基がエポキシ基であるＧＭＡなる官能基モノマー（ｃ）の８重量部とを用いて乳化重合させて、ゲル分率が９２％である（メタ）アクリル酸エステル系エマルジョンを調製して、これを粘着剤主成分（Ａ）とした。
次いで、この粘着剤主成分（Ａ）の１００重量部当たり、ポリオキシエチレンアルキルリン酸エステル（以後、ＰＯＥＡＰＥと略記する）のリン酸エステル系界面活性剤（Ｂ）の２重量部と、更に、澱粉の１００重量部とＪＩＳＫ５１０１の煮アマニ油法に準拠させて得られた吸油量２３０（ｍｌ／１００ｇ）のシリカ粉末の１００重量部との組合わせ充填剤（Ｃ）の２００重量部とからなる本発明による圧着性再剥離型粘着剤組成物を調製した。この再剥離性粘着剤−１を上質紙の片面に塗工量が６．２（ｇ／ｍ２）坪量で、塗膜２μｍで塗工させた。 (Comparative example)
In order to clarify the relationship with the “sealer processability” of the removable pressure-sensitive adhesive according to the present invention, the gel fraction of the (meth) acrylic acid ester emulsion as the main component of the pressure-sensitive adhesive deviates from the range of 60 to 90%. A releasable pressure-sensitive adhesive-ratio 1 and a re-peelable pressure-sensitive adhesive-ratio 2 made of a resinous component were prepared as comparative examples, and their relationship with "sealer processability" was evaluated.
<Removable adhesive-Ratio 1>
74.5 parts by weight of the main component BA, 20 parts by weight of the subcomponent EA, 94.5 parts by weight of the (meth) acrylic acid ester (a) having 2 or 4 carbon atoms, and acrylic acid Emulsion polymerization is performed using 4 parts by weight of the carboxyl group-containing monomer (b) and 8 parts by weight of the functional group monomer (c) whose functional group is an epoxy group, and the gel fraction is 92% ( A (meth) acrylic ester emulsion was prepared and used as the main component (A) of the pressure-sensitive adhesive.
Next, 2 parts by weight of a polyoxyethylene alkyl phosphate ester (hereinafter abbreviated as POEAPE) phosphate ester-based surfactant (B) per 100 parts by weight of the adhesive main component (A), Composed of 200 parts by weight of filler (C) in combination with 100 parts by weight of starch and 100 parts by weight of silica powder having an oil absorption of 230 (ml / 100 g) obtained in accordance with the boiled linseed oil method of JISK5101 A pressure-sensitive re-peelable pressure-sensitive adhesive composition according to the present invention was prepared. This re-peelable pressure-sensitive adhesive-1 was applied to one surface of fine paper with a coating weight of 6.2 (g / m 2 ) basis weight and a coating film of 2 μm.

次いで、調製した片面に粘着剤層を設けた２０ｃｍ×４５ｃｍの塗工紙について、フォーム印刷機で粘着剤塗布面にオフセットで印刷をし、次いで市販のキャノン社製のＢＪインクジェットプリンターで、印字を行った結果、ブディングやフェザリング等のインク滲みがなかったが、色味が不鮮明で、印字品質が不良で、紙支持体の印字走行性がスムーズでなかった。また、この塗工紙の粘着剤層特性である圧着下の貼合接着性が不十分で、特に剥離感もスッキリせず、また、耐ブロッキング性も低下した。その結果、再剥離性粘着剤−比１では、充分に「シーラー加工性」を発揮させることができなかった。   Next, about 20cm x 45cm coated paper provided with a pressure-sensitive adhesive layer on one side, it was printed on the pressure-sensitive adhesive coated surface with a foam printer, and then printed with a commercially available BJ inkjet printer manufactured by Canon. As a result, there was no ink bleeding such as padding or feathering, but the color was unclear, the printing quality was poor, and the printing support of the paper support was not smooth. In addition, the adhesiveness under pressure bonding, which is the pressure-sensitive adhesive layer characteristic of the coated paper, was insufficient, particularly the feeling of peeling was not refreshed, and the blocking resistance was also lowered. As a result, the re-peelable pressure-sensitive adhesive ratio 1 could not sufficiently exhibit “sealer processability”.

