JP2549576B2 - Adhesive sheet - Google Patents
Adhesive sheetInfo
- Publication number
- JP2549576B2 JP2549576B2 JP2170479A JP17047990A JP2549576B2 JP 2549576 B2 JP2549576 B2 JP 2549576B2 JP 2170479 A JP2170479 A JP 2170479A JP 17047990 A JP17047990 A JP 17047990A JP 2549576 B2 JP2549576 B2 JP 2549576B2
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- sensitive adhesive
- pressure
- weight
- styrene
- 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
- Medicinal Preparation (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、切れ目を有する離型紙を備えた粘着シート
に関し、詳しくは、長期間にわたつて放置した後も、上
記切れ目間に空隙が生じない粘着シートに関する。Description: TECHNICAL FIELD The present invention relates to a pressure-sensitive adhesive sheet provided with a release paper having a cut line, and more specifically, a pressure-sensitive adhesive sheet having no gap between the cut lines even after being left for a long period of time. Regarding the seat.
従来の技術 粘着シートは種々の用途に使用されているが、例え
ば、皮膚刺激剤や消炎鎮痛剤等の薬剤を含有する粘着剤
を基材シート上に積層してなる貼付薬が医療用途に使用
されている。このような貼付薬においては、例えば、特
開昭54−138124号公報に記載されているように、貼付薬
を皮膚に貼付した際に良好な粘着性及び弾性を有するの
みならず、剥離時に皮膚に刺激を与えず、容易に剥離し
得るところから、粘着剤としてはジエン系共重合体で、
特に、ジエン系ブロツク共重合体が好適であることが知
られている。Conventional technology Adhesive sheets are used for various purposes. For example, a patch containing an adhesive containing a drug such as a skin stimulant or an anti-inflammatory analgesic on a base sheet is used for medical purposes. Has been done. In such a patch, for example, as described in JP-A-54-138124, not only does it have good adhesiveness and elasticity when the patch is applied to the skin, but also the skin during peeling. Since it can be easily peeled off without giving irritation to the adhesive, it is a diene copolymer as an adhesive,
In particular, diene block copolymers are known to be suitable.
一方、上記のような貼付薬においては、その基材シー
トとしては、柔軟で皮膚になじみよい塩化ビニル系樹脂
が好適であるが、反面、塩化ビニル系樹脂シートは粘着
剤としての上記したジエン系ブロツク共重合体との親和
性に乏しく、特に、貼付薬においては、粘着剤としての
ジエン系ブロツク共重合体が薬剤と共に可塑剤としての
高級脂肪酸や流動パラフイン等を含有するために、塩化
ビニル系樹脂基材シートとの親和性が一層乏しい。その
結果、ジエン系ブロツク共重合体からなる粘着剤を塩化
ビニル系樹脂基材シート上に単に直接に塗布して貼付薬
とした場合、粘着剤の基材シートに対する接着性に劣る
問題がある。On the other hand, in the patch as described above, as the base sheet, a vinyl chloride resin which is soft and conforms to the skin is preferable, but on the other hand, the vinyl chloride resin sheet is a diene-based adhesive as an adhesive. Poor affinity with block copolymer, especially in patch, since diene block copolymer as an adhesive contains higher fatty acid and fluid paraffin as a plasticizer together with the drug, vinyl chloride-based Poor affinity with resin base sheet. As a result, when a pressure-sensitive adhesive composed of a diene-based block copolymer is simply applied directly onto a vinyl chloride-based resin base sheet to form a patch, there is a problem in that the adhesiveness of the pressure-sensitive adhesive to the base sheet is poor.
そこで、塩化ビニル系樹脂シートに適宜のプライマー
処理を施して、ジエン系ブロツク共重合体に対する親和
性を高めることも可能ではあるが、しかし、この方法に
よれば、工程数の増加に伴なつて、製造費用が高くなら
ざるを得ない。Therefore, it is possible to increase the affinity for the diene block copolymer by subjecting the vinyl chloride resin sheet to an appropriate primer treatment, but with this method, as the number of steps increases, However, the manufacturing cost must be high.
かかる問題を解決するために、例えば、特開平１−22
3186号公報には、第１図に示すように、塩化ビニルグラ
フトポリウレタン共重合体とエチレン−酢酸ビニル共重
合体からなり、可塑剤を含有させない樹脂組成物にて基
材シート１を形成し、その上にエチレン−ジエン−スチ
レンブロツク共重合体からなる粘着剤２を積層接着し、
更に、その上に離型紙３を積層してなる粘着シート４が
提案されている。第２図に示すように、このように、粘
着シート４が離型紙３を有する場合、離型紙は、それを
剥がしやすいように、通常、粘着シートを横断して、切
れ目５が入れられている。このように、離型紙に切れ目
を有する粘着シートは、製造工程上、原反の移送方向、
即ち、縦方向に形成される。In order to solve such a problem, for example, Japanese Patent Laid-Open No. 1-22
In Japanese Patent No. 3186, as shown in FIG. 1, a base sheet 1 is formed of a resin composition containing a vinyl chloride graft polyurethane copolymer and an ethylene-vinyl acetate copolymer, and containing no plasticizer, A pressure-sensitive adhesive 2 made of an ethylene-diene-styrene block copolymer was laminated and adhered thereon,
Further, a pressure-sensitive adhesive sheet 4 having a release paper 3 laminated thereon has been proposed. As shown in FIG. 2, when the pressure-sensitive adhesive sheet 4 has the release paper 3 as described above, the release paper is usually cut across the pressure-sensitive adhesive sheet so that the release paper 3 can be easily peeled off. . In this way, the pressure-sensitive adhesive sheet having a break in the release paper is
That is, it is formed in the vertical direction.
