JPH05163480A - Acrylic tacky agent composition - Google Patents
Acrylic tacky agent compositionInfo
- Publication number
- JPH05163480A JPH05163480A JP3330331A JP33033191A JPH05163480A JP H05163480 A JPH05163480 A JP H05163480A JP 3330331 A JP3330331 A JP 3330331A JP 33033191 A JP33033191 A JP 33033191A JP H05163480 A JPH05163480 A JP H05163480A
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- pressure
- acrylic
- acrylic acid
- weight
- 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.)
- Granted
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、例えばラベル、粘着テ
ープもしくはシート等に使用されるアクリル系粘着剤組
成物に関し、特に、安定剤を含有している軟質塩化ビニ
ル樹脂への貼付性に優れており、かつエージング時間を
短縮することができ、従って、ラベル、粘着テープもし
くはシート等の生産性を高め得るアクリル系粘着剤組成
物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic pressure-sensitive adhesive composition used for, for example, labels, pressure-sensitive adhesive tapes, sheets, etc., and is particularly excellent in sticking property to a soft vinyl chloride resin containing a stabilizer. In addition, the present invention relates to an acrylic pressure-sensitive adhesive composition capable of shortening the aging time and thus improving the productivity of labels, pressure-sensitive adhesive tapes, sheets and the like.
【０００２】[0002]
【従来の技術】従来、紙もしくは合成樹脂よりなる基材
の一面にアクリル系粘着剤組成物よりなる粘着剤層を形
成してなる粘着テープもしくはシートが幅広く用いられ
ている。ところが、上記粘着テープもしくはシートの
基材が、安定剤を含有する軟質塩化ビニル樹脂を主成分
とするフィルムで構成されている場合、被着体が軟質
塩化ビニル樹脂からなり、これに上記粘着テープもしく
はシートを貼付した場合、並びに両面粘着テープで軟
質塩化ビニル樹脂製品を接合する場合等においては、経
時により粘着性能が著しく低下するという問題があっ
た。これは、軟質塩化ビニル樹脂中の安定剤が、経時に
より粘着剤層中に移行し、粘着剤中の官能基、特にカル
ボキシル基と化学的に反応することにより、粘着剤にお
いて架橋が過度に進行し、粘着性能が低下するためであ
る。上記のような問題を解決するものとして、特開昭６
３−２２８８４号公報には、アクリル系粘着剤に金属イ
オン封鎖剤を配合し、それによって軟質塩化ビニル樹脂
中の金属安定剤の粘着剤側への移行を防止した粘着剤が
開示されている。2. Description of the Related Art Conventionally, a pressure-sensitive adhesive tape or sheet in which a pressure-sensitive adhesive layer made of an acrylic pressure-sensitive adhesive composition is formed on one surface of a substrate made of paper or synthetic resin has been widely used. However, when the base material of the adhesive tape or sheet is composed of a film containing a soft vinyl chloride resin containing a stabilizer as a main component, the adherend is made of a soft vinyl chloride resin, and the adhesive tape Alternatively, when a sheet is attached, or when a soft vinyl chloride resin product is joined with a double-sided pressure-sensitive adhesive tape, there is a problem that the adhesive performance remarkably decreases with time. This is because the stabilizer in the soft vinyl chloride resin migrates into the pressure-sensitive adhesive layer with the passage of time and chemically reacts with the functional group in the pressure-sensitive adhesive, particularly the carboxyl group, so that crosslinking in the pressure-sensitive adhesive excessively progresses. However, this is because the adhesive performance is reduced. As a means for solving the above-mentioned problems, Japanese Patent Laid-Open No.
JP-A-3-22884 discloses a pressure-sensitive adhesive in which a metal ion sequestering agent is mixed with an acrylic pressure-sensitive adhesive to prevent migration of a metal stabilizer in a soft vinyl chloride resin to the pressure-sensitive adhesive side.
【０００３】他方、架橋起点としての水酸基を含有する
モノマーを用いたアクリル系共重合体において、架橋剤
としてポリイソシアネート化合物を配合した粘着剤組成
物が公知であり、有効な粘着物性が期待できる。しかし
ながら、この粘着剤組成物の粘着物性、特に耐熱性は、
粘着剤組成物を基材にキャストした後、室温で５〜７日
エージングしなければ、あるいは４０〜８０℃程度の温
度に加熱した状態で８〜２４時間エージングしなけれ
ば、充分に発現しない。従って、粘着剤をキャストした
後に、基材をスリット、カッティング又は打ち抜き等の
二次加工に供するに先立ち、粘着剤組成物がキャストさ
れた基材を長時間、工場内に堆積しておかねばならなか
った。上記のように、従来、軟質塩化ビニル樹脂中の安
定剤の移行に基因する粘着性能の低下を防止することが
でき、かつ短時間のエージングにより十分な耐熱性を発
現し得る粘着剤組成物が渇望されているにも関わらず、
未だ存在しなかった。On the other hand, in an acrylic copolymer using a monomer having a hydroxyl group as a cross-linking origin, a pressure-sensitive adhesive composition containing a polyisocyanate compound as a cross-linking agent is known, and effective pressure-sensitive adhesive properties can be expected. However, the adhesive physical properties of this adhesive composition, especially the heat resistance,
After the pressure-sensitive adhesive composition is cast on a substrate, it is not sufficiently expressed unless it is aged at room temperature for 5 to 7 days or aged at a temperature of about 40 to 80 ° C. for 8 to 24 hours. Therefore, after casting the pressure-sensitive adhesive, the substrate on which the pressure-sensitive adhesive composition is cast must be deposited in the factory for a long time before subjecting the substrate to secondary processing such as slitting, cutting or punching. There wasn't. As described above, conventionally, a pressure-sensitive adhesive composition capable of preventing the deterioration of the pressure-sensitive adhesive performance due to the migration of the stabilizer in the soft vinyl chloride resin, and capable of exhibiting sufficient heat resistance by aging for a short time is provided. Despite being craved,
It didn't exist yet.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、上記
要望を満たし、軟質塩化ビニル樹脂に対する貼付性に優
れており、かつ短時間のエージングによって十分な耐熱
性を発現し得る、生産性に優れたアクリル系粘着剤組成
物を提供することにある。The object of the present invention is to satisfy the above-mentioned demands, to have excellent sticking properties to a soft vinyl chloride resin, and to exhibit sufficient heat resistance by aging for a short time. An object is to provide an excellent acrylic pressure-sensitive adhesive composition.
