JPH0813961B2 - Removable solid adhesive - Google Patents
Removable solid adhesiveInfo
- Publication number
- JPH0813961B2 JPH0813961B2 JP1028295A JP2829589A JPH0813961B2 JP H0813961 B2 JPH0813961 B2 JP H0813961B2 JP 1028295 A JP1028295 A JP 1028295A JP 2829589 A JP2829589 A JP 2829589A JP H0813961 B2 JPH0813961 B2 JP H0813961B2
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- adhesive
- pressure
- polymer
- solid pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、何回でも剥がしては又貼着し得る再剥離性
固形粘着剤に関する。TECHNICAL FIELD The present invention relates to a removable solid pressure-sensitive adhesive which can be peeled off and adhered any number of times.
（従来の技術） この種の再剥離性固形粘着剤としては、特公昭47−25
448号に開示された接着ステックがよく知られている。
この接着ステックは、炭素数８〜36個の脂肪族カルボン
酸のアルカリ金属塩又はアンモニウム塩などのゲル化剤
と、水溶性又は水分散性の接着物質からなるもので、接
着物質として高分子量アクリルエマルジョン等が配合さ
れている。(Prior Art) As a removable solid pressure-sensitive adhesive of this type, Japanese Patent Publication No.
The adhesive stick disclosed in No. 448 is well known.
This adhesive stick is composed of a gelling agent such as an alkali metal salt or ammonium salt of an aliphatic carboxylic acid having 8 to 36 carbon atoms and a water-soluble or water-dispersible adhesive substance. Emulsion etc. are mixed.
（発明が解決しようとする課題） しかしながら、上記の接着ステックのようにアクリル
エマルジョンを含む固形粘着剤は、その凝集力が大きい
ため、紙等を貼付けた場合にしっとりとした貼付き感が
なく、しかも、貼付けと剥離を繰り返して行うと、接着
力が大幅に低下するという問題があった。(Problems to be solved by the invention) However, since the solid pressure-sensitive adhesive containing an acrylic emulsion like the above-mentioned adhesive stick has a large cohesive force, there is no moist sticking feeling when a paper or the like is stuck, Moreover, there is a problem that the adhesive strength is significantly reduced when the application and the peeling are repeated.
また、アクリルエマルジョンは一般に架橋されてな
く、且つ乳化剤を含んでいるので、熱安定性に劣ってお
り、そのため粘着剤を溶融注型して所定形状に成形する
ときの熱で変質しやすいという問題もあった。In addition, since acrylic emulsions are generally not cross-linked and contain an emulsifier, they have poor thermal stability, and are therefore susceptible to heat deterioration when melt-casting the adhesive to a predetermined shape. There was also.
本発明は上記問題に鑑みてなされたもので、その目的
とするところは、しっとりとした貼付き感があり、貼付
けと剥離を何回繰り返しても接着力の大幅な低下を生じ
ることがなく、溶融注型時の熱で変質する心配も殆どな
い再剥離性固形粘着剤を提供することにある。The present invention has been made in view of the above problems, and the purpose thereof is to have a moist feeling of sticking, without causing a significant decrease in adhesive strength even if the sticking and peeling are repeated many times. An object of the present invention is to provide a removable solid pressure-sensitive adhesive that is hardly affected by heat during melt casting.
（課題を解決するための手段） 本発明の再剥離性固形粘着剤は、微球状重合体とゲル
化剤を含有して成り、該微球状重合体は、一般式 （但しR1は水素またはメチル基であり、R2は炭素数が４
〜12のアルキル基である）で示されるアルキル（メタ）
アクリレートを油溶性重合開始剤と界面活性剤存在下に
水懸濁重合させたものであることを特徴としており、そ
のことによって上記目的が達成される。(Means for Solving the Problems) The removable solid pressure-sensitive adhesive of the present invention comprises a fine spherical polymer and a gelling agent, and the fine spherical polymer has the general formula (However, R 1 is hydrogen or a methyl group, and R 2 has 4 carbon atoms.
