JP2619830B2 - Adhesive - Google Patents
AdhesiveInfo
- Publication number
- JP2619830B2 JP2619830B2 JP62300346A JP30034687A JP2619830B2 JP 2619830 B2 JP2619830 B2 JP 2619830B2 JP 62300346 A JP62300346 A JP 62300346A JP 30034687 A JP30034687 A JP 30034687A JP 2619830 B2 JP2619830 B2 JP 2619830B2
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- Japan
- Prior art keywords
- weight
- monomer
- adhesive
- pressure
- sensitive adhesive
- 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 - Lifetime
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- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、粘着テープ、粘着ラベル等の各種粘着加工
品に使用される粘着剤で、特に加工適性に優れた粘着剤
を１段重合で提供するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an adhesive used for various kinds of adhesive processed products such as an adhesive tape and an adhesive label. To provide.
［従来の技術］ 粘着剤には、適切な粘着力、接着力、凝集力が必要で
あるが、特に、ラベル、ステッカー、シール等の粘着ラ
ベル用粘着剤には加工適性も要求される。[Prior Art] Adhesives require appropriate adhesive strength, adhesive strength, and cohesive strength, but in particular, adhesives for adhesive labels such as labels, stickers, and seals also require processability.
一般に、サイドタック、打ち抜き加工等の加工適性を
良くしようとすると、粘着剤の凝集力を増す（硬くす
る）ことになり、凝集力を増すと接着力、粘着力が低下
するという現象がみられ、物性と加工適性のバランスを
適切にとることが必要とされる。Generally, when trying to improve workability such as side tacking and punching, the cohesive strength of the adhesive increases (hardens), and when the cohesive strength increases, the adhesive strength and the adhesive strength decrease. It is necessary to properly balance physical properties and workability.
従来、代表的な粘着ラベル用粘着剤としては、アクリ
ル系粘着剤が知られており、該粘着剤は架橋密度を増し
たり、可塑剤を添加したり、粘着付与剤、その他硬質成
分のブレンドなどの手段により、サイドタックや打ち抜
き加工等に適した硬さに調整されて実用に供されてい
る。Conventionally, as a typical pressure-sensitive adhesive for pressure-sensitive adhesive labels, an acrylic pressure-sensitive adhesive is known, and the pressure-sensitive adhesive increases a crosslinking density, adds a plasticizer, a tackifier, a blend of other hard components, and the like. By the means described above, the hardness is adjusted to be suitable for side tacking, punching, and the like, and is put to practical use.
かかる加工適性の改善された粘着剤は文献にも記載が
あり、例えば特開昭57−2374号公報には、アクリル酸エ
ステルモノマーと官能基（カルボキシル基や水酸基）含
有アクリルモノマーとをグラフト重合、即ち、２段重合
して製造された粘着剤が示されている。該公報の実施例
の１つに、（ａ）アクリル酸エステルモノマー、（ｂ）
カルボキシル基含有モノマー、（ｃ）ヒドロキシル基含
有モノマー、（ｄ）前記以外のビニルモノマー、を使用
した例もあり、本願と重合方法及びモノマーの使用割合
の点では異なるが、同一のモノマー種を組合わせた点で
は軌を一にした実例が挙げられている。Such pressure-sensitive adhesives with improved workability are also described in the literature. For example, JP-A-57-2374 discloses graft polymerization of an acrylic acid ester monomer and a functional group (carboxyl group or hydroxyl group) -containing acrylic monomer. That is, an adhesive produced by two-stage polymerization is shown. One example of the publication is (a) an acrylate monomer, (b)
There are also examples in which a carboxyl group-containing monomer, (c) a hydroxyl group-containing monomer, and (d) a vinyl monomer other than those described above are used. In terms of the combined points, there is an example of the same gauge.