上記した粘着シートは、基材シートが粘着剤層に強い
接着力を有する反面、製造された粘着シートを長期間に
わたつて保存したとき、離型紙の切れ目間に空隙が形成
され、外観を損ない、製品価値が著しく低下する。The above-mentioned pressure-sensitive adhesive sheet, while the base material sheet has a strong adhesive force to the pressure-sensitive adhesive layer, when the produced pressure-sensitive adhesive sheet is stored over a long period of time, a void is formed between the cuts of the release paper, impairing the appearance. , Product value is significantly reduced.
発明が解決しようとする課題 本発明者らは、離型紙の切れ目に上記したような空隙
が生じる原因について鋭意研究した結果、粘着剤中の薬
剤が経時的に僅かながら、基材シートに移行して、経時
的に基材シートを縦及び横方向に膨潤させると共に、基
材シートの原反の製造時に原反が縦方向に延伸され、そ
の後の放置によつて基材シートが横方向に伸び（縦方向
に収縮）を生じ、これらの複合された結果として、製造
された粘着シートを長期間にわたつて保存したとき、離
型紙が膨潤する基材シートに追随し、上記切れ目間に空
隙が形成されることを究明した。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As a result of diligent research on the cause of the above-described voids in the break of release paper, the present inventors migrated to the base sheet with a slight amount of the drug in the adhesive over time. The base sheet is swelled in the vertical and horizontal directions over time, and the raw sheet is stretched in the vertical direction during the production of the base sheet, and the base sheet is stretched in the horizontal direction by leaving it unattended. (Shrinking in the longitudinal direction) occurs, and as a result of these composites, when the manufactured pressure-sensitive adhesive sheet is stored for a long period of time, the release paper follows the swelling base material sheet, resulting in voids between the cuts. It was confirmed that it was formed.
そこで、本発明者らは、上記した知見に基づいて、上
記した離型紙の切れ目間に空隙が生じるのを防止する方
法について、更に研究を重ねた結果、基材シートに所定
の可塑剤を適量含有させ、この可塑剤を粘着剤中に適度
に移行させ、上記切れ目において接着剤として作用させ
ることによつて、上記切れ目における空隙の発生が効果
的に防止されることを見出して、本発明に至つたもので
ある。Therefore, based on the above-mentioned findings, the present inventors further researched a method for preventing the formation of voids between the cuts of the release paper, and as a result, obtained an appropriate amount of a predetermined plasticizer on the base sheet. By including this, the plasticizer is appropriately transferred into the pressure-sensitive adhesive, by acting as an adhesive in the cut, it was found that the occurrence of voids in the cut is effectively prevented, the present invention It is the ultimate.
即ち、本発明は、風合及び柔軟性にすぐれる基材シー
ト上にジエン系ブロツク共重合体からなる粘着剤が直接
に強固に積層接着されており、しかも、長期間にわたる
保存によつても、離型紙の切れ目間に空隙が生じない粘
着シートを提供することを目的とする。That is, in the present invention, a pressure-sensitive adhesive comprising a diene block copolymer is directly and strongly laminated and adhered on a base material sheet having excellent feeling and flexibility, and further, it can be stored for a long period of time. An object of the present invention is to provide a pressure-sensitive adhesive sheet in which voids are not formed between the cut lines of the release paper.
課題を解決するための手段 本発明は、樹脂からなる基材シート上に粘着剤が積層
され、更に、その上に切れ目を有する離型紙が積層され
ている粘着シートにおいて、 （ａ） ポリ塩化ビニル、塩化ビニル−酢酸ビニル共重
合体、塩化ビニル−エチレン共重合体及び塩化ビニル−
プロピレン共重合体から選ばれる少なくとも１種のポリ
塩化ビニル系重合体、塩化ビニルグラフトポリウレタン
共重合体又はこれらの混合物からなる基材樹脂100重量
部について、 （ｂ） スチレン−エチレン−ブチレン−スチレンブロ
ツク共重合体１〜20重量部、 （ｃ） エチレン−酢酸ビニル共重合体樹脂１〜50重量
部、及び （ｄ） 平均分子量1000以上のポリエステル系可塑剤10
〜30重量部 を含有する樹脂組成物からなる基材シート上にスチレン
−ジエン−スチレンブロツク共重合体からなる粘着剤が
積層接着されていることを特徴とする。Means for Solving the Problems The present invention relates to a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive is laminated on a base material sheet made of a resin, and release paper having cuts is further laminated thereon (a) polyvinyl chloride , Vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer and vinyl chloride-
For 100 parts by weight of a base resin composed of at least one polyvinyl chloride polymer selected from propylene copolymers, vinyl chloride graft polyurethane copolymer or a mixture thereof, (b) styrene-ethylene-butylene-styrene block 1 to 20 parts by weight of copolymer, (c) 1 to 50 parts by weight of ethylene-vinyl acetate copolymer resin, and (d) polyester plasticizer having an average molecular weight of 1000 or more 10
It is characterized in that a pressure sensitive adhesive comprising a styrene-diene-styrene block copolymer is laminated and adhered on a base material sheet comprising a resin composition containing 30 to 30 parts by weight.