【０００５】[0005]
【課題を解決するための手段】本発明のアクリル系粘着
剤組成物は、炭素数２〜１２のアルキル基を有するアク
リル酸アルキルエステル、窒素含有ビニル単量体、及び
カプロラクトン変成（メタ）アクリル酸エステルを共重
合してなり、かつ重合性不飽和カルボン酸を実質的に含
有しないアクリル系共重合体樹脂に、架橋剤としてポリ
イソシアネート化合物を配合してなることを特徴とし、
それによって上記課題を解決するものである。The acrylic pressure-sensitive adhesive composition of the present invention comprises an alkyl acrylate having an alkyl group having 2 to 12 carbon atoms, a nitrogen-containing vinyl monomer, and caprolactone-modified (meth) acrylic acid. Acrylic copolymer resin, which is obtained by copolymerizing an ester and does not substantially contain a polymerizable unsaturated carboxylic acid, characterized by comprising a polyisocyanate compound as a crosslinking agent,
This solves the above problem.
【０００６】本発明において用い得る上記アクリル酸ア
ルキルエステルとしては、例えば、アクリル酸エチルエ
ステル、アクリル酸ブチルエステル、アクリル酸オクチ
ルエステル、アクリル酸２−エチルヘキシルエステル、
アクリル酸ノニルエステル、アクリル酸ラウリルエステ
ル等が挙げられる。また、上記窒素含有ビニル単量体と
しては、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラク
タム、アクリロイルモルホリン、ジメチルアミノエチル
メタクリレート等が挙げられる。Examples of the acrylic acid alkyl ester usable in the present invention include acrylic acid ethyl ester, acrylic acid butyl ester, acrylic acid octyl ester, acrylic acid 2-ethylhexyl ester,
Examples include acrylic acid nonyl ester and acrylic acid lauryl ester. Examples of the nitrogen-containing vinyl monomer include N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine and dimethylaminoethylmethacrylate.
【０００７】窒素含有ビニル単量体の上記アクリル系共
重合体樹脂中の共重合比率は、好ましくは、３〜３０重
量％、より好ましくは、５〜２０重量％である。３重量
％未満では、凝集力が小さく、製品としたときに、粘着
剤のはみ出し、及び保持力や耐クリープ性の低下をきた
してしまう。逆に、３０重量％を越える場合には、粘着
剤が硬くなりすぎ、特に低温下での粘着力が低下し、粘
着剤として不適当となる。The copolymerization ratio of the nitrogen-containing vinyl monomer in the acrylic copolymer resin is preferably 3 to 30% by weight, more preferably 5 to 20% by weight. If it is less than 3% by weight, the cohesive force is small, and when it is made into a product, the pressure-sensitive adhesive is squeezed out, and the holding force and the creep resistance are deteriorated. On the other hand, if it exceeds 30% by weight, the pressure-sensitive adhesive becomes too hard and the adhesive strength is lowered particularly at low temperature, which makes it unsuitable as a pressure-sensitive adhesive.
【０００８】さらに、上記カプロラクトン変成（メタ）
アクリル酸エステルは、下記の式（Ｉ）で示される化合
物である。この式（Ｉ）で示される化合物は、他の重合
性ビニル化合物と共重合させた場合には、官能基である
−ＯＨ基が、高分子主鎖よりもフレキシブルに運動可能
な−Ｏ−（ＣＯＣ5 Ｈ10Ｏ）n −結合を介し、かつ離れ
た位置に存在するため反応性に富む。従って、上記、−
ＯＨ基が、架橋剤として用いるポリイソシアネート化合
物の−Ｎ＝Ｃ＝Ｏ基と速やかに反応するため、粘着物
性、特に耐熱性を発現させるために要するエージング時
間が大幅に短縮され得る。Further, the caprolactone modification (meta)
Acrylic acid ester is a compound represented by the following formula (I). When the compound represented by the formula (I) is copolymerized with another polymerizable vinyl compound, the —OH group, which is a functional group, can move more flexibly than the polymer main chain —O— ( It is highly reactive due to the presence of COC 5 H 10 O) n -bonds and a distant position. Therefore,
Since the OH group reacts rapidly with the -N = C = O group of the polyisocyanate compound used as the cross-linking agent, the aging time required to develop the adhesive physical properties, particularly heat resistance, can be significantly shortened.