＜再剥離性粘着剤−比２＞
主成分ＢＡの７８．０重量部と、副成分ＥＡの２０重量部とのアルキル基の炭素数が１〜４の（メタ）アクリル酸エステル（ａ）の９８．０重量部と、アクリル酸のカルボキシル基含有モノマー（ｂ）の２重量部と、連鎖移動剤ノルマルドデシルメルカプタン０．２重量部を用いて乳化重合させて、ゲル分率が１８％である（メタ）アクリル酸エステル系エマルジョンを調製して、これを粘着剤主成分（Ａ）とした。
次いで、この粘着剤主成分（Ａ）の１００重量部当たり、ポリオキシエチレンアルキルリン酸エステル（以後、ＰＯＥＡＰＥと略記する）のリン酸エステル系界面活性剤（Ｂ）の２重量部と、更に、澱粉の１００重量部とＪＩＳＫ５１０１の煮アマニ油法に準拠させて得られた吸油量２３０（ｍｌ／１００ｇ）のシリカ粉末の１００重量部との組合わせ充填剤（Ｃ）の２００重量部とからなる本発明による圧着性再剥離型粘着剤組成物を調製した。この再剥離性粘着剤−１を上質紙の片面に塗工量が６．２（ｇ／ｍ２）坪量で、塗膜２μｍで塗工させた。 <Removable adhesive-Ratio 2>
78.0 parts by weight of the main component BA and 20 parts by weight of the subcomponent EA, 98.0 parts by weight of the (meth) acrylic acid ester (a) having 1 to 4 carbon atoms, and acrylic acid Emulsion polymerization is performed using 2 parts by weight of the carboxyl group-containing monomer (b) and 0.2 parts by weight of the chain transfer agent normal dodecyl mercaptan to prepare a (meth) acrylic acid ester emulsion having a gel fraction of 18%. And this was made into the adhesive main component (A).
Next, 2 parts by weight of a polyoxyethylene alkyl phosphate ester (hereinafter abbreviated as POEAPE) phosphate ester-based surfactant (B) per 100 parts by weight of the adhesive main component (A), Composed of 200 parts by weight of filler (C) in combination with 100 parts by weight of starch and 100 parts by weight of silica powder having an oil absorption of 230 (ml / 100 g) obtained in accordance with the boiled linseed oil method of JISK5101 A pressure-sensitive re-peelable pressure-sensitive adhesive composition according to the present invention was prepared. This re-peelable pressure-sensitive adhesive-1 was applied to one surface of fine paper with a coating weight of 6.2 (g / m 2 ) basis weight and a coating film of 2 μm.

次いで、調製した片面に粘着剤層を設けた２０ｃｍ×４５ｃｍの塗工紙について、フォーム印刷機で粘着剤塗布面にオフセットで印刷をし、次いで市販のキャノン社製のＢＪインクジェットプリンターで、印字を行った結果、色味が不鮮明で、印字品質が不良で、紙支持体の印字走行性がスムーズでなく、紙支持体が撓んでしまった。また、この塗工紙の粘着剤層特性である圧着下の貼合接着性が不十分で、特に剥離感もスッキリせず、また、耐ブロッキング性も著しく低下した。その結果、再剥離性粘着剤−比２では、貼合製品加工をすることができなかった。   Next, about 20cm x 45cm coated paper provided with a pressure-sensitive adhesive layer on one side, it was printed on the pressure-sensitive adhesive coated surface with a foam printer, and then printed with a commercially available BJ inkjet printer manufactured by Canon. As a result, the color was unclear, the printing quality was poor, the printing runnability of the paper support was not smooth, and the paper support was bent. Moreover, the adhesiveness under pressure bonding, which is the pressure-sensitive adhesive layer characteristic of the coated paper, was insufficient, the feeling of peeling was not particularly refreshed, and the blocking resistance was significantly reduced. As a result, it was not possible to process the bonded product with the releasable adhesive-ratio 2.

以上から、製法が著しく簡便で、コスト的にも低廉で、支持体に粘着剤用として加工させる又は実使用時のハンドリング及び作業性に優れる（メタ）アクリル酸エステル系エマルジョンを粘着剤主成分とする本発明による圧着性再剥離型粘着剤組成物を、片面又は両面に粘着剤層として設けた二つ折り又は三つ折り連続帳票用紙を、シーラーに連続供給させて一連の圧着・貼合・搬送下に、連続的に隠蔽ハガキ、親展ハガキ、封書に貼合製品化させるに、本発明の粘着剤組成物による塗布粘着剤層は、シーラーの回転ローラーに係わる加工作業性を低下させず、高効率で貼合製品化させる「シーラー加工性」に優れる隠蔽ハガキ、親展ハガキ、封書等の粘着剤層用の圧着性再剥離型粘着剤組成物を提供することができた。
From the above, the production method is extremely simple, low in cost, processed as a pressure-sensitive adhesive for the support, or (meth) acrylic acid ester emulsion having excellent handling and workability in actual use as the main component of the pressure-sensitive adhesive. A series of pressure-bonding / bonding / carrying under pressure-removable pressure-sensitive adhesive composition according to the present invention, by continuously supplying a bi-fold or tri-fold continuous form paper provided as a pressure-sensitive adhesive layer on one or both sides to a sealer In addition, the coated adhesive layer by the pressure-sensitive adhesive composition of the present invention is highly efficient without reducing the workability related to the rotating roller of the sealer, so that it can be continuously bonded to concealed postcards, confidential postcards and sealed letters. It was possible to provide a pressure-removable pressure-sensitive adhesive composition for pressure-sensitive adhesive layers such as concealment postcards, confidential postcards, and sealed letters, which is excellent in “sealer processability” to be made into a bonded product.