Is an alkyl group of ~ 12) alkyl (meth)
It is characterized in that it is obtained by subjecting an acrylate to water suspension polymerization in the presence of an oil-soluble polymerization initiator and a surfactant, thereby achieving the above object.
本発明において微球状重合体の合成に用いるアルキル
（メタ）アクリレートの代表例としては、ブチル（メ
タ）アクリレート、ヘキシル（メタ）アクリレート、オ
クチル（メタ）アクリレート、ノニル（メタ）アクリレ
ート等が挙げられ、これらは単独で又は適宜混合して使
用される。また、保水性等を付与するために必要に応じ
て（メタ）アクリル酸やアクリルアミド等の極性モノマ
ーを混合することもできる。Representative examples of the alkyl (meth) acrylate used for the synthesis of the microspherical polymer in the present invention include butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, and the like. These are used alone or in an appropriate mixture. In addition, polar monomers such as (meth) acrylic acid and acrylamide may be mixed as necessary to impart water retention and the like.
このアルキル（メタ）アクリレートの重合に用いる油
溶性重合開始剤は、通常のラジカル重合で開始剤として
使用されるものであり、好適なものとしては、ベンゾイ
ルパーオキシドやジクミルパーオキシド等が挙げられ
る。また界面活性剤としては、ドデシルベンゼンスルホ
ン酸ナトリウム等が好適に使用される。The oil-soluble polymerization initiator used for the polymerization of this alkyl (meth) acrylate is used as an initiator in the usual radical polymerization, and preferable examples thereof include benzoyl peroxide and dicumyl peroxide. . As the surfactant, sodium dodecylbenzene sulfonate or the like is preferably used.
本発明の粘着成分である微球状重合体は、上記のアル
キル（メタ）アクリレートに上記の重合開始剤を溶解
し、これを上記の界面活性剤を含む水に懸濁させ、撹拌
しながら所定温度で重合反応させて得られるポリマー粒
子であり、10〜200μｍの平均粒径を有するものが粘着
成分として適当である。微球状重合体の平均粒径が200
μｍより大きい場合は、塗布性の良好な固形粘着剤を得
ることが困難となり、10μｍより小さい場合は、微球状
重合体が紙等の被着体表面の微細空隙内に埋もれるため
再剥離性の良好な固形粘着剤を得ることが困難となるか
らである。微球状重合体の一層好ましい平均粒径の範囲
は30〜150μｍである。The microspherical polymer, which is the adhesive component of the present invention, is prepared by dissolving the above-mentioned polymerization initiator in the above-mentioned alkyl (meth) acrylate, suspending it in water containing the above-mentioned surfactant, and stirring at a predetermined temperature. Polymer particles obtained by the polymerization reaction in (1) and having an average particle size of 10 to 200 μm are suitable as an adhesive component. The average particle size of the fine spherical polymer is 200
If it is larger than μm, it becomes difficult to obtain a solid pressure-sensitive adhesive having good coatability, and if it is smaller than 10 μm, the fine spherical polymer is buried in the fine voids on the surface of the adherend such as paper and the removability of This is because it becomes difficult to obtain a good solid pressure-sensitive adhesive. A more preferable range of the average particle size of the microspherical polymer is 30 to 150 μm.
この微球状重合体の含有量は、固形粘着剤全体の５〜
85重量％の範囲とするのが適当である。85重量％より多
量に含有させることは、微球状重合体が細密充填構造に
近くなるので実質的に不可能であり、一方、５重量％よ
り少なくなると、固形粘着剤の接着力が乏しくなるから
である。The content of the fine spherical polymer is 5 to 5% of the whole solid pressure-sensitive adhesive.
A range of 85% by weight is suitable. If the content is more than 85% by weight, it is practically impossible because the fine spherical polymer is close to a close-packed structure, while if it is less than 5% by weight, the adhesive strength of the solid adhesive becomes poor. Is.