【０００９】[0009]
【化２】 [Chemical 2]
【００１０】但し、上記式（Ｉ）において、Ｒは、Ｈ又
はＣＨ3 を示し、ｎは１〜５の整数である。上記式
（Ｉ）で示したカプロラクトン変成（メタ）アクリル酸
エステルは、上記アクリル系共重合体樹脂を構成する全
モノマー中、０．１重量％〜２重量％の範囲で含有する
ことが好ましい。０．１重量％未満では、粘着剤の架橋
度が上昇せず十分なクリープ特性が得られないからであ
り、２重量％を超えると、粘着剤溶液のゲル化を招き、
実用性が低下するからである。However, in the above formula (I), R represents H or CH 3 , and n is an integer of 1 to 5. The caprolactone-modified (meth) acrylic acid ester represented by the above formula (I) is preferably contained in the range of 0.1% by weight to 2% by weight based on all monomers constituting the acrylic copolymer resin. If it is less than 0.1% by weight, the degree of crosslinking of the pressure-sensitive adhesive does not increase and sufficient creep characteristics cannot be obtained. If it exceeds 2% by weight, the pressure-sensitive adhesive solution may gel.
This is because the practicality is reduced.
【００１１】（メタ）アクリル酸、イタコン酸、フマル
酸、又はマレイン酸等の重合性不飽和カルボン酸、特に
アクリル酸は、粘着剤の物性バランスをはかるうえで、
通常は必須の成分である。しかしながら、重合性不飽和
カルボン酸含有量が、アクリル系共重合体樹脂を構成す
るモノマー全体の０．５重量％を超えると、該アクリル
系共重合体樹脂を主成分とする粘着剤組成物を用いて作
成された粘着テープもしくはシートを軟質塩化ビニル樹
脂に貼付すると、軟質塩化ビニル樹脂から粘着剤層に経
時的に移行してきた軟質塩化ビニル樹脂中の安定剤と上
記重合性不飽和カルボン酸とが化学反応を起こす。その
結果、粘着剤層において架橋が極度に進行し、粘着物性
が著しく低下することになる。A polymerizable unsaturated carboxylic acid such as (meth) acrylic acid, itaconic acid, fumaric acid, or maleic acid, especially acrylic acid, is used to balance the physical properties of the adhesive.
It is usually an essential component. However, when the content of the polymerizable unsaturated carboxylic acid exceeds 0.5% by weight of all the monomers constituting the acrylic copolymer resin, the pressure-sensitive adhesive composition containing the acrylic copolymer resin as a main component is When a pressure-sensitive adhesive tape or sheet prepared by using is attached to a soft vinyl chloride resin, a stabilizer in the soft vinyl chloride resin that has migrated from the soft vinyl chloride resin to the pressure-sensitive adhesive layer over time and the polymerizable unsaturated carboxylic acid Causes a chemical reaction. As a result, the crosslinking in the pressure-sensitive adhesive layer is extremely advanced, and the physical properties of the pressure-sensitive adhesive are significantly lowered.
【００１２】従って、本発明の粘着剤組成物では、上記
のような重合性不飽和カルボン酸は含有させないことが
好ましく、例え上記重合性不飽和カルボン酸を共重合さ
せるにしても、上記重合性不飽和カルボン酸の含有量
は、アクリル系共重合体樹脂を構成するモノマー全体の
０．５重量％以下、すなわち実質的に含有しない程度と
することが必要である。Therefore, it is preferable that the above-mentioned polymerizable unsaturated carboxylic acid is not contained in the pressure-sensitive adhesive composition of the present invention. For example, even if the polymerizable unsaturated carboxylic acid is copolymerized, It is necessary that the content of the unsaturated carboxylic acid is 0.5% by weight or less based on the total amount of the monomers constituting the acrylic copolymer resin, that is, substantially no content.
【００１３】本発明の粘着剤組成物に用いられる上記ア
クリル系共重合体樹脂は、溶液重合、塊状重合等の任意
の重合方法により得られるが、通常、上記アクリル酸ア
ルキルエステル、窒素含有ビニル単量体及びカプロラク
トン変成（メタ）アクリル酸エステルを、例えば、酢酸
エチル等の適当な溶剤に溶解させ、重合開始剤を用いた
溶液重合法により容易に得ることができる。また、上記
アクリル酸アルキルエステル、窒素含有ビニル単量体、
カプロラクトン変成（メタ）アクリル酸エステル、光重
合開始剤及び光活性架橋剤よりなる無溶媒液状混合物を
支持体に塗布し、窒素等の不活性気体中において紫外線
照射することにより重合させ、粘着テープを得ることも
可能である。The acrylic copolymer resin used in the pressure-sensitive adhesive composition of the present invention can be obtained by any polymerization method such as solution polymerization and bulk polymerization. Usually, the above-mentioned alkyl acrylate ester and nitrogen-containing vinyl monomer are used. The polymer and the caprolactone-modified (meth) acrylic acid ester can be easily obtained by a solution polymerization method using a polymerization initiator by dissolving in a suitable solvent such as ethyl acetate. Further, the acrylic acid alkyl ester, a nitrogen-containing vinyl monomer,
A solventless liquid mixture consisting of a caprolactone modified (meth) acrylic acid ester, a photopolymerization initiator and a photoactive cross-linking agent is applied to a support and polymerized by irradiating with ultraviolet light in an inert gas such as nitrogen to form an adhesive tape. It is also possible to obtain.