本発明において、基材樹脂は、ポリ塩化ビニル、塩化
ビニル−酢酸ビニル共重合体、塩化ビニル−エチレン共
重合体及び塩化ビニル−プロピレン共重合体から選ばれ
る少なくとも１種のポリ塩化ビニル系重合体、塩化ビニ
ルグラフトポリウレタン共重合体又はこれらの混合物か
らなる。In the present invention, the base resin is at least one polyvinyl chloride-based polymer selected from polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer and vinyl chloride-propylene copolymer. , A vinyl chloride graft polyurethane copolymer or a mixture thereof.
基材樹脂としての塩化ビニルグラフトポリウレタン共
重合体は、例えば、東ソー（株）から「ドミナス」とし
て市販されているものを好適に用いることができる。こ
の「ドミナス」とは、塩化ビニルをポリウレタン樹脂に
グラフトしてなるグラフト共重合体であつて、このよう
なグラフト共重合体における塩化ビニルの重合度やポリ
ウレタン樹脂の組成等は種々に変わり得るが、本発明に
おいては、JIS A硬度の100〜70、抗張力250〜450kg/c
m2、延び200〜600％である共重合体が好ましく用いられ
る。As the vinyl chloride graft polyurethane copolymer as the base resin, for example, those commercially available as "Dominus" from Tosoh Corporation can be preferably used. The "dominous" is a graft copolymer obtained by grafting vinyl chloride onto a polyurethane resin, and the degree of polymerization of vinyl chloride and the composition of the polyurethane resin in such a graft copolymer may vary. In the present invention, JIS A hardness of 100 to 70, tensile strength of 250 to 450 kg / c
A copolymer having m 2 and an elongation of 200 to 600% is preferably used.
また、上記ポリ塩化ビニル、塩化ビニル−酢酸ビニル
共重合体、塩化ビニル−エチレン共重合体及び塩化ビニ
ル−プロピレン共重合体から選ばれる少なくとも１種を
いうものとするが、これらのなかでも、平均重合度400
〜2000、特に平均重合度700〜1400のポリ塩化ビニルが
好ましく用いられる。Further, it means at least one selected from the above polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer and vinyl chloride-propylene copolymer, but among these, the average Degree of polymerization 400
.About.2000, especially polyvinyl chloride having an average degree of polymerization of 700 to 1400 is preferably used.
上記塩化ビニルグラフトポリウレタン共重合体又は塩
化ビニル系重合体又は、後述する樹脂組成物の成形加工
法、特に、カレンダー加工や押出加工に必要な加熱下で
の流動性を与えると共に、基材シートに所要の強度を与
える。The vinyl chloride-grafted polyurethane copolymer or vinyl chloride-based polymer or a molding method of the resin composition described below, in particular, imparts fluidity under heating necessary for calendering and extrusion, and to a base sheet. Gives the required strength.
本発明によれば、基材シートは、かかる基材樹脂100
重量部について、スチレン−エチレン−ブチレン−スチ
レンブロツク共重合体１〜20重量部、エチレ−酢酸ビニ
ル共重合体樹脂１〜50重量部、及び平均分子量1000以上
のポリエステル系可塑剤10〜30重量部とを含有する樹脂
組成物からなる。According to the present invention, the base sheet is such a base resin 100.
Regarding parts by weight, 1 to 20 parts by weight of styrene-ethylene-butylene-styrene block copolymer, 1 to 50 parts by weight of ethylene-vinyl acetate copolymer resin, and 10 to 30 parts by weight of polyester plasticizer having an average molecular weight of 1000 or more. And a resin composition containing.
上記エチレン−酢酸ビニル共重合体は、通常、酢酸ビ
ニル含量が５〜85重量％であるものが用いられるが、特
に、樹脂組成物がカレンダー加工性にすぐれるように、
酢酸ビニル含量が45重量％以上であるものが好ましく用
いられる。尚、エチレン−酢酸ビニル共重合体には、エ
チレン−酢酸ビニル−塩化ビニル共重合体を含むものと
する。As the ethylene-vinyl acetate copolymer, one having a vinyl acetate content of 5 to 85% by weight is usually used, and in particular, in order that the resin composition has excellent calenderability,
Those having a vinyl acetate content of 45% by weight or more are preferably used. The ethylene-vinyl acetate copolymer includes an ethylene-vinyl acetate-vinyl chloride copolymer.