本発明に用いるゲル化剤は、水懸濁重合で合成した微
球状重合体の懸濁液をゼリー状又はワックス状に固形化
するもので、例えば炭素数が８〜16の脂肪族カルボン酸
のアルカリ金属塩もしくはアンモニウム塩、1,2−ヒド
ロキシステアリン酸塩、ジ又はトリ−ベンジリデンソル
ビトール、或いはＮ−ラウロイルグルタミン酸ジブチル
アミド等のＮ−アシルアミノ酸のアミド、エステル、ア
ミン塩などの誘導体が使用される。このゲル化剤は、微
球状重合体の懸濁液を適度な硬さに固形化して、紙等の
表面に塗付ける時の保形性及び展伸性が良好な固形粘着
剤を得るために配合されるものであるから、その配合量
はゲル化剤のゲル化能を考慮して適宜決定する必要があ
り、例えば、ステアリン酸ナトリウム等の脂肪族カルボ
ン酸のアルカリ金属塩を用いる場合は、１〜10重量％程
度の配合量とするのが適当である。The gelling agent used in the present invention solidifies a suspension of a microspherical polymer synthesized by water suspension polymerization into a jelly-like or wax-like substance, for example, an aliphatic carboxylic acid having 8 to 16 carbon atoms. Alkali metal salts or ammonium salts, 1,2-hydroxystearate salts, di- or tri-benzylidene sorbitol, or derivatives of N-acyl amino acid amides, esters, amine salts and the like such as N-lauroyl glutamic acid dibutylamide are used. . This gelling agent solidifies the suspension of the fine spherical polymer to an appropriate hardness to obtain a solid pressure-sensitive adhesive having good shape retention and spreadability when applied to the surface of paper or the like. Since it is to be blended, its blending amount must be appropriately determined in consideration of the gelling ability of the gelling agent, for example, when using an alkali metal salt of an aliphatic carboxylic acid such as sodium stearate, A blending amount of about 1 to 10% by weight is suitable.
本発明の固形粘着剤は、上記の微球状重合体よりなる
粘着成分とゲル化剤の他に、液体成分として水、エタノ
ールやメタノール等のアルコール、メチルエチルケトン
等の有機溶剤を含むものである。この液体成分の含有量
は、固形粘着剤全体の５〜85重量％の範囲とするのが適
当である。液体成分の水は、微球状重合体を水懸濁重合
したとき懸濁液に含まれるものであるが、水以外の液体
成分を含有させる場合は、水懸濁重合後に微球状重合体
を凝集分離し、これを水以外の液体成分に再び分散させ
て、その分散液にゲル化剤を加えて固形化すればよい。The solid pressure-sensitive adhesive of the present invention contains, as a liquid component, water, an alcohol such as ethanol or methanol, and an organic solvent such as methyl ethyl ketone, in addition to the pressure-sensitive adhesive component made of the fine spherical polymer and the gelling agent. The content of this liquid component is appropriately in the range of 5 to 85% by weight based on the whole solid pressure-sensitive adhesive. Water, which is a liquid component, is contained in the suspension when the microspherical polymer is subjected to water suspension polymerization, but when a liquid component other than water is contained, the microspherical polymer is aggregated after the water suspension polymerization. It may be separated, redispersed in a liquid component other than water, and a gelling agent may be added to the dispersion to solidify.
なお、本発明の固形粘着剤は、必要に応じて、グリセ
リン、ポリエチレングリコール等の保水剤や、ポリビニ
ルピロリドン、アクリル系エマルジョン、ニトロセルロ
ース等のバインダーや、アルキル（メタ）アクリレート
以外の粘着付与樹脂等を適量含有させてもよいものであ
る。In addition, the solid pressure-sensitive adhesive of the present invention is, if necessary, a water retention agent such as glycerin or polyethylene glycol, a binder such as polyvinylpyrrolidone, an acrylic emulsion, or nitrocellulose, a tackifying resin other than an alkyl (meth) acrylate, and the like. May be contained in an appropriate amount.