【００１４】本発明の粘着剤組成物では、上記アクリル
系共重合体樹脂に架橋剤としてポリイソシアネート化合
物が配合される。使用し得るポリイソシアネート化合物
としては、トリレンジイソシアネートもしくはその水素
化物またはトリレンジイソシアネートのトリメチロール
プロパンとの付加物、トリフェニルメタントリイソシア
ネート、メチレンビス−ジ−フェニルイソシアネートも
しくはその水素化物、ヘキサメチレンジイソシアネー
ト、キシリレンジイソシアネート、４，４´−ジシクロ
ヘキシルメタンジイソシアネート、あるいはこれらの重
合物のように、分子内に２個以上のイソシアネート基を
有するものが挙げられる。In the pressure-sensitive adhesive composition of the present invention, a polyisocyanate compound is blended with the above acrylic copolymer resin as a crosslinking agent. As the polyisocyanate compound that can be used, tolylene diisocyanate or its hydride or an adduct of tolylene diisocyanate with trimethylolpropane, triphenylmethane triisocyanate, methylenebis-di-phenyl isocyanate or its hydride, hexamethylene diisocyanate, Examples include xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and polymers thereof having two or more isocyanate groups in the molecule.
【００１５】ポリイソシアネート化合物は、上記アクリ
ル系共重合体樹脂の粘着力、凝集力及びタッキネス等の
粘着物性のバランスを保つのに効果がある。上記ポリイ
ソシアネート化合物の配合量は、アクリル系共重合体樹
脂１００重量部に対し、０．１〜２重量部程度の範囲と
するのが適当である。０．１重量部未満では、ポリイソ
シアネート化合物配合による効果、すなわち粘着物性の
バランス改善効果が十分ではなく、２重量部を超えて配
合した場合には、粘着剤の架橋度が高くなりすぎるため
に充分な粘着力が得られないからである。なお、本発明
のアクリル粘着剤組成物には、本発明の目的を阻害しな
い範囲で、上記アクリル系共重合体樹脂及びポリイソシ
アネート化合物の他に、例えば、石油樹脂、テルペン樹
脂、ロジン樹脂、クマロンインデン樹脂もしくはフェノ
ール樹脂等の粘着付与樹脂、または各種安定剤もしくは
充填剤等の適宜の添加剤を配合してもよい。The polyisocyanate compound is effective in maintaining the balance of adhesive properties such as adhesive strength, cohesive strength and tackiness of the acrylic copolymer resin. The blending amount of the polyisocyanate compound is appropriately in the range of about 0.1 to 2 parts by weight with respect to 100 parts by weight of the acrylic copolymer resin. If the amount is less than 0.1 part by weight, the effect of the polyisocyanate compound is not sufficient, that is, the effect of improving the balance of the adhesive properties is not sufficient. This is because sufficient adhesive strength cannot be obtained. Incidentally, the acrylic pressure-sensitive adhesive composition of the present invention includes, for example, a petroleum resin, a terpene resin, a rosin resin, and Tackifying resin such as malonindene resin or phenol resin, or appropriate additives such as various stabilizers or fillers may be added.
【００１６】[0016]
【作用】本発明のアクリル系粘着剤組成物では、主成分
である上記アクリル系共重合体樹脂にカプロラクトン変
成（メタ）アクリル酸エステルが含有されており、該カ
プロラクトン変成（メタ）アクリル酸エステルの−ＯＨ
基が架橋剤としてのポリイソシアネート化合物の−Ｎ＝
Ｃ＝Ｏ基と速やかに反応するため、粘着物性、特に耐熱
性を発現させるのに必要なエージング時間が大幅に短縮
される。また、本発明の粘着剤組成物は、アクリル酸の
ような重合性不飽和カルボン酸を実質的に含有していな
い。従って、軟質塩化ビニル樹脂と接触された場合に、
該軟質塩化ビニル樹脂中から移行してきた安定剤と上記
重合性不飽和カルボン酸との化学反応に起因する過度の
架橋が生じない。よって、軟質塩化ビニル樹脂からなる
基材や被着体に本発明の粘着剤組成物を接触させても、
粘着物性が経時により低下する恐れがない。In the acrylic pressure-sensitive adhesive composition of the present invention, the above-mentioned acrylic copolymer resin as the main component contains a caprolactone-modified (meth) acrylic acid ester, and the caprolactone-modified (meth) acrylic acid ester -OH
-N = of polyisocyanate compound whose group is a crosslinking agent
Since it rapidly reacts with the C = O group, the aging time required for developing the adhesive physical properties, particularly heat resistance, is significantly shortened. Further, the pressure-sensitive adhesive composition of the present invention does not substantially contain a polymerizable unsaturated carboxylic acid such as acrylic acid. Therefore, when contacted with a soft vinyl chloride resin,
Excessive crosslinking due to the chemical reaction between the stabilizer that has migrated from the soft vinyl chloride resin and the polymerizable unsaturated carboxylic acid does not occur. Therefore, even if the pressure-sensitive adhesive composition of the present invention is brought into contact with a substrate or an adherend made of a soft vinyl chloride resin,
There is no fear that the adhesive properties will deteriorate over time.