［発明が解決しようとする問題点］ しかし、アクリル系粘着剤に可塑剤の添加や、粘着付
与剤、あるいは硬質成分をブレンドする場合には、着
色、耐候性低下等の点で障害の出る恐れがあり、できれ
ば共重合体の組成の改善のみで、かかる要求を満足させ
ることが有利であると考えられる。その点特開昭57−23
74号公報の方法の場合実用化が期待できるが、本発明者
の検討では粘着剤の物性、加工適性の面では満足できて
も、２段重合であるため、重合時の拘束時間が長い、重
合開始剤の使用量が多い、得られる粘着剤がゲル化しや
すく保存安定性が悪い等、工業的規模での製造面で制約
が多いことが明らかとなった。[Problems to be Solved by the Invention] However, when a plasticizer is added to an acrylic pressure-sensitive adhesive, or a tackifier or a hard component is blended, there is a possibility that problems may occur in terms of coloring, deterioration of weather resistance, and the like. It is considered that it is advantageous to satisfy such requirements only by improving the composition of the copolymer if possible. In that regard, JP-A-57-23
In the case of the method of No. 74, practical application can be expected, but in the study of the present inventor, even if it is satisfactory in terms of the physical properties of the pressure-sensitive adhesive and processability, because of the two-stage polymerization, the binding time during polymerization is long, It has been clarified that there are many restrictions in terms of production on an industrial scale, for example, the amount of the polymerization initiator used is large, the obtained pressure-sensitive adhesive easily gels, and the storage stability is poor.
そこで本発明者等は前記２段重合法よりも工業的に有
利な方法である１段重合、即ち各モノマーを一括混合し
重合する方法を試みたが、該公報に記載される条件をそ
のまま採用し、単に２段重合に変更しただけでは目的が
達成できなかった。Therefore, the present inventors have attempted a single-stage polymerization, which is an industrially more advantageous method than the two-stage polymerization method, that is, a method in which each monomer is mixed at a time and polymerized, but the conditions described in the publication are employed as they are. However, the objective could not be achieved simply by changing to the two-stage polymerization.
［問題点を解決するための手段］ そこで本発明者等は、更に研究を重ねた結果、 （ａ）ヒドロキシル基を含有しないアクリル酸エステル
モノマーの少なくとも１種が 70〜82重量％ （ｂ）カルボキシル基含有モノマーの少なくとも１種が ３〜５重量％ （ｃ）ヒドロキシル基含有（メタ）アクリル酸エステル
モノマーの少なくとも１種が 0.04〜0.4重量％ （ｄ）酢酸ビニルモノマーが 10〜17重量％ （ｅ）上記以外のビニルモノマーの少なくとも１種が １〜10重量％ の組成である共重合体であって、かつ上記モノマーの混
合物を１段重合させて得られる共重合体からなる粘着剤
が上記目的を達成できることを見出し、本発明を完成す
るに至った。[Means for Solving the Problems] Accordingly, the present inventors have further studied and found that: (a) at least one of the acrylate monomer having no hydroxyl group is 70 to 82% by weight; (C) at least one of the hydroxyl group-containing (meth) acrylate monomers is 0.04 to 0.4% by weight (d) 10 to 17% by weight of the vinyl acetate monomer (e) A) a pressure-sensitive adhesive comprising a copolymer in which at least one of the other vinyl monomers has a composition of 1 to 10% by weight, and a copolymer obtained by one-stage polymerization of a mixture of the above monomers; Have been achieved, and the present invention has been completed.
本発明の特徴点は、上述した如く１段重合により共重
合体を得ると共に、（ｂ）カルボキシル基含有モノマー
と（ｃ）ヒドロキシル基含有（メタ）アクリル酸エステ
ルモノマー成分の含有率をある特定した範囲内に限定し
た点にある。この結果得られた粘着剤は、特開昭57−23
74号公報の粘着剤と同等の物性及び加工適性が得られる
上、本願の方が、製造拘束時間が短く、重合開始剤の使
用量が少なく、得られた粘着剤の保存性も優れている
等、工業的な製造面で顕著な効果を有する。A feature of the present invention is that a copolymer is obtained by one-stage polymerization as described above, and the content of (b) a carboxyl group-containing monomer and (c) a hydroxyl group-containing (meth) acrylate monomer component is specified. It is limited to the range. The resulting pressure-sensitive adhesive is described in JP-A-57-23.