更に、このようなエチレン−酢酸ビニル共重合体は、
樹脂組成物を基材シートに加熱成形加工する際に、金属
滑性を与えると共に、得られる基材シートに柔軟性を与
え、更に、粘着剤を構成するスチレン−ジエン−スチレ
ンブロツク共重合体に対する高い親和性を与える。樹脂
組成物において、基剤樹脂100重量部について、エチレ
ン−酢酸ビニル共重合体の配合量が１重量部よりも少な
いときは、上記効果を十分に得ることができず、成形加
工性及びスチレン−ジエン−スチレンブロツク共重合体
に対する親和性のいずれにおいても劣る。他方、50重量
部を越えるときは、得られる基材シートが過度に弾性を
有し、例えば、貼付薬として用いる場合、皮膚へのなじ
みが悪くなる。また、樹脂組成物が高温で軟化しやす
く、加工性に劣る。Further, such ethylene-vinyl acetate copolymer,
When the resin composition is heat-molded into a base material sheet, it imparts metal lubricity and gives flexibility to the base material sheet to be obtained, and further, to the styrene-diene-styrene block copolymer constituting the pressure-sensitive adhesive. Gives high affinity. In the resin composition, when the blending amount of the ethylene-vinyl acetate copolymer is less than 1 part by weight with respect to 100 parts by weight of the base resin, the above effects cannot be sufficiently obtained, and the moldability and styrene- It is inferior in both affinity to diene-styrene block copolymer. On the other hand, when it exceeds 50 parts by weight, the obtained base sheet has excessive elasticity, and when it is used as a patch, for example, it does not fit well on the skin. In addition, the resin composition is likely to soften at high temperatures, resulting in poor processability.
スチレン−エチレン−ブチレン−スチレンブロツク共
重合体は、基材シートに粘着剤層との親和性を与える。
本発明においては、スチレン−エチレン−ブチレン−ス
チレンブロツク共重合体は、前記基材樹脂100重量部に
ついて、１〜20重量部の範囲で含まれる。The styrene-ethylene-butylene-styrene block copolymer gives the base sheet an affinity for the pressure-sensitive adhesive layer.
In the present invention, the styrene-ethylene-butylene-styrene block copolymer is contained in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the base resin.
このように、本発明の粘着シートにおける基材シート
は、基材樹脂及び後述する所定の可塑剤と共に、スチレ
ン−エチレン−ブチレン−スチレンブロツク共重合体と
エチレン−酢酸ビニル共重合体樹脂を含有する。これら
のなかで弾性重合体は、塩化ビニルグラフトポリウレタ
ン共重合体、スチレン−エチレン−ブチレン−スチレン
ブロツク共重合体及びエチレン−酢酸ビニル共重合体樹
脂である。しかし、エチレン−酢酸ビニル共重合体樹脂
は、熱変色性が大きく、多量に配合すれば、基材シート
に過度の粘着性を与え、滑性が悪くなり、他方、スチレ
ン−エチレン−ブチレン−スチレンブロツク共重合体
は、ゴム弾性が強いので、余りに多くを配合することは
好ましくない。Thus, the base sheet in the pressure-sensitive adhesive sheet of the present invention contains a styrene-ethylene-butylene-styrene block copolymer and an ethylene-vinyl acetate copolymer resin together with a base resin and a predetermined plasticizer described later. . Among these, the elastic polymers are vinyl chloride graft polyurethane copolymers, styrene-ethylene-butylene-styrene block copolymers and ethylene-vinyl acetate copolymer resins. However, the ethylene-vinyl acetate copolymer resin has a large thermochromic property, and if it is blended in a large amount, it imparts excessive tackiness to the base sheet, resulting in poor lubricity, while styrene-ethylene-butylene-styrene resin is used. Since the block copolymer has strong rubber elasticity, it is not preferable to add too much of it.
そこで、本発明によれば、前述したように、基材シー
トにおけるスチレン−エチレン−ブチレン−スチレンブ
ロツク共重合体量を１〜20重量部とし、エチレン−酢酸
ビニル共重合体樹脂量を１〜50重量部として、上記した
望ましい特性を基材シートに付与しつつ、基材シートの
柔軟性が基本的に可塑剤と塩化ビニルグラフトポリウレ
タン共重合体の配合割合によつて設計されている。この
ような観点から、本発明においては、基材樹脂は、好ま
しくは、塩化ビニルグラフトポリウレタン共重合体20〜
80重量％とポリ塩化ビニル系共重合体80〜20重量％とか
らなる。Therefore, according to the present invention, as described above, the amount of styrene-ethylene-butylene-styrene block copolymer in the base sheet is 1 to 20 parts by weight, and the amount of ethylene-vinyl acetate copolymer resin is 1 to 50. As weight parts, the flexibility of the base sheet is basically designed by the blending ratio of the plasticizer and the vinyl chloride graft polyurethane copolymer while imparting the above-mentioned desirable properties to the base sheet. From such a viewpoint, in the present invention, the base resin is preferably a vinyl chloride graft polyurethane copolymer 20 to
80% by weight and 80 to 20% by weight of polyvinyl chloride copolymer.