【００１７】[0017]
【実施例】以下、本発明の実施例及び比較例を挙げるこ
とにより、本発明を明らかにする。実施例１ 冷却管、攪拌器及び温度計を備えたセパラブルフラスコ
に、アクリル酸ブチルエステル９４．８重量部、Ｎ−ビ
ニルピロリドン５重量部及びカプロラクトン変成（メ
タ）アクリル酸エステル（ダイセル化学社、商品名：プ
ラクセルＦＭ−２Ｄ）０．２重量部を、上記モノマー合
計量が酢酸エチルに対して重量比で５５／４５となるよ
うに酢酸エチルに溶解し、さらに得られた溶液に重合開
始剤としてベンゾイルパーオキサイド０．０６２重量部
を添加した。上記混合溶液を窒素還流下で８０℃で８時
間攪拌して重合反応を行い、粘着剤溶液、すなわちアク
リル系共重合体樹脂溶液を得た。EXAMPLES The present invention will be clarified by giving Examples and Comparative Examples of the present invention. Example 1 In a separable flask equipped with a cooling tube, a stirrer and a thermometer, 94.8 parts by weight of butyl acrylate, 5 parts by weight of N-vinylpyrrolidone and caprolactone modified (meth) acrylic acid ester (Daicel Chemical Co., Ltd., Trade name: Praxel FM-2D) 0.2 part by weight is dissolved in ethyl acetate so that the total amount of the above monomers is 55/45 by weight ratio with respect to ethyl acetate, and a polymerization initiator is added to the resulting solution. Was added as 0.062 parts by weight of benzoyl peroxide. The above mixed solution was stirred under nitrogen reflux at 80 ° C. for 8 hours to carry out a polymerization reaction to obtain an adhesive solution, that is, an acrylic copolymer resin solution.
【００１８】上記アクリル系共重合体樹脂溶液に、架橋
剤として、日本ポリウレタン工業社製、商品名：コロネ
ートＬ（トリレンジイソシアネートとトリメチロールプ
ロパンとの付加物の５５重量％溶液）０．２重量部を配
合し、実施例１の粘着剤組成物を調製した。上記のよう
にして得た粘着剤組成物を、厚さ３８μｍのポリエステ
ルフィルムの一面に乾燥後の厚みが２５μｍとなるよう
に塗工し、しかる後１１０℃の温度で５分間乾燥し、粘
着テープを得た。0.2% by weight of the above acrylic copolymer resin solution as a crosslinking agent, made by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate L (55% by weight solution of an adduct of tolylene diisocyanate and trimethylolpropane). Parts were blended to prepare the pressure-sensitive adhesive composition of Example 1. The pressure-sensitive adhesive composition obtained as described above is applied to one surface of a polyester film having a thickness of 38 μm so that the thickness after drying becomes 25 μm, and then dried at a temperature of 110 ° C. for 5 minutes to give a pressure-sensitive adhesive tape. Got
【００１９】実施例２ 架橋剤としてのコロネートＬの配合量を１．５重量部と
したこと以外は、実施例１と同様にして粘着テープを得
た。実施例３ カプロラクトン変成（メタ）アクリル酸エステルとして
のダイセル化学社製、商品名：プラクセルＦＭ−２Ｄの
使用量を１．５重量部としたこと以外は、実施例１と同
様にして粘着テープを得た。実施例４ 架橋剤としてのコロネートＬの配合量を１．５重量部と
したこと以外は、実施例３と同様にして、粘着テープを
得た。 Example 2 An adhesive tape was obtained in the same manner as in Example 1 except that the amount of Coronate L as a crosslinking agent was 1.5 parts by weight. Example 3 An adhesive tape was prepared in the same manner as in Example 1 except that the amount of the caprolactone modified (meth) acrylic acid ester manufactured by Daicel Chemical Industries, Ltd., trade name: Praxel FM-2D, was 1.5 parts by weight. Obtained. Example 4 An adhesive tape was obtained in the same manner as in Example 3 except that the amount of Coronate L as a crosslinking agent was 1.5 parts by weight.
【００２０】比較例１ カプロラクトン変成（メタ）アクリル酸エステルの代わ
りにメタクリル酸２−ヒドロキシエチルエステルを用い
たことを除いては、実施例４と同様にして粘着テープを
得た。比較例２ カプロラクトン変成（メタ）アクリル酸エステルとして
のダイセル化学社製、商品名：プラクセルＦＭ−２Ｄの
使用量を０．０５重量部としたことを除いては、実施例
４と同様にして粘着テープを得た。 Comparative Example 1 An adhesive tape was obtained in the same manner as in Example 4, except that methacrylic acid 2-hydroxyethyl ester was used instead of caprolactone modified (meth) acrylic acid ester. Comparative Example 2 Adhesion was performed in the same manner as in Example 4 except that the amount of Caprolactone modified (meth) acrylic acid ester manufactured by Daicel Chemical Industries, Ltd., trade name: Praxel FM-2D was 0.05 part by weight. Got the tape.