In addition to obtaining the same physical properties and processability as the pressure-sensitive adhesive of No. 74, the present application has a shorter production restraint time, uses less polymerization initiator, and has excellent storage stability of the obtained pressure-sensitive adhesive. It has a remarkable effect in industrial production.
本発明中のアクリル系共重合体は、適当な溶媒に
（ａ），（ｂ），（ｃ），（ｄ）、（ｅ）の単量体混合
モノマーを溶解し、重合開始剤を加えて昇温し、反応さ
せるか、場合によっては反応熱除去のために混合モノマ
ー又は重合開始剤を滴下仕込みする等して反応させる。
重合形式としては溶液重合、乳化重合、懸濁重合等の任
意の方法が実施可能であるが、溶液重合、乳化重合が実
用的である。溶液重合にあたって溶媒としては、一般に
酢酸メチル、酢酸エチル等のエステル類、ベンゼン、ト
ルエン、キシレン等の芳香族炭化水素、シクロヘキサン
等の脂環族炭化水素、及びアセトン、メチルエチルケト
ン等のケトン類等が単独または混合して使用されるが、
これらに限定されない。溶媒の決定には、溶媒の沸点、
得られた共重合体の溶解性や分子量、更に作業性などを
考慮に入れることが必要で、例えば、酢酸エチルや酢酸
エチルとトルエンの混合溶媒等が特に好ましい。乳化重
合にあたっては、乳化剤としてグリセリンモノステアレ
ート、ポリオキシエチレンフェニルエーテル、ラウリル
硫酸ソーダ等が使用できる。The acrylic copolymer in the present invention is obtained by dissolving the monomer mixture of (a), (b), (c), (d), and (e) in an appropriate solvent, and adding a polymerization initiator. The reaction is carried out by raising the temperature, or in some cases, for example, by dropping a mixed monomer or a polymerization initiator to remove the reaction heat.
As the polymerization method, any method such as solution polymerization, emulsion polymerization and suspension polymerization can be performed, but solution polymerization and emulsion polymerization are practical. In the solution polymerization, esters such as methyl acetate and ethyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane, and ketones such as acetone and methyl ethyl ketone are generally used alone in the solution polymerization. Or used mixed,
It is not limited to these. To determine the solvent, the boiling point of the solvent,
It is necessary to take into account the solubility and molecular weight of the obtained copolymer, the workability, and the like. For example, ethyl acetate or a mixed solvent of ethyl acetate and toluene is particularly preferable. In emulsion polymerization, glycerin monostearate, polyoxyethylene phenyl ether, sodium lauryl sulfate and the like can be used as emulsifiers.
また、重合開始剤としては、ベンゾイルパーオキサイ
ド、ラウリルパーオキサイド等の各種過酸化物、アゾビ
スイソブチロニトリル等のアゾ化合物等の公知の重合開
始剤が単独または併用して使用される。これらは通常、
モノマー100重量部に対して0.2〜0.5重量部の割合で使
用される。As the polymerization initiator, known polymerization initiators such as various peroxides such as benzoyl peroxide and lauryl peroxide, and azo compounds such as azobisisobutyronitrile are used alone or in combination. These are usually
It is used in a ratio of 0.2 to 0.5 part by weight based on 100 parts by weight of the monomer.
