JP2011080088A - Method of producing adhesive composition for adhesive plaster - Google Patents

Method of producing adhesive composition for adhesive plaster Download PDF

Info

Publication number
JP2011080088A
JP2011080088A JP2011000019A JP2011000019A JP2011080088A JP 2011080088 A JP2011080088 A JP 2011080088A JP 2011000019 A JP2011000019 A JP 2011000019A JP 2011000019 A JP2011000019 A JP 2011000019A JP 2011080088 A JP2011080088 A JP 2011080088A
Authority
JP
Japan
Prior art keywords
adhesive
solution
acrylic
pressure
producing
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
Application number
JP2011000019A
Other languages
Japanese (ja)
Other versions
JP5337172B2 (en
Inventor
Akio Iwama
昭男 岩間
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lintec Corp
Original Assignee
Lintec Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Lintec Corp filed Critical Lintec Corp
Priority to JP2011000019A priority Critical patent/JP5337172B2/en
Publication of JP2011080088A publication Critical patent/JP2011080088A/en
Application granted granted Critical
Publication of JP5337172B2 publication Critical patent/JP5337172B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Landscapes

  • Adhesives Or Adhesive Processes (AREA)
  • Medicinal Preparation (AREA)
  • Materials For Medical Uses (AREA)
  • Adhesive Tapes (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of producing an adhesive composition for an adhesive plaster, which is carried out by formulating a liquid component to an adhesive of an acrylic polymer, where the composition has good compatibility of the acrylic polymer with the liquid component, together with good adhesion to the skin, generating no stimulation to the skin. <P>SOLUTION: An acrylic oligomer formed by polymerizing at least one alkyl acrylate or alkyl methacrylate having 4-10C alkyl and having a prescribed number average molecular weight, is used as the liquid component. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

この発明は、ベースシート(プラスチックフイルム、不織布、織布、紙など)の片面に、全体にわたる(べた一面)或いは適宜のパターン(水玉パターン、市松パターン、格子パターン、縦縞又は横縞パターンなど)の粘着層を設けた粘着絆創膏において、粘着層を構成する粘着剤組成物の改良に関するものである。   In the present invention, the entire surface (solid surface) or an appropriate pattern (polka dot pattern, checkered pattern, lattice pattern, vertical stripe or horizontal stripe pattern, etc.) is adhered to one side of a base sheet (plastic film, nonwoven fabric, woven fabric, paper, etc.) The present invention relates to an improvement of an adhesive composition constituting an adhesive layer in an adhesive bandage provided with a layer.

周知のように、この種の粘着絆創膏は皮膚に貼り付けて使用することから、その粘着層は、皮膚にしっかりと接着する皮膚接着性とともに、皮膚の角質層に剥離損傷による皮膚刺激やかぶれを発症させない剥離性を有するものが求められている。   As is well known, since this type of adhesive bandage is applied to the skin, its adhesive layer adheres to the skin firmly, and the skin stratum corneum is subject to skin irritation and rash caused by peeling damage. What has the peelability which does not make it develop is calculated | required.

しかしこのような粘着層に求められる皮膚接着性と剥離性は、実質上相反する性質であるため、従来においては、一方についてのある程度の犠牲は止むを得ないと考えれてきているが、近年、粘着層の皮膚接着強さを左右する特性値である微小な凹凸のある皮膚に対する粘着層の接触面積(濡れ面積)及び粘着剤としての粘着ポリマーの単位接触面積当たりの接着力の点からの検討により、粘着ポリマーに各種の液状成分を配合することが試みられ、この面から幾つかの粘着剤組成物も提案されている。   However, since skin adhesion and peelability required for such an adhesive layer are substantially contradictory properties, in the past, it has been considered that some sacrifice on one side is inevitable, Examination in terms of the contact area (wetting area) of the adhesive layer to the skin with minute irregularities, which is a characteristic value that affects the skin adhesion strength of the adhesive layer, and the adhesive force per unit contact area of the adhesive polymer as an adhesive Therefore, it is attempted to add various liquid components to the pressure-sensitive adhesive polymer, and several pressure-sensitive adhesive compositions have been proposed from this aspect.

しかしながら既提案のものは、液状成分と粘着ポリマーとの相溶性が悪く、液状成分の配合量が少ない場合でも、液状成分が粘着層の表面に染み出して、皮膚接着性を著しく低下させたり、液状成分自体が皮膚刺激を発生するなどの問題があり、実用段階に達していない。   However, the proposed one has poor compatibility between the liquid component and the pressure-sensitive adhesive polymer, and even when the amount of the liquid component is small, the liquid component oozes out to the surface of the pressure-sensitive adhesive layer, significantly reducing the skin adhesion, The liquid component itself has problems such as causing skin irritation and has not yet reached the practical stage.