【００２１】比較例３ カプロラクトン変成（メタ）アクリル酸エステルとして
のダイセル化学社製、商品名：プラクセルＦＭ−２Ｄの
使用量を１０重量部としたこと以外は、実施例４と同様
にして粘着テープを得た。比較例４ アクリル酸ブチルエステル９３．８重量部、Ｎ−ビニル
ピロリドン５重量部、アクリル酸１重量部及びカプロラ
クトン変成（メタ）アクリル酸エステル（ダイセル化学
社製、商品名：プラクセルＦＭ−２Ｄ）０．２重量部を
用いてアクリル系共重合体樹脂溶液を得たことを除いて
は、実施例４と同様にして粘着テープを得た。 Comparative Example 3 An adhesive tape was prepared in the same manner as in Example 4 except that the amount of the caprolactone modified (meth) acrylic acid ester manufactured by Daicel Chemical Co., Ltd. under the trade name of Praxel FM-2D was 10 parts by weight. Got Comparative Example 4 Acrylic acid butyl ester 93.8 parts by weight, N-vinylpyrrolidone 5 parts by weight, acrylic acid 1 part by weight and caprolactone modified (meth) acrylic acid ester (manufactured by Daicel Chemical Industries, Ltd., trade name: Praxel FM-2D) 0 A pressure-sensitive adhesive tape was obtained in the same manner as in Example 4, except that the acrylic copolymer resin solution was obtained by using 1.2 parts by weight.
【００２２】比較例５ カプロラクトン変成（メタ）アクリル酸エステルとして
のダイセル化学社製、商品名：プラクセルＦＭ−２Ｄの
使用量を１．５重量部としたことを除いては、比較例４
と同様にして粘着テープを得た。上記実施例１〜４及び
比較例１〜５の各粘着剤組成物の組成を表１に示す。 Comparative Example 5 Comparative Example 4 except that the amount of Praxel FM-2D manufactured by Daicel Chemical Co., Ltd. as the caprolactone modified (meth) acrylic acid ester was 1.5 parts by weight.
An adhesive tape was obtained in the same manner as in. Table 1 shows the composition of each pressure-sensitive adhesive composition of Examples 1 to 4 and Comparative Examples 1 to 5.
【００２３】[0023]
【表１】 [Table 1]
【００２４】なお、表１中、ＢＡはアクリル酸ブチルエ
ステルを、ＶｐはＮ−ビニルピロリドンを、ＡＡｃはア
クリル酸を示す。In Table 1, BA is butyl acrylate, Vp is N-vinylpyrrolidone, and AAc is acrylic acid.
【００２５】評 価 実施例１〜４及び比較例１〜５で得た各粘着テープにつ
いて、下記のＳＰ粘着力、保持力、対軟質塩化ビニル
（経時）剥離力、及び対軟質塩化ビニル（経時）保持力
を下記の要領で測定し、評価した。結果を表２に示す。 ＳＰ粘着力…ＪＩＳ Ｚ０２３７に準じて、ＳＵＳ
−３０４からなるステンレス板に粘着テープを１５ｍｍ
幅で貼り合わせ、２３℃の温度で２０分間経過した後の
１８０°剥離強度を引っ張り速度３００ｍｍ／分の条件
で測定した。 保持力…ＪＩＳ Ｚ０２３７に準じ、ＳＵＳ−３０
４からなるステンレス板に２０ｍｍ×２０ｍｍの粘着テ
ープを貼り合わせ、粘着テープを下側として８０℃の恒
温槽に入れ、１ｋｇの懸垂荷重をかけ、１時間後のテー
プのずれあるいは落下時間を測定した。 Evaluation For each of the pressure-sensitive adhesive tapes obtained in Examples 1 to 4 and Comparative Examples 1 to 5, the following SP adhesive strength, holding power, soft vinyl chloride (aging) peeling force, and soft vinyl chloride (aging) ) The holding power was measured and evaluated according to the following procedure. The results are shown in Table 2. SP adhesive strength ... SUS according to JIS Z0237
-304 mm stainless steel plate with 15 mm adhesive tape
The 180 ° peel strength after 20 minutes of bonding at a width of 23 ° C. was measured under a pulling speed of 300 mm / min. Holding power ... SUS-30 according to JIS Z0237
A 20 mm × 20 mm adhesive tape was attached to a stainless steel plate consisting of 4, the adhesive tape was placed in a constant temperature bath at 80 ° C. with the adhesive tape on the lower side, a suspending load of 1 kg was applied, and the shift or drop time of the tape after 1 hour was measured. ..