本発明の粘着剤は、（ａ）ヒドロキシル基を含有しな
いアクリル酸エステルモノマー70〜82重量％、（ｂ）カ
ルボキシル基含有モノマー３〜５重量％、好ましくは、
3.0〜4.6重量％、（ｃ）ヒドロキシル基含有（メタ）ア
クリル酸エステルモノマー0.04〜0.4重量％、（ｄ）酢
酸ビニルモノマーが10〜17重量％、（ｅ）上記以外のビ
ニルモノマーの少なくとも１種が１〜10重量％の組成で
ある共重合体である。The pressure-sensitive adhesive of the present invention comprises (a) 70 to 82% by weight of an acrylate monomer containing no hydroxyl group, (b) 3 to 5% by weight of a carboxyl group-containing monomer, preferably
3.0 to 4.6% by weight, (c) 0.04 to 0.4% by weight of hydroxyl group-containing (meth) acrylate monomer, (d) 10 to 17% by weight of vinyl acetate monomer, and (e) at least one kind of vinyl monomer other than the above. Is a copolymer having a composition of 1 to 10% by weight.
ヒドロキシル基を含有しないアクリル酸エステルモノ
マーが70重量％未満では、粘着剤が硬くなりすぎ、サイ
ドタック、打ち抜き加工等の加工適性は良くなるが、接
着力、粘着力が低下する。一方、82重量％より多い場合
には軟らかくなりすぎ、凝集力が低下し、サイドタッ
ク、打ち抜き加工等の加工適性は悪くなる。If the amount of the acrylate monomer containing no hydroxyl group is less than 70% by weight, the pressure-sensitive adhesive becomes too hard, and the workability such as side tack and punching is improved, but the adhesive strength and the adhesive strength are reduced. On the other hand, when the content is more than 82% by weight, the material becomes too soft, the cohesive force is reduced, and the workability such as side tack and punching becomes poor.
カルボキシル基含有モノマーが３重量％未満では凝集
力が低下し、剪断強度が低下する。一方、５重量％より
多い場合は硬くなりすぎ、接着力が低下する。If the amount of the carboxyl group-containing monomer is less than 3% by weight, the cohesive strength is reduced and the shear strength is reduced. On the other hand, if it is more than 5% by weight, it becomes too hard, and the adhesive strength decreases.
ヒドロキシル基含有（メタ）アクリル酸エステルモノ
マーが0.04重量％未満では凝集力が低下する。一方、0.
4重量％より多い場合には、架橋剤使用時に架橋密度が
高くなりすぎて、接着力が低下する。If the amount of the hydroxyl group-containing (meth) acrylate monomer is less than 0.04% by weight, the cohesive strength is reduced. On the other hand, 0.
If it is more than 4% by weight, the crosslinking density becomes too high when the crosslinking agent is used, and the adhesive strength is reduced.
酢酸ビニルモノマー及び上記以外のビニルモノマーが
特定量未満では、粘着剤が軟らかくなりすぎ凝集力が低
下する。一方、特定量より多い場合には硬くなりすぎ、
接着力が低下する。If the vinyl acetate monomer and the vinyl monomer other than those described above are less than the specified amounts, the pressure-sensitive adhesive becomes too soft and the cohesive strength is reduced. On the other hand, if it exceeds a certain amount, it becomes too hard,
Adhesive strength decreases.
以上のように、１段重合では本願の組成範囲の他は、
粘着剤の物性と加工適性の両面を満足できない。As described above, in the one-stage polymerization, except for the composition range of the present application,
It is not possible to satisfy both physical properties and processability of the adhesive.
ヒドロキシル基を含有しないアクリル酸エステルモノ
マーのエステルとしては、メチル、エチル、プロピル、
ブチル、ヘキシル等任意のものであってよい。Esters of acrylic acid ester monomers not containing a hydroxyl group include methyl, ethyl, propyl,
Any one such as butyl and hexyl may be used.
カルボキシル基含有モノマーとしては、アクリル酸、
メタクリル酸、クロトン酸等のモノカルボン酸、マレイ
ン酸、フマール酸、シトラコン酸、グルタコン酸、イタ
コ酸等の多価カルボン酸、及びこれらの無水物がある。As the carboxyl group-containing monomer, acrylic acid,
There are monocarboxylic acids such as methacrylic acid and crotonic acid, and polycarboxylic acids such as maleic acid, fumaric acid, citraconic acid, glutaconic acid and itaconic acid, and anhydrides thereof.