以上のような本発明の再剥離性固形粘着剤は、粘着成
分としてアルキル（メタ）アクリレートの水懸濁重合で
得られる微球状重合体を含有させているため、アクリル
エマルジョン粘着剤のような凝集によるザラザラした貼
付け感がなく、しっとりとした感じで貼付けることがで
き、しかも、再剥離性が良好で貼付けと剥離を何回繰り
返しても接着力が大幅に低下することはない。また、微
球状重合体は架橋されおり、乳化剤も含まれていないの
で、本発明の固形粘着剤は耐熱性が良好で溶融注型時の
熱で変質する心配もない。更に、アクリルエマルジョン
粘着剤よりも含水率を減少させることができるので、乾
燥性も向上する。Since the removable solid pressure-sensitive adhesive of the present invention as described above contains a fine spherical polymer obtained by water suspension polymerization of alkyl (meth) acrylate as a pressure-sensitive adhesive component, it can be aggregated like an acrylic emulsion pressure-sensitive adhesive. There is no rough sticking feeling due to, and it can be applied with a moist feeling, and the removability is good, and the adhesive strength does not significantly decrease even if the application and peeling are repeated many times. Further, since the fine spherical polymer is cross-linked and does not contain an emulsifier, the solid pressure-sensitive adhesive of the present invention has good heat resistance and there is no fear of being deteriorated by heat during melt casting. Further, since the water content can be reduced as compared with the acrylic emulsion pressure-sensitive adhesive, the drying property is also improved.
（実施例） 本発明の実施例について以下に説明する。(Example) The Example of this invention is described below.
実施例１ ２−エチルヘキシルアクリレート100部（重量部、以
下同様）にベンゾイルパーオキシドを0.1部添加し、こ
れをドデシルベンゼンスルホン酸ナトリウム2gを含む水
300mlに分散させて、撹拌しながら75℃で５時間反応さ
せ、平均粒径が50μｍの微球状重合体を得た。そして、
この微球状重合体の懸濁液を、固形分濃度が60％になる
まで濃縮した。Example 1 0.1 part of benzoyl peroxide was added to 100 parts of 2-ethylhexyl acrylate (parts by weight, the same applies hereinafter), and this was added to water containing 2 g of sodium dodecylbenzenesulfonate.
The mixture was dispersed in 300 ml and reacted with stirring at 75 ° C. for 5 hours to obtain a fine spherical polymer having an average particle size of 50 μm. And
This suspension of the microspherical polymer was concentrated until the solid content concentration became 60%.
この濃縮した微球状重合体懸濁液100部を80℃に保っ
たまま、ステアリン酸ナトリウム５部を該懸濁液に添加
して30分撹拌し、更にグリセリン20部を添加して30分撹
拌してから、直径10mmの試験管に流し込んで常温まで冷
却し、スティック状の固形粘着剤を得た。While maintaining 100 parts of this concentrated microspherical polymer suspension at 80 ° C, 5 parts of sodium stearate was added to the suspension and stirred for 30 minutes, and 20 parts of glycerin was further added and stirred for 30 minutes. Then, it was poured into a test tube having a diameter of 10 mm and cooled to room temperature to obtain a stick-shaped solid adhesive.
この固形粘着剤を上質紙に擦りつけて粘着層を形成
し、乾燥させてから下記（ａ）及び（ｂ）の方法によっ
て接着力（初期接着力）と再剥離接着力を測定した。The solid pressure-sensitive adhesive was rubbed on a high-quality paper to form a pressure-sensitive adhesive layer, which was dried and then the adhesive force (initial adhesive force) and re-peelable adhesive force were measured by the following methods (a) and (b).
（ａ）接着力（初期接着力）の測定：粘着層を形成した
上質紙に同種の上質紙を貼合わせて、2kgのゴムローラ
で一往復圧着し、300mm/分の引張速度でＴ剥離力を測定
する。(A) Measurement of adhesive strength (initial adhesive strength): The same kind of high-quality paper is pasted on the high-quality paper with the adhesive layer, and it is pressure-bonded back and forth once with a 2 kg rubber roller, and the T-peel strength is obtained at a pulling speed of 300 mm / min. taking measurement.