【００２６】 対軟質塩化ビニル（経時）剥離力…重
合度１１００のポリ塩化ビニル１００重量部に対し可塑
剤としてジオクチルフタレート５０重量部並びに各種安
定剤及び充填剤としての炭酸カルシウム１５重量部が混
合されてなる組成を有する厚さ５ｍｍの軟質塩化ビニル
板に、粘着テープを１５ｍｍ幅で貼り合わせ、１８０°
剥離強度を引っ張り速度３００ｍｍ／分で測定した。 対軟質塩化ビニル（経時）保持力…で用いた軟質
塩化ビニル板に２０×２０ｍｍの粘着テープを貼り合わ
せ、５００ｇの荷重を加えて４０℃における剪断保持力
を測定した。 なお、上記ＳＰ粘着力、保持力、対軟質塩化ビニル剥離
力及び対軟質塩化ビニル保持力については、粘着テープ
を作成し、常温で２４時間放置した後に測定し、さらに
対軟質塩化ビニル経時剥離力及び対軟質塩化ビニル経時
保持力については８０℃の恒温槽内に１週間各粘着テー
プを放置した後において測定した。Peel strength against soft vinyl chloride (aging): 50 parts by weight of dioctyl phthalate as a plasticizer and 15 parts by weight of calcium carbonate as a stabilizer and a filler are mixed with 100 parts by weight of polyvinyl chloride having a polymerization degree of 1100. Adhesive tape of 15 mm width is attached to a soft vinyl chloride plate having a composition of
Peel strength was measured at a pull rate of 300 mm / min. 20.times.20 mm adhesive tape was attached to the soft vinyl chloride plate used for soft vinyl chloride (aging) holding force, and a shear holding force at 40.degree. C. was measured by applying a load of 500 g. The SP adhesive force, holding force, soft vinyl chloride peeling force and soft vinyl chloride holding force were measured after the pressure-sensitive adhesive tape was prepared and allowed to stand at room temperature for 24 hours. The retention of soft vinyl chloride with time was measured after each adhesive tape was left in a thermostat at 80 ° C. for 1 week.
【００２７】[0027]
【表２】 [Table 2]
【００２８】表２から明らかなように、比較例１，２の
粘着テープでは、常温で２４時間放置した後において、
ステンレス板に貼付した場合及び軟質塩化ビニル板に貼
付した場合のいずれにおいても凝集破壊が生じ、十分な
粘着物性を実現し得ないことがわかる。また、比較例３
では、カプロラクトン変成（メタ）アクリル酸エステル
としてのダイセル化学社製、商品名：プラクセルＦＭ−
２Ｄのアクリル系共重合体樹脂中の配合割合が１０重量
部と本発明の範囲外であるため、重合時にゲル化し、上
記各測定に供し得るのに十分な粘着テープを得ることが
できなかった。As is clear from Table 2, the pressure-sensitive adhesive tapes of Comparative Examples 1 and 2 were left at room temperature for 24 hours,
It can be seen that cohesive failure occurs in both cases of sticking to a stainless steel plate and soft vinyl chloride plate, and sufficient adhesive properties cannot be realized. In addition, Comparative Example 3
Then, as a caprolactone-modified (meth) acrylic acid ester, manufactured by Daicel Chemical Co., Ltd., trade name: Praxel FM-
Since the blending ratio in the 2D acrylic copolymer resin was 10 parts by weight, which is outside the range of the present invention, it was not possible to obtain an adhesive tape sufficient to be gelated during the polymerization and to be used for each of the above measurements. ..
【００２９】さらに、比較例４及び５の粘着テープで
は、重合性不飽和単量体としてアクリル酸が１重量部配
合されていたため、軟質塩化ビニル板に貼付した場合、
８０℃で１週間放置した後において、剥離力及び保持力
が著しく低下することがわかる。これに対して、実施例
１〜４では、塗工直後から十分な接着力及び凝集力を示
し、かつ軟質塩化ビニル板に貼付し、高温で長期間放置
した後であっても、剥離力及び保持力が十分な値に維持
され得ることがわかる。Further, in the pressure-sensitive adhesive tapes of Comparative Examples 4 and 5, 1 part by weight of acrylic acid was blended as the polymerizable unsaturated monomer, so that when it was attached to a soft vinyl chloride plate,
It can be seen that the peeling force and the holding force are remarkably lowered after standing at 80 ° C. for 1 week. On the other hand, in Examples 1 to 4, even after exhibiting sufficient adhesive force and cohesive force immediately after coating and sticking to a soft vinyl chloride plate and left at high temperature for a long time, peeling force and It can be seen that the holding power can be maintained at a sufficient value.
【００３０】[0030]
【発明の効果】以上のように、本発明のアクリル系粘着
剤組成物では、炭素数２〜１２のアルキル基を有するア
クリル酸アルキルエステル、窒素含有ビニル単量体及び
カプロラクトン変成（メタ）アクリル酸エステルを共重
合してなり、重合性不飽和カルボン酸を実質的に含有し
ていないアクリル系共重合体樹脂に、ポリイソシアネー
ト化合物を上記特定の割合で配合してなるため、軟質塩
化ビニル樹脂からなる基材に塗工されたり、軟質塩化ビ
ニル樹脂からなる被着体に貼付されたりした場合におい
ても、経時による粘着性能の低下が生じ難く、かつ使用
直後から十分な粘着物性を示し、かつ短時間エージング
によっても十分な耐熱性を発現し得る粘着剤を提供する
ことが可能となる。よって、本発明によれば、軟質塩化
ビニル樹脂からなる基材を用いたラベル、粘着テープも
しくはシートや、塩化ビニル樹脂を被着体とする接着用
途に最適な粘着剤組成物を高い生産性でもって供給する
ことが可能となる。As described above, in the acrylic pressure-sensitive adhesive composition of the present invention, the acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms, the nitrogen-containing vinyl monomer and the caprolactone-modified (meth) acrylic acid are used. An acrylic copolymer resin which is obtained by copolymerizing an ester and does not substantially contain a polymerizable unsaturated carboxylic acid, and a polyisocyanate compound in a specific proportion as described above. When it is applied to a base material that is made of vinyl chloride or is adhered to an adherend that is made of soft vinyl chloride resin, the adhesive performance is unlikely to deteriorate over time, and it exhibits sufficient adhesive physical properties immediately after use and is short-lived. It is possible to provide a pressure-sensitive adhesive that can exhibit sufficient heat resistance even with time aging. Therefore, according to the present invention, a label, a pressure-sensitive adhesive tape or sheet using a base material made of a soft vinyl chloride resin, and a pressure-sensitive adhesive composition most suitable for an adhesive application using a vinyl chloride resin as an adherend with high productivity. It becomes possible to supply it.