ヒドロキシル基含有（メタ）アクリル酸エステルモノ
マーとしては、２−ヒドロキシエチル（メタ）アクリレ
ート、２−ヒドロキシプロピル（メタ）アクリレート、
３−クロロ−２−ヒドロキシプロピル（メタ）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
等がある。Examples of the hydroxyl group-containing (meth) acrylate monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
There are 3-chloro-2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate and the like.
上記以外のビニルモノマーとしては、メタクリル酸メ
チル、メタクリル酸エチル等のメタクリル酸アルキルエ
ステル、スチレン、アクリルニトリル、アクリルアミド
等がある。Other vinyl monomers include alkyl methacrylates such as methyl methacrylate and ethyl methacrylate, styrene, acrylonitrile, acrylamide and the like.
本発明の粘着剤は、各種の粘着加工品に使用しても充
分な粘着力、接着力、凝集力を示すものであるが、特
に、粘着ラベル等の加工適性を必要とする製品への使用
に適し、極めて実用性の高いものである。The pressure-sensitive adhesive of the present invention exhibits sufficient adhesive strength, adhesive strength, and cohesive force even when used for various kinds of pressure-sensitive adhesive products, but is particularly used for products requiring processability such as pressure-sensitive adhesive labels. It is very practical.
本発明の粘着剤は、他にロジン、ロジンエステル、水
添ロジンエステル、フェノール樹脂、芳香族変性テルペ
ン樹脂、脂肪族系石油樹脂、脂環族系石油樹脂、スチレ
ン系樹脂、キシレン系樹脂等の粘着付与剤、フタル酸
系、リン酸エステル、アジピン酸エステル、セバチン酸
エステル、リシノール酸エステル、ポリエステル型、エ
ポキシ系、塩化パラフィン等の可塑剤、動・植物油、鉱
物油、シリコーン油などの油脂類、酸化チタン、亜鉛
華、炭酸カルシウム等の着色剤、ベンゾフェノン系、サ
ルチレート系、ベンゾトリアゾール系、置換アクリロニ
トリル系等の紫外線防止剤、亜ヒ酸、亜酸化銅、酸化水
銀など無機化合物と有機水銀化物、有機硫黄化合物、フ
ェノール系化合物、有機銅系化合物など有機化合物の防
カビ剤、シリコーンエマルジョン、アルコール類等の消
泡剤、ポリビニルアルコール、ポリアクリル酸ソーダ、
カルボキシメチルセルロース、メチルセルロース等の増
粘剤等、公知の添加剤が添加できる。The pressure-sensitive adhesive of the present invention includes rosin, rosin ester, hydrogenated rosin ester, phenol resin, aromatic modified terpene resin, aliphatic petroleum resin, alicyclic petroleum resin, styrene resin, xylene resin and the like. Tackifiers, plasticizers such as phthalic acid type, phosphate ester, adipic acid ester, sebacate ester, ricinoleate ester, polyester type, epoxy type, chlorinated paraffin, oils and fats such as animal and vegetable oils, mineral oils, and silicone oils Coloring agents such as titanium oxide, zinc oxide, calcium carbonate, etc., UV inhibitors such as benzophenone type, salicylate type, benzotriazole type, substituted acrylonitrile type, inorganic compounds such as arsenous acid, cuprous oxide, mercury oxide, and organic mercury compounds Fungicides for organic compounds such as organic sulfur compounds, phenolic compounds, and organic copper compounds, silicone emulsifiers John, antifoaming agents such as alcohols, polyvinyl alcohol, sodium polyacrylate,
Known additives such as a thickener such as carboxymethylcellulose and methylcellulose can be added.