（ｂ）再剥離接着力の測定：上記（ａ）の操作を10回繰
り返して行い、10回目のＴ剥離力を再剥離力とする。(B) Measurement of re-peeling adhesive force: The above operation (a) is repeated 10 times, and the 10th T-peeling force is taken as the re-peeling force.
その結果を下記の表１に示す。 The results are shown in Table 1 below.
実施例２ 実施例１と同様にして得た微球状重合体懸濁液をアセ
トン中に入れて微球状重合体を凝集させ、これを取り出
して再びメチルエチルケトンに分散させ、固形分濃度15
％の分散液とした。Example 2 A fine spherical polymer suspension obtained in the same manner as in Example 1 was put into acetone to aggregate the fine spherical polymer, which was taken out and dispersed again in methyl ethyl ketone to obtain a solid content concentration of 15
% Dispersion.
この分散液100部を75℃に保ったままジベンジリデン
ソルビトール（商品名：ゲルオールＤ、新日本理化
（株）製）６部とニトロセルロース10部を添加して30分
撹拌し、この均一な溶液を直径10mmの試験管に流し込ん
で常温まで冷却し、スティック状の固形粘着剤を得た。While maintaining 100 parts of this dispersion liquid at 75 ° C, 6 parts of dibenzylidene sorbitol (trade name: Gelol D, manufactured by Shin Nippon Rika Co., Ltd.) and 10 parts of nitrocellulose were added and stirred for 30 minutes to obtain a uniform solution. Was poured into a test tube having a diameter of 10 mm and cooled to room temperature to obtain a stick-shaped solid pressure-sensitive adhesive.
この固形粘着剤について、実施例１と同様の方法で接
着力と再剥離接着力を測定した結果を下記の表１に示
す。With respect to this solid pressure-sensitive adhesive, the results of measuring the adhesive force and the re-peelable adhesive force in the same manner as in Example 1 are shown in Table 1 below.
次に比較例を挙げる。 Next, a comparative example will be described.
比較例１ ２エチルヘキシルアクリレートを乳化重合してポリ２
エチルヘキシルアクリレートのエマルジョン（固形分濃
度60％）を得た。このエマルジョンに、実施例１と同様
にしてステアリン酸ナトリウムとグリセリンを添加混合
し、試験管に入れてスティック状の固形粘着剤を得た。Comparative Example 1 2 Ethylhexyl acrylate was emulsion-polymerized to obtain poly 2
An emulsion of ethylhexyl acrylate (solid content concentration 60%) was obtained. To this emulsion, sodium stearate and glycerin were added and mixed in the same manner as in Example 1 and placed in a test tube to obtain a stick-shaped solid pressure-sensitive adhesive.
この固形粘着剤について、実施例１と同様の方法で接
着力と再剥離接着力を測定した結果を下記の表１に示
す。With respect to this solid pressure-sensitive adhesive, the results of measuring the adhesive force and the re-peelable adhesive force in the same manner as in Example 1 are shown in Table 1 below.
比較例２ ２エチルヘキシルアクリレートをメチルエチルケトン
中で溶液重合し、ポリ２エチルヘキシルアクリレートの
メチルエチルケトン溶液（固形分濃度60％）を得た。こ
の溶液にメチルエチルケトンを更に加えて固形分濃度を
15％とし、実施例２と同様にしてジベンジリデンソルビ
トールとニトロセルロースを添加混合し、試験管に入れ
てスティック状の固形粘着剤を得た。Comparative Example 2 2-Ethylhexyl acrylate was solution polymerized in methyl ethyl ketone to obtain a solution of poly 2-ethylhexyl acrylate in methyl ethyl ketone (solid content concentration 60%). Methyl ethyl ketone was further added to this solution to adjust the solid content concentration.
15%, and dibenzylidene sorbitol and nitrocellulose were added and mixed in the same manner as in Example 2 and placed in a test tube to obtain a stick-shaped solid pressure-sensitive adhesive.