更に、本発明によれば、比較的高分子量のポリエステ
ル系可塑剤の所定量を基材シートに含有させることによ
つて、基材シートの柔軟性を確保すると共に、かかる可
塑剤の適量の配合によつて、基材シートから粘着剤層中
に適度に移行させ、離型紙の切れ目間に滲みださせて、
いわば接着剤として作用させることによつて、長期間の
保存の際に、離型紙の切れ目間に空隙が生じるのを防止
する。Further, according to the present invention, by containing a predetermined amount of a relatively high molecular weight polyester-based plasticizer in the base material sheet, the flexibility of the base material sheet is ensured, and an appropriate amount of such plasticizer is blended. Therefore, it is appropriately transferred from the base sheet into the pressure-sensitive adhesive layer, and oozes between the cuts of the release paper,
By acting as an adhesive, so to speak, voids are prevented from occurring between the cuts of the release paper during long-term storage.
本発明において用いる可塑剤は、平均分子量が1000以
上であることが必要であり、好ましくは2000以上であ
る。このような高分子量ポリエステル系可塑剤は、種々
の市販品を用いることができる。平均分子量が1000より
も小さい可塑剤は、粘着シートを長期間にわたつて保存
したときに、粘着剤の接着性を低下させるので好ましく
ない。The plasticizer used in the present invention needs to have an average molecular weight of 1000 or more, preferably 2000 or more. As such a high molecular weight polyester plasticizer, various commercial products can be used. A plasticizer having an average molecular weight of less than 1000 deteriorates the adhesiveness of the pressure-sensitive adhesive when the pressure-sensitive adhesive sheet is stored over a long period of time, which is not preferable.
基材シートにおけるこれら可塑剤の配合量は、基材樹
脂100重量部について、10〜30重量部の範囲である。可
塑剤の配合量が基材樹脂100重量部について、10重量部
よりも少ないときは、離型紙の切れ目に空隙が発生する
のを防止する効果に乏しく、他方、30重量部を越えると
きは、基材樹脂シートと粘着剤との間の密着性を低減さ
は、或いは可塑剤が粘着剤層中に過度に移行して、粘着
力を低減させ、或いは粘着剤層を変質させるので、貼付
薬のための粘着シートとしては実用し難くなる。特に、
本発明においては、可塑剤の配合量は、基材樹脂100重
量部に対して、15〜25重量部の範囲が好ましい。The compounding amount of these plasticizers in the base sheet is in the range of 10 to 30 parts by weight with respect to 100 parts by weight of the base resin. When the amount of the plasticizer compounded is 100 parts by weight of the base resin, when it is less than 10 parts by weight, the effect of preventing the occurrence of voids at the break of the release paper is poor, while when it exceeds 30 parts by weight, The adhesiveness between the base resin sheet and the pressure-sensitive adhesive is reduced, or the plasticizer excessively migrates into the pressure-sensitive adhesive layer to reduce the pressure-sensitive adhesive force or deteriorate the pressure-sensitive adhesive layer. It becomes difficult to put it into practical use as an adhesive sheet for. In particular,
In the present invention, the blending amount of the plasticizer is preferably in the range of 15 to 25 parts by weight with respect to 100 parts by weight of the base resin.
本発明によれば、このように、基材シートに含まれる
可塑剤が少量であるので、離型紙間に切れ目を発生させ
のを有効に防止するが、しかし、粘着剤には殆ど影響を
与えず、従つて、粘着力が経時低下もない。更に、可塑
剤を基材シートに配合することによつて、基材シート中
の塩化ビニルグラフトポリウレタン共重合体を低減する
ことができ、かくして、樹脂組成物の流動性が改善さ
れ、加工時の熱変色もなく、しかも、透明性にすぐれる
基材シートを得ることができる。According to the present invention, as described above, since the plasticizer contained in the base material sheet is small in amount, it is possible to effectively prevent the occurrence of a break between the release papers, but the adhesive is hardly affected. Therefore, the adhesive strength does not decrease with time. Furthermore, by blending the plasticizer into the base sheet, the vinyl chloride graft polyurethane copolymer in the base sheet can be reduced, and thus the fluidity of the resin composition is improved and the plastic composition during processing can be improved. It is possible to obtain a base sheet which is free from heat discoloration and has excellent transparency.
本発明において、基材シートの厚みは、用途によつて
適宜に選ばれるが、通常、0.05〜0.20mmである。In the present invention, the thickness of the substrate sheet is appropriately selected depending on the application, but is usually 0.05 to 0.20 mm.
本発明による粘着シートは、かかる基材シート上に粘
着剤としてのスチレン−ジエン−スチレンブロツク共重
合体の層が直接に積層接着されている。本発明によれ
ば、上記樹脂組成物からなる基材シートがスチレン−エ
チレン−ブチレン−スチレンブロツク共重合体を含有
し、スチレン−ジエン−スチレン共重合体に対する親和
性にすずれるので、その上にスチレン−ジエン−スチレ
ン共重合体からなる粘着剤を塗布するとき、その間に高
い接着性を得ることができるのである。In the pressure-sensitive adhesive sheet according to the present invention, a layer of styrene-diene-styrene block copolymer as a pressure-sensitive adhesive is directly laminated and adhered on the base sheet. According to the present invention, the base material sheet made of the above resin composition contains a styrene-ethylene-butylene-styrene block copolymer, and since it has an affinity for styrene-diene-styrene copolymer, it is further formed thereon. When a pressure-sensitive adhesive composed of a styrene-diene-styrene copolymer is applied, high adhesiveness can be obtained during that time.