［作用］ （ａ）ヒドロキシル基を含有しないアクリル酸エステル
モノマーの少なくとも１種が 70〜82重量％ （ｂ）カルボキシル基含有モノマーの少なくとも１種が ３〜５重量％ （ｃ）ヒドロキシル基含有（メタ）アクリル酸エステル
モノマーの少なくとも１種が 0.04〜0.4重量％ （ｄ）酢酸ビニルモノマーが 10〜17重量％ （ｅ）上記以外のビニルモノマーの少なくとも１種が １〜10重量％ の組成である共重合体であって、かつ上記モノマーの混
合物を１段重合させて得られる共重合体からなる粘着剤
は、従来の粘着剤に比較して同等の粘着力、接着力、凝
集力を示し、かつ、特に加工適性に優れ、更に１段重合
で簡便に得られるという長所を有する。[Action] (a) 70 to 82% by weight of at least one acrylate monomer not containing a hydroxyl group; (b) 3 to 5% by weight of at least one carboxy group-containing monomer. ) At least one acrylate monomer is 0.04 to 0.4% by weight; (d) 10 to 17% by weight of vinyl acetate monomer; and (e) at least one of the other vinyl monomers is 1 to 10% by weight. A pressure-sensitive adhesive comprising a copolymer obtained by one-stage polymerization of a mixture of the above-mentioned monomers, which is a polymer, exhibits the same adhesive strength, adhesive strength, and cohesive strength as a conventional pressure-sensitive adhesive, and In particular, they have the advantage that they are excellent in processability and can be easily obtained by one-stage polymerization.
実施例１ 攪拌機付フラスコに、酢酸エチルを75g、トルエンを4
0g、重合開始剤としてアゾビスイソブチロニトリル（AI
BN）0.20gを仕込み、攪拌しながら昇温し、86℃となっ
た時点より２−エチルヘキシルアクリレート67.2g、ｎ
−ブチルアリレート120g、酢酸ビニル36g、スチレン2.4
g、メチルメタクリレート3.85g、アクリル酸9.6g、メタ
クリル酸0.24g、２−ヒドロキシエチルメタクリレート
0.72gの混合モノマーを、２時間かけて滴下して、更
に、トルエン溶剤20gに溶解したAIBN0.15gを３時間目及
び５時間目に仕込んで、沸点にて７時間反応を行い共重
合体を得た。Example 1 In a flask equipped with a stirrer, 75 g of ethyl acetate and 4 g of toluene were added.
0g, azobisisobutyronitrile (AI
BN) 0.20 g, and the temperature was increased while stirring. From the time when the temperature reached 86 ° C., 67.2 g of 2-ethylhexyl acrylate, n
-Butyl allylate 120 g, vinyl acetate 36 g, styrene 2.4
g, methyl methacrylate 3.85 g, acrylic acid 9.6 g, methacrylic acid 0.24 g, 2-hydroxyethyl methacrylate
0.72 g of the mixed monomer was added dropwise over 2 hours. Further, 0.15 g of AIBN dissolved in 20 g of toluene solvent was charged at the third and fifth hours, and the copolymer was reacted at the boiling point for 7 hours to form a copolymer. Obtained.
希釈剤としてトルエン163gを加えて樹脂分43.0重量
％、年度3800cpsの樹脂溶液を得た。163 g of toluene was added as a diluent to obtain a resin solution having a resin content of 43.0% by weight and a yearly amount of 3800 cps.
得られた共重合体の組成は、２−エチルヘキシルアク
リレート28重量％、ｎ−ブチルアクリレート50重量％、
酢酸ビニル15重量％、スチレン１重量％、メチルメタク
リレート1.6重量％、アクリル酸４重量％、メタクリル
酸0.1重量％、２−ヒドロキシエチルメタクリレート0.3
重量％であった。The composition of the obtained copolymer was 2-ethylhexyl acrylate 28% by weight, n-butyl acrylate 50% by weight,
15% by weight of vinyl acetate, 1% by weight of styrene, 1.6% by weight of methyl methacrylate, 4% by weight of acrylic acid, 0.1% by weight of methacrylic acid, 0.3% of 2-hydroxyethyl methacrylate
% By weight.