Claims (3)
クリル酸アルキルエステルと、窒素含有ビニル単量体
と、下記の式（Ｉ）で示す（但し、式（Ｉ）において、
ＲはＨ又はＣＨ3 、ｎは１〜５の整数を示す。）カプロ
ラクトン変成（メタ）アクリル酸エステルとを共重合し
てなり、かつ重合性不飽和カルボン酸を実質的に含有し
ていないアクリル系共重合体樹脂と、 架橋剤としてのポリイソシアネート化合物とを含むこと
を特徴とする、アクリル系粘着剤組成物。 【化１】 1. An alkyl acrylate having an alkyl group having 2 to 12 carbon atoms, a nitrogen-containing vinyl monomer, and the following formula (I) (wherein, in the formula (I),
R represents H or CH 3 , and n represents an integer of 1 to 5. ) An acrylic copolymer resin obtained by copolymerizing a caprolactone-modified (meth) acrylic acid ester and containing substantially no polymerizable unsaturated carboxylic acid, and a polyisocyanate compound as a crosslinking agent An acrylic pressure-sensitive adhesive composition characterized by the following. [Chemical 1]
前記カプロラクトン変成（メタ）アクリル酸エステルの
共重合比率が０．１〜２重量％である請求項１に記載の
アクリル系粘着剤組成物。2. The acrylic pressure-sensitive adhesive composition according to claim 1, wherein the copolymerization ratio of the caprolactone-modified (meth) acrylic acid ester in the acrylic copolymer resin is 0.1 to 2% by weight.
ルピロリドン、Ｎ−ビニルカプロラクタム、アクリロイ
ルモルホリン及びジメチルアミノエチルメタクリレート
の内少なくとも１種であり、かつ前記アクリル系共重合
体樹脂中における窒素含有ビニル単量体の共重合比率が
３〜３０重量％である、請求項１又は２に記載のアクリ
ル系粘着剤組成物。3. The nitrogen-containing vinyl monomer is at least one of N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine and dimethylaminoethylmethacrylate, and nitrogen in the acrylic copolymer resin. The acrylic pressure-sensitive adhesive composition according to claim 1, wherein the copolymerization ratio of the contained vinyl monomer is 3 to 30% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3330331A JP2614682B2 (en) | 1991-12-13 | 1991-12-13 | Acrylic adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3330331A JP2614682B2 (en) | 1991-12-13 | 1991-12-13 | Acrylic adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05163480A true JPH05163480A (en) | 1993-06-29 |
| JP2614682B2 JP2614682B2 (en) | 1997-05-28 |
Family
ID=18231432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3330331A Expired - Fee Related JP2614682B2 (en) | 1991-12-13 | 1991-12-13 | Acrylic adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2614682B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001012129A1 (en) * | 1999-08-13 | 2001-02-22 | Jeneric/Pentron Incorporated | Dental compositions comprising degradable polymers |
| KR100446664B1 (en) * | 2002-02-20 | 2004-09-04 | 주식회사 엘지화학 | Acrylic pressure sensitive adhesive composition for the polarizing firm |
| US7275933B2 (en) | 2000-08-11 | 2007-10-02 | Pentron Clinical Technologies, Llc | Method of manufacturing dental restorations |
| US7371460B2 (en) | 2001-05-30 | 2008-05-13 | Nitto Denko Corporation | Highly adhesive pressure sensitive adhesive compositions and sheets |
| US7374815B2 (en) | 2001-05-30 | 2008-05-20 | Nitto Denko Corporation | Removable pressure sensitive adhesive compositions and sheets |
-
1991
- 1991-12-13 JP JP3330331A patent/JP2614682B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001012129A1 (en) * | 1999-08-13 | 2001-02-22 | Jeneric/Pentron Incorporated | Dental compositions comprising degradable polymers |
| US7275933B2 (en) | 2000-08-11 | 2007-10-02 | Pentron Clinical Technologies, Llc | Method of manufacturing dental restorations |
| US7371460B2 (en) | 2001-05-30 | 2008-05-13 | Nitto Denko Corporation | Highly adhesive pressure sensitive adhesive compositions and sheets |
| US7374815B2 (en) | 2001-05-30 | 2008-05-20 | Nitto Denko Corporation | Removable pressure sensitive adhesive compositions and sheets |
| KR100446664B1 (en) * | 2002-02-20 | 2004-09-04 | 주식회사 엘지화학 | Acrylic pressure sensitive adhesive composition for the polarizing firm |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2614682B2 (en) | 1997-05-28 |
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