本発明において、粘着剤を構成するスチレン−ジエン
−スチレンブロツク共重合体としては、具体例として、
スチレン−ブタジエン−スチレンブロツク共重合体及び
スチレン−イソプレン−スチレンブロツク共重合体を挙
げることができる。これらスチレン−ジエン−スチレン
ブロツク共重合体は、粘着剤として単独又は混合物とし
て用いられてもよく、又はこれらブロツク共重合体と共
に可塑剤、粘着付与樹脂、充填剤、老化防止剤等を含有
する組成物として用いられてもよい。更に、前記した貼
付薬の場合のように、必要な薬剤を含有していてもよ
い。In the present invention, the styrene-diene-styrene block copolymer constituting the pressure-sensitive adhesive, as a specific example,
Mention may be made of styrene-butadiene-styrene block copolymers and styrene-isoprene-styrene block copolymers. These styrene-diene-styrene block copolymers may be used alone or as a mixture as a pressure-sensitive adhesive, or a composition containing a plasticizer, a tackifying resin, a filler, an antioxidant and the like together with these block copolymers. It may be used as a product. Further, it may contain a necessary drug as in the case of the above-mentioned patch.
かかるスチレン−ジエン−スチレンブロツク共重合体
は、例えば、前記した特開昭54−138124号公報に詳細に
記載されているように既に知られており、Ａをスチレン
からなるガラス状或いは硬質の非弾性熱可塑性重合体の
ブロツクとし、Ｂをブタジエン又はイソプレンのような
共役ジエンの弾性重合体のブロツクとするとき、Ａ−Ｂ
−Ａの構造を有するブロツク共重合体であつて、ブロツ
クＡが全重合体重量の10〜50重量％を占める。このよう
なスチレン−ブタジエン−スチレンブロツク共重合体は
カリフレツクスTR−1101、TR−1102等として、また、ス
チレン−イソプレン−スチレンブロツク共重合体はカリ
フレツクスTR−1107（いずれもシエル化学（株）製）と
して市販されており、入手することができる。Such a styrene-diene-styrene block copolymer is already known as described in detail in, for example, Japanese Patent Laid-Open No. 138124/1979 mentioned above, and A is a glass-like or hard non-polymer made of styrene. When the block is an elastic thermoplastic polymer and B is the block of an elastic polymer of a conjugated diene such as butadiene or isoprene, AB
In the block copolymer having the structure of -A, the block A accounts for 10 to 50% by weight of the total weight of the polymer. Such a styrene-butadiene-styrene block copolymer is used as Califlex TR-1101, TR-1102, etc., and a styrene-isoprene-styrene block copolymer is Califlex TR-1107 (all manufactured by Shell Chemical Co., Ltd.). It is commercially available as and can be obtained.
本発明による粘着シートは、前記樹脂組成物をシート
に成形し、必要に応じて薬剤及びその他の添加剤を含有
するスチレン−ジエン−スチレンブロツク共重合体を溶
融塗布し、更にその上に離型紙を貼着することによつて
得ることができる。The pressure-sensitive adhesive sheet according to the present invention is obtained by molding the resin composition into a sheet, melt-coating a styrene-diene-styrene block copolymer containing a drug and other additives as necessary, and further releasing the release paper. It can be obtained by attaching.
発明の効果 以上のように、本発明による粘着シートによれば、基
材シートが塩化ビニルグラフトポリウレタン共重合体、
ポリ塩化ビニル系重合体又は好ましくはこれらの混合物
からなる基材樹脂に加え、更に、樹脂分としてエチレン
−酢酸ビニル共重合体とスチレン−エチレン−ブチレン
−スチレン共重合体とを含有する樹脂組成物からなるの
で、風合及び柔軟性にすぐれ、更に、スチレン−ジエン
−スチレンブロツク共重合体との親和性にすぐれるの
で、基材シートに粘着材としてのスチレン−ジエン−ス
チレンブロツク共重合体が直接に強固に接着されてお
り、例えば、貼付薬として好適に使用することができ
る。Effects of the Invention As described above, according to the pressure-sensitive adhesive sheet of the present invention, the substrate sheet is a vinyl chloride graft polyurethane copolymer,
A resin composition containing, in addition to a polyvinyl chloride polymer or preferably a base resin composed of a mixture thereof, an ethylene-vinyl acetate copolymer and a styrene-ethylene-butylene-styrene copolymer as resin components. Therefore, the styrene-diene-styrene block copolymer as a pressure-sensitive adhesive is added to the base material sheet because it has excellent feel and flexibility, and further has excellent affinity with the styrene-diene-styrene block copolymer. It is directly and firmly adhered, and can be suitably used, for example, as a patch.
特に、本発明の粘着シートによれば、基材シートが比
較的高分子量の可塑剤を適量含有しているので、この可
塑剤が粘着剤層中に適度に機構し、前述したように、離
型紙の切れ目間に滲みだして、離型紙の切れ目の間を接
着するので、粘着シートの長期間にわたる保存によつて
も、離型紙の切れ目間に空隙を生じない。In particular, according to the pressure-sensitive adhesive sheet of the present invention, since the base material sheet contains an appropriate amount of a relatively high molecular weight plasticizer, this plasticizer functions appropriately in the pressure-sensitive adhesive layer, and as described above, Since bleeding occurs between the cuts of the pattern paper and the gaps between the cuts of the release paper are adhered to each other, even when the pressure-sensitive adhesive sheet is stored for a long period of time, no void is generated between the cuts of the release paper.