次に、上記で得られた共重合体について、粘着剤とし
ての性能を評価した。Next, the performance of the copolymer obtained above as an adhesive was evaluated.
共重合体100重量部（固形分43重量％溶液）に、架橋
剤としてコロネートＬ（日本ポリウレタン株式会社製:N
CO13重量％のポリイソシアネート）を1.0重量部添加
し、粘着剤を製造した。この粘着剤を用い下記測定法で
物性及び加工適性を評価し、第１表に示した。To 100 parts by weight of the copolymer (43% by weight solid content solution), as a crosslinking agent, Coronate L (Nippon Polyurethane Co., Ltd .: N
1.0 part by weight of polyisocyanate (CO 13% by weight) was added to produce an adhesive. Using this pressure-sensitive adhesive, physical properties and workability were evaluated by the following measurement methods, and the results are shown in Table 1.
○剪断強度 オートグラフ測定機使用、引張速度10mm/min 試料幅 10mm×10mm ○接着力及びボールタック（20℃） JIS Ｚ 0237に基づいて測定。○ Shear strength Using an autograph measuring machine, Tensile speed 10mm / min Sample width 10mm × 10mm ○ Adhesive strength and ball tack (20 ° C) Measured based on JIS Z0237.
○サイドタック 幅50×50mmの試験片を所定の紙で挟み、更にガラス板
で押さえて50g/cm2の荷重をかけ、40℃で保存して７日
後と28日後の粘着剤のはみ出し付着量を調べた。○ sandwiched specimen side tack width 50 × 50 mm with a predetermined paper, further a load of 50 g / cm 2 by pressing with a glass plate, extrusion of the adhesive after 7 days and after 28 days stored at 40 ° C. deposition The amount was checked.
○打ち抜き加工 フラット加工方式の打ち抜き加工機を用い、実際に粘
着ラベルの打ち抜き加工を行った際の観察結果。○ Punching process Observation results when the punching process of an adhesive label was actually performed using a flat processing type punching machine.
実施例１〜6,対照例１〜９ 第1,2表に示す試薬を用いて、実施例１の方法に準じ
て実験を行った。結果を第1,2表に示す。Examples 1 to 6 and Control Examples 1 to 9 Using the reagents shown in Tables 1 and 2, an experiment was conducted according to the method of Example 1. The results are shown in Tables 1 and 2.
［効果］ 前記の如く本発明の粘着剤は、 （ａ）ヒドロキシル基を含有しないアクリル酸エステル
モノマーの少なくとも１種が 70〜82重量％ （ｂ）カルボキシル基含有モノマーの少なくとも１種が ３〜５重量％ （ｃ）ヒドロキシル基含有（メタ）アクリル酸エステル
モノマーの少なくとも１種が 0.04〜0.4重量％ （ｄ）酢酸ビニルモノマーが 10〜17重量％ （ｅ）上記以外のビニルモノマーの少なくとも１種が １〜10重量％ の組成である共重合体であって、かつ上記モノマーの混
合物を１段重合させて得られる共重合体からなる。本発
明は、粘着力、接着力、凝集力もさることながら、特
に、加工適性に優れた粘着剤を１段重合で簡便に提供す
３点で、産業上極めて有用である。 [Effect] As described above, the pressure-sensitive adhesive of the present invention comprises: (a) 70 to 82% by weight of at least one kind of acrylate monomer containing no hydroxyl group; and (b) 3 to 5% of at least one kind of monomer containing carboxyl group. (C) at least one of the hydroxyl group-containing (meth) acrylate monomers is 0.04 to 0.4% by weight (d) 10 to 17% by weight of the vinyl acetate monomer (e) at least one of the other vinyl monomers is It is a copolymer having a composition of 1 to 10% by weight and obtained by subjecting a mixture of the above monomers to one-stage polymerization. INDUSTRIAL APPLICABILITY The present invention is extremely useful in industry, particularly in the point of easily providing a pressure-sensitive adhesive excellent in processability by one-stage polymerization, in addition to adhesive force, adhesive force and cohesive force.