この固形粘着剤について、実施例１と同様の方法で接
着力と再剥離接着力を測定した結果を下記の表１に示
す。With respect to this solid pressure-sensitive adhesive, the results of measuring the adhesive force and the re-peelable adhesive force in the same manner as in Example 1 are shown in Table 1 below.
この表１をみれば、本発明の実施例１及び実施例２の
再剥離性固形粘着剤は、乳化重合した比較例１の粘着剤
や溶液重合した比較例２の粘着剤よりも、初期の接着力
が遥かに大きく、貼付けと剥離を10回繰り返した後でも
接着力の低下が僅か10〜13％程度であり、再剥離性に優
れたものであることが判る。 As shown in Table 1, the removable solid pressure-sensitive adhesives of Examples 1 and 2 of the present invention are more effective than the pressure-sensitive adhesives of Comparative Example 1 emulsion-polymerized and the pressure-sensitive adhesives of Comparative Example 2 solution-polymerized. The adhesive strength is much higher, and even after 10 times of application and peeling, the decrease in adhesive strength is only about 10 to 13%, which shows that the removability is excellent.
（発明の効果） 本発明の再剥離性固形粘着剤は、このように、しっと
りとした貼付け感があり、再剥離性が良好で、貼付けと
剥離を繰り返しても接着力の大幅な低下を生じることが
なく、また耐熱性にも優れるため溶融注型時に熱変質す
る心配がなく、更にアクリルエマルジョン粘着剤より含
水率を少なくして乾燥性を向上させることもできるとい
った効果を奏する。(Effects of the Invention) The removable solid pressure-sensitive adhesive of the present invention thus has a moistened sticking feeling, has good removability, and causes a significant decrease in adhesive strength even after repeated sticking and peeling. In addition, since it is excellent in heat resistance, there is no concern that it will be thermally deteriorated during melt casting, and further, the moisture content can be made smaller than that of the acrylic emulsion pressure-sensitive adhesive to improve the drying property.
Claims (1)
上記の微球状重合体は、一般式 （但しR1は水素またはメチル基であり、R2は炭素数が４
〜12のアルキル基である）で示されるアルキル（メタ）
アクリレートを油溶性重合開始剤と界面活性剤存在下に
水懸濁重合させたものであることを特徴とする再剥離性
固形粘着剤。1. A microsphere polymer and a gelling agent are contained,
The above microspherical polymer has the general formula (However, R 1 is hydrogen or a methyl group, and R 2 has 4 carbon atoms.
Is an alkyl group of ~ 12) alkyl (meth)
A releasable solid pressure-sensitive adhesive, which is obtained by subjecting an acrylate to water-suspension polymerization in the presence of an oil-soluble polymerization initiator and a surfactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1028295A JPH0813961B2 (en) | 1989-02-06 | 1989-02-06 | Removable solid adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1028295A JPH0813961B2 (en) | 1989-02-06 | 1989-02-06 | Removable solid adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02206672A JPH02206672A (en) | 1990-08-16 |
| JPH0813961B2 true JPH0813961B2 (en) | 1996-02-14 |
Family
ID=12244627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1028295A Expired - Fee Related JPH0813961B2 (en) | 1989-02-06 | 1989-02-06 | Removable solid adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0813961B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9206344A (en) * | 1991-08-09 | 1995-04-11 | Minnesota Mining & Mfg | Repositionable glue stick and process for providing repositionable adhesive on an individual sheet of paper. |
| JP4355405B2 (en) * | 1998-10-13 | 2009-11-04 | リンテック株式会社 | Ninhydrin-containing pressure-sensitive adhesive composition and sheet for fingerprint detection, or for collecting handprint or footprint |
| JP2011246700A (en) * | 2010-04-27 | 2011-12-08 | Nippon Synthetic Chem Ind Co Ltd:The | Acrylic resin solution, acrylic adhesive composition, acrylic adhesive, adhesive sheet, acrylic adhesive for optical element, and optical element with adhesive layer |
-
1989
- 1989-02-06 JP JP1028295A patent/JPH0813961B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02206672A (en) | 1990-08-16 |
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