実施例 以下に実施例を挙げて本発明を説明する。尚、以下に
おいて部は重量部を意味する。EXAMPLES The present invention will be described below with reference to examples. In the following, parts mean parts by weight.
実施例 第１表に示すように、平均重合度800のポリ塩化ビニ
ル、塩化ビニルグラフトポリウレタン共重合体、エチレ
ン−酢酸ビニル共重合体及びスチレン−エチレン−ブチ
レン−スチレンブロツク共重合体を樹脂成分とし、これ
に安定剤及び可塑剤を配合し、厚さ130μｍのフイルム
に成形した。Example As shown in Table 1, polyvinyl chloride having an average degree of polymerization of 800, vinyl chloride graft polyurethane copolymer, ethylene-vinyl acetate copolymer and styrene-ethylene-butylene-styrene block copolymer were used as resin components. Then, a stabilizer and a plasticizer were added thereto, and a film having a thickness of 130 μm was formed.
得られたフイルムを基材シートとして、これにスチレ
ン−イソプレン−スチレンブロツク共重合体を粘着剤と
して厚さ0.1mmに溶融塗布した後、10cm角のダンベルで
打ち抜き、これに切れ目を入れた離型紙を貼着した。こ
れを試料として、アルミニウム袋内に密封し、ギヤーオ
ーブン中で50℃で１日間放置した後、離型紙の切れ目の
間に生じた空隙を測定した。空隙が1.0mm以下であれ
ば、実用上、支障ない。結果を第１表に示す。The obtained film was used as a base sheet, and a styrene-isoprene-styrene block copolymer was melt-coated as a pressure-sensitive adhesive to a thickness of 0.1 mm, punched with a 10 cm square dumbbell, and a release paper was cut into it. I stuck it. Using this as a sample, it was sealed in an aluminum bag and allowed to stand in a gear oven at 50 ° C. for 1 day, after which the voids formed between the cuts in the release paper were measured. If the gap is 1.0 mm or less, there is no problem in practical use. The results are shown in Table 1.
また、試料をアルミニウム袋内に密封し、ギヤーオー
ブン中で50℃で１日間放置した後、25mm幅に裁断し、離
型紙を剥離し、粘着剤層の面をベークライト板に貼着
し、10分間放置した後、200mm/分にて180゜ピーリング
剥離試験を行なつて、ベークライト板上の糊残りを調べ
た。結果を第１表に示す。○は糊残りが全くない、△は
糊残りが１〜５％、×は糊残りが５％を越える、を意味
する。 Also, the sample was sealed in an aluminum bag, left in a gear oven at 50 ° C for 1 day, cut into a width of 25 mm, the release paper was peeled off, and the surface of the adhesive layer was attached to a bakelite plate. After leaving for a minute, a 180 ° peeling peeling test was performed at 200 mm / min to examine the adhesive residue on the Bakelite plate. The results are shown in Table 1. O means that there is no adhesive residue, Δ means that the adhesive residue is 1 to 5%, and × means that the adhesive residue exceeds 5%.
第１図は、本発明による離型紙を備えた粘着シートを示
す断面図、第２図は、本発明による離型紙の平面図であ
る。 １……基材シート、２……粘着剤、３……離型紙、４…
…粘着シート、５……切れ目。FIG. 1 is a sectional view showing an adhesive sheet provided with a release paper according to the present invention, and FIG. 2 is a plan view of the release paper according to the present invention. 1 ... Base material sheet, 2 ... Adhesive, 3 ... Release paper, 4 ...
… Adhesive sheets, 5 …… breaks.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｊ 7/02 ＪＫＸ Ｃ０９Ｊ 7/02 ＪＫＸ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location C09J 7/02 JKX C09J 7/02 JKX
Claims (2)
され、更に、その上に切れ目を有する離型紙が積層され
ている粘着シートにおいて、 （ａ） ポリ塩化ビニル、塩化ビニル−酢酸ビニル共重
合体、塩化ビニル−エチレン共重合体及び塩化ビニル−
プロピレン共重合体から選ばれる少なくとも１種のポリ
塩化ビニル系重合体、塩化ビニルグラフトポリウレタン
共重合体又はこれらの混合物からなる基材樹脂100重量
部について、 （ｂ） スチレン−エチレン−ブチレン−スチレンブロ
ツク共重合体１〜20重量部、 （ｃ） エチレン−酢酸ビニル共重合体樹脂１〜50重量
部、及び （ｄ） 平均分子量1000以上のポリエステル系可塑剤10
〜30重量部 を含有する樹脂組成物からなる基材シート上にスチレン
−ジエン−スチレンブロツク共重合体からなる粘着剤が
積層接着されていることを特徴とする粘着シート。1. A pressure-sensitive adhesive sheet comprising a base material sheet made of a resin, a pressure-sensitive adhesive layered on the base sheet, and a release paper having a slit formed thereon, comprising: (a) polyvinyl chloride, vinyl chloride-vinyl acetate Copolymer, vinyl chloride-ethylene copolymer and vinyl chloride-
For 100 parts by weight of a base resin composed of at least one polyvinyl chloride polymer selected from propylene copolymers, vinyl chloride graft polyurethane copolymer or a mixture thereof, (b) styrene-ethylene-butylene-styrene block 1 to 20 parts by weight of copolymer, (c) 1 to 50 parts by weight of ethylene-vinyl acetate copolymer resin, and (d) polyester plasticizer having an average molecular weight of 1000 or more 10
A pressure-sensitive adhesive sheet, characterized in that a pressure-sensitive adhesive comprising a styrene-diene-styrene block copolymer is laminated and adhered onto a base material sheet comprising a resin composition containing 30 to 30 parts by weight.