Claims (5)

紙支持体の片面又は両面に印刷適性を有する圧着性で、再剥離性の粘着剤層を設け、その粘着剤層が印刷及び印字済みである二つ折り又は三つ折り状態の連続帳票用紙を、シーラー装置に連続供給させて圧着・貼合・搬送させながら隠蔽貼合製品に加工させるに、シーラー装置の加工作業性を損ねることのない圧着性再剥離型の粘着剤組成物において、
（１）アルキル基の炭素数が１〜１２の（メタ）アクリル酸アルキルエステル（ａ）の９０〜９８．９５重量部と、
（２）カルボキシル基含有モノマー（ｂ）の１〜５重量部と、
（３）エポキシ基、水酸基、シラノール基及びメチロール基から選ばれる何れかの官能基を有するモノマー（ｃ）の０．０５〜５重量部と、
を用いて乳化重合させて得られる（メタ）アクリル酸エステル系エマルジョンであって、且つゲル分率が６０％以上８５％以下の範囲にある粘着剤主成分（Ａ）の１００重量部当たり、リン酸エステル系界面活性剤（Ｂ）の０．５〜５重量部と、
有機系及び無機系微細粉末の組み合わせ充填剤（Ｃ）の４０〜３００重量部と、
を含有していることを特徴とする圧着性再剥離型粘着剤組成物。 A double-folded or tri-fold continuous form paper with a pressure-removable and re-peelable pressure-sensitive adhesive layer having printability on one or both sides of a paper support, which has been printed and printed, is used as a sealer. In the pressure-sensitive adhesive re-peelable pressure-sensitive adhesive composition that does not impair the workability of the sealer device in order to process it into a concealed bonded product while being continuously supplied to the device and crimped, bonded, and conveyed,
(1) 90 to 98.95 parts by weight of an alkyl group (meth) acrylic acid alkyl ester (a) having 1 to 12 carbon atoms;
(2) 1 to 5 parts by weight of the carboxyl group-containing monomer (b);
(3) 0.05 to 5 parts by weight of the monomer (c) having any functional group selected from an epoxy group, a hydroxyl group, a silanol group, and a methylol group;
Per 100 parts by weight of the main component of the pressure-sensitive adhesive (A), which is a (meth) acrylic ester emulsion obtained by emulsion polymerization using an adhesive and has a gel fraction in the range of 60 % to 85%. 0.5 to 5 parts by weight of the acid ester surfactant (B);
40 to 300 parts by weight of a combination filler (C) of organic and inorganic fine powders;
A pressure-sensitive adhesive re-peelable pressure-sensitive adhesive composition comprising: 前記有機系微細粉末が、澱粉で、且つ前記無機系微細粉体が、ＪＩＳＫ５１０１法に準拠する煮アマニ油法による吸油量が１００〜２５０ｍｌ／１００ｇのシリカ粉末であることを特徴とする請求項１に記載の圧着性再剥離型粘着剤組成物。   The organic fine powder is starch, and the inorganic fine powder is a silica powder having an oil absorption of 100 to 250 ml / 100 g according to a boiled linseed oil method in accordance with the JISK5101 method. The pressure-sensitive adhesive re-peelable pressure-sensitive adhesive composition described in 1. 澱粉とシリカ粉末との組み合わせ充填剤（Ｃ）中、重量％で表してシリカ粉末が１０〜
９０％であることを特徴とする請求項２に記載の圧着性再剥離型粘着剤組成物。 In the combination filler (C) of starch and silica powder, the silica powder is expressed as 10% by weight.
The pressure-sensitive adhesive peelable pressure-sensitive adhesive composition according to claim 2, wherein the pressure-sensitive adhesive composition is 90%. 前記連続帳票の紙支持体の片面又は両面に設ける前記粘着剤層に、請求項１〜３の何れか一項に記載の圧着性再剥離型粘着剤組成物が、塗工膜厚１〜５０μmの範囲になるように施されていることを特徴とする隠蔽ハガキ。 The pressure-sensitive adhesive re-peelable pressure-sensitive adhesive composition according to any one of claims 1 to 3 has a coating thickness of 1 to 50 µm on the pressure-sensitive adhesive layer provided on one or both sides of the paper support of the continuous form. Concealment postcard characterized by being applied to the range. 前記連続帳票の紙支持体の片面又は両面に設ける前記粘着剤層に、請求項１〜３の何れか一項に記載の圧着性再剥離型粘着剤組成物が、塗工膜厚１〜５０μmの範囲になるように施されていることを特徴とする封書。 The pressure-sensitive adhesive re-peelable pressure-sensitive adhesive composition according to any one of claims 1 to 3 has a coating thickness of 1 to 50 µm on the pressure-sensitive adhesive layer provided on one or both sides of the paper support of the continuous form. A sealed letter characterized in that it is applied in the range of.
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