Claims (1)
ル酸エステルモノマーの少なくとも１種が 70〜82重量％ （ｂ）カルボキシル基含有モノマーの少なくとも１種が ３〜５重量％ （ｃ）ヒドロキシル基含有（メタ）アクリル酸エステル
モノマーの少なくとも１種が 0.04〜0.4重量％ （ｄ）酢酸ビニルモノマーが 10〜17重量％ （ｅ）上記以外のビニルモノマーの少なくとも１種が １〜10重量％ の組成である共重合体であって、かつ上記モノマーの混
合物を一段重合させて得られる共重合体からなる粘着
剤。1. (a) 70 to 82% by weight of at least one acrylate monomer having no hydroxyl group; (b) 3 to 5% by weight of at least one of carboxyl group-containing monomers. (C) Hydroxyl group-containing. At least one of the (meth) acrylate monomers is 0.04 to 0.4% by weight; (d) the vinyl acetate monomer is 10 to 17% by weight; and (e) the at least one other vinyl monomer is 1 to 10% by weight. An adhesive comprising a copolymer, which is obtained by one-step polymerization of a mixture of the above monomers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62300346A JP2619830B2 (en) | 1987-11-28 | 1987-11-28 | Adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62300346A JP2619830B2 (en) | 1987-11-28 | 1987-11-28 | Adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01141970A JPH01141970A (en) | 1989-06-02 |
| JP2619830B2 true JP2619830B2 (en) | 1997-06-11 |
Family
ID=17883672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62300346A Expired - Lifetime JP2619830B2 (en) | 1987-11-28 | 1987-11-28 | Adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2619830B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2642263B2 (en) * | 1991-10-21 | 1997-08-20 | 積水化学工業株式会社 | Method for producing solvent-based acrylic pressure-sensitive adhesive |
| DE10229733A1 (en) * | 2002-07-02 | 2004-01-22 | Basf Ag | Pressure sensitive adhesives for carriers made of soft PVC |
| JP4837311B2 (en) * | 2005-06-21 | 2011-12-14 | リンテック株式会社 | Adhesive sheet for blood bag |
| JP6974405B2 (en) * | 2016-08-18 | 2021-12-01 | 積水化学工業株式会社 | (Meta) Acrylic adhesives and adhesive tapes |
| CN110028616B (en) * | 2019-03-22 | 2021-03-02 | 广东银洋环保新材料有限公司 | High-elasticity acrylate adhesive for glue-sprayed cotton and preparation method thereof |
| CN112266731A (en) * | 2020-09-28 | 2021-01-26 | 湖南省和祥润新材料有限公司 | UV-cured acrylate pressure-sensitive adhesive containing chlorinated paraffin |
| CN115340835A (en) * | 2022-08-16 | 2022-11-15 | 东莞理工学院 | High-stripping conductive polyacrylate pressure-sensitive adhesive and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE788440A (en) * | 1971-09-07 | 1973-01-02 | Goodrich Co B F | PRESSURE SENSITIVE ADHESIVES |
| JPS51132233A (en) * | 1975-04-03 | 1976-11-17 | Nitto Electric Ind Co Ltd | Pressure-sensitive adhesive composition |
| JPS5614565A (en) * | 1979-07-13 | 1981-02-12 | Nitto Electric Ind Co Ltd | Self-adhesive for surface protecting film |
| JPS6191277A (en) * | 1984-10-12 | 1986-05-09 | Mitsui Toatsu Chem Inc | Releasable self-adhesive |
| JPS627777A (en) * | 1985-07-05 | 1987-01-14 | Showa Highpolymer Co Ltd | Pressure-sensitive adhesive composition |
-
1987
- 1987-11-28 JP JP62300346A patent/JP2619830B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01141970A (en) | 1989-06-02 |
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