ン共重合体20〜80重量％とポリ塩化ビニル、塩化ビニル
−酢酸ビニル共重合体、塩化ビニル−エチレン共重合体
及び塩化ビニル−プロピレン共重合体から選ばれる少な
くとも１種のポリ塩化ビニル系重合体80〜20重量％とか
らなることを特徴とする請求項第１項記載の粘着シー
ト。2. A base resin comprising 20 to 80% by weight of a vinyl chloride graft polyurethane copolymer, polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-ethylene copolymer and a vinyl chloride-propylene copolymer. The pressure-sensitive adhesive sheet according to claim 1, which comprises 80 to 20% by weight of at least one polyvinyl chloride polymer selected from the group consisting of:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2170479A JP2549576B2 (en) | 1990-06-28 | 1990-06-28 | Adhesive sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2170479A JP2549576B2 (en) | 1990-06-28 | 1990-06-28 | Adhesive sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0457874A JPH0457874A (en) | 1992-02-25 |
| JP2549576B2 true JP2549576B2 (en) | 1996-10-30 |
Family
ID=15905712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2170479A Expired - Fee Related JP2549576B2 (en) | 1990-06-28 | 1990-06-28 | Adhesive sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2549576B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8263713B2 (en) | 2009-10-13 | 2012-09-11 | Kraton Polymers U.S. Llc | Amine neutralized sulfonated block copolymers and method for making same |
| US8377514B2 (en) | 2008-05-09 | 2013-02-19 | Kraton Polymers Us Llc | Sulfonated block copolymer fluid composition for preparing membranes and membrane structures |
| US8445631B2 (en) | 2009-10-13 | 2013-05-21 | Kraton Polymers U.S. Llc | Metal-neutralized sulfonated block copolymers, process for making them and their use |
| US9365662B2 (en) | 2010-10-18 | 2016-06-14 | Kraton Polymers U.S. Llc | Method for producing a sulfonated block copolymer composition |
| US9394414B2 (en) | 2010-09-29 | 2016-07-19 | Kraton Polymers U.S. Llc | Elastic, moisture-vapor permeable films, their preparation and their use |
| US9429366B2 (en) | 2010-09-29 | 2016-08-30 | Kraton Polymers U.S. Llc | Energy recovery ventilation sulfonated block copolymer laminate membrane |
| US9861941B2 (en) | 2011-07-12 | 2018-01-09 | Kraton Polymers U.S. Llc | Modified sulfonated block copolymers and the preparation thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000069422A1 (en) * | 1999-05-13 | 2000-11-23 | Hisamitsu Pharmaceutical Co., Inc. | Patch |
| JP6172312B1 (en) * | 2016-02-18 | 2017-08-02 | 東洋インキＳｃホールディングス株式会社 | Re-peelable adhesive and surface protective film |
-
1990
- 1990-06-28 JP JP2170479A patent/JP2549576B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8377514B2 (en) | 2008-05-09 | 2013-02-19 | Kraton Polymers Us Llc | Sulfonated block copolymer fluid composition for preparing membranes and membrane structures |
| US8377515B2 (en) | 2008-05-09 | 2013-02-19 | Kraton Polymers U.S. Llc | Process for preparing membranes and membrane structures from a sulfonated block copolymer fluid composition |
| US8263713B2 (en) | 2009-10-13 | 2012-09-11 | Kraton Polymers U.S. Llc | Amine neutralized sulfonated block copolymers and method for making same |
| US8445631B2 (en) | 2009-10-13 | 2013-05-21 | Kraton Polymers U.S. Llc | Metal-neutralized sulfonated block copolymers, process for making them and their use |
| US9394414B2 (en) | 2010-09-29 | 2016-07-19 | Kraton Polymers U.S. Llc | Elastic, moisture-vapor permeable films, their preparation and their use |
| US9429366B2 (en) | 2010-09-29 | 2016-08-30 | Kraton Polymers U.S. Llc | Energy recovery ventilation sulfonated block copolymer laminate membrane |
| US9365662B2 (en) | 2010-10-18 | 2016-06-14 | Kraton Polymers U.S. Llc | Method for producing a sulfonated block copolymer composition |
| US9861941B2 (en) | 2011-07-12 | 2018-01-09 | Kraton Polymers U.S. Llc | Modified sulfonated block copolymers and the preparation thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0457874A (en) | 1992-02-25 |
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