この発明は、上記のような粘着剤としての粘着ポリマーに液状成分を配合する粘着絆創膏用粘着剤組成物として、粘着ポリマーと液状成分の相溶性及び皮膚接着性が良好で、皮膚刺激を発生しないものを提供すること、特にこの粘着絆創膏用粘着剤組成物の形成に用いる液状成分として、粘着ポリマーとの相溶性が良いとともに皮膚刺激性がなく、かつ粘着ポリマーの凝集力を緩和して、その単位接触面積当たりの接着力を減少させると同時に皮膚接触面積を増加させるものを見出して、液状成分の添加量を調整することにより、粘着ポリマーの単位接触面積当たりの接着力を小さく抑える形で、粘着層の皮膚接着強さを調整可能にする粘着絆創膏用粘着剤組成物の製造方法を提供することを課題としている。 This invention is a pressure-sensitive adhesive composition for a pressure-sensitive adhesive bandage in which a liquid component is blended with the pressure-sensitive adhesive polymer as the pressure-sensitive adhesive as described above, and the compatibility between the pressure-sensitive adhesive polymer and the liquid component and the skin adhesiveness are good, and skin irritation does not occur. In particular, as a liquid component used for forming the adhesive composition for adhesive adhesive plaster, the compatibility with the adhesive polymer is good and the skin is not irritating. Finding what reduces the adhesive force per unit contact area and at the same time increases the skin contact area, and by adjusting the addition amount of the liquid component, in a form to suppress the adhesive force per unit contact area of the adhesive polymer, It has an object to provide a method for producing a pressure-sensitive adhesive plaster pressure-sensitive adhesive composition that allows adjust the skin adhesion strength of the adhesive layer.

本発明者は、上記の課題を解決するために、粘着剤として粘着ポリマー(特にアクリルポリマー)を用いる粘着絆創膏について種々実験検討を行った結果、数平均分子量が2,000〜40,000のアクリル系オリゴマー(より好ましくは、数平均分子量が2,000〜4,400のアクリル系オリゴマー)は、粘着ポリマー(特にアクリルポリマー)との相溶性が良く、粘着層を形成する粘着剤組成物中に配合した際に、粘着層の皮膚に対する濡れ面積を増加させるが、皮膚内部に浸透することがなく、従って皮膚内部の脂質構造に無影響で、皮膚刺激性がないことを見出し、この発明を完成した。 In order to solve the above problems, the present inventor has conducted various experimental studies on adhesive bandages using an adhesive polymer (particularly an acrylic polymer) as an adhesive, and as a result, an acrylic having a number average molecular weight of 2,000 to 40,000. -Based oligomers (more preferably acrylic oligomers having a number average molecular weight of 2,000 to 4,400 ) have good compatibility with pressure-sensitive adhesive polymers (particularly acrylic polymers), and in the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer When blended, increases the wetted area of the adhesive layer to the skin, but does not penetrate into the skin, and therefore has no effect on the lipid structure inside the skin and is non-irritating to the skin, completing the present invention. did.

即ちこの発明に係る粘着絆創膏用粘着剤組成物の製造方法は、アクリルポリマーの溶液に、所定量のアクリル系オリゴマーの溶液を溶解させた後、所定量の反応性架橋剤を添加してなる粘着絆創膏用粘着剤組成物の製造方法であって、
(1)アルキル基の炭素数が4〜10のアクリル酸アルキルエステル又はメタアクリル酸アルキルエステルの一種以上を溶液重合して形成したアクリル系オリゴマーの溶液を製造する工程
(2)アルキル基の炭素数が4〜10のアクリル酸アルキルエステル又はメタアクリル酸アルキルエステルと、アクリル酸モノマー、メタクリル酸モノマー、2−ヒドロキシルエチルアクリレート、あるいは2−ヒドロキシエチルメタアクリレートから選択されるモノマーと、を含むモノマー混合液を溶液重合して形成したアクリルポリマーを含んでなるアクリルポリマーの溶液を製造する工程
(3)アクリル系オリゴマーの溶液およびアクリルポリマーの溶液を混合してなる溶液に対して、前記反応性架橋剤を、前記アクリルポリマーの0.01〜5重量%の範囲内の値となるように添加する工程と、を含むことを基本的な特徴としている。
That is, the method for producing a pressure-sensitive adhesive composition for adhesive bandages according to the present invention comprises an acrylic polymer solution in which a predetermined amount of an acrylic oligomer solution is dissolved and then a predetermined amount of a reactive crosslinking agent is added. A method for producing an adhesive composition for adhesive bandages,
(1) A step of producing a solution of an acrylic oligomer formed by solution polymerization of one or more of alkyl alkyl ester having 4 to 10 carbon atoms of alkyl group or alkyl methacrylate.
(2) Acrylic acid alkyl ester or methacrylic acid alkyl ester having 4 to 10 carbon atoms in the alkyl group, and selected from acrylic acid monomer, methacrylic acid monomer, 2-hydroxylethyl acrylate, or 2-hydroxyethyl methacrylate A process for producing an acrylic polymer solution comprising an acrylic polymer formed by solution polymerization of a monomer mixture containing the monomer
(3) With respect to the solution obtained by mixing the acrylic oligomer solution and the acrylic polymer solution, the reactive crosslinking agent is set to a value within the range of 0.01 to 5% by weight of the acrylic polymer. The basic feature is to include an adding step .

この発明の粘着剤組成物においてアクリル系オリゴマーの数平均分子量を2,000〜40,000の範囲とするのは、数平均分子量が40,000を上回ると、硬くなって、必要な液状の状態が保持できなくなり、又2,000を下回ると、皮膚内部に浸透しやすくなり、この結果皮膚内部の脂質構造に影響が及んで、種々の皮膚刺激が発現しやすくなることの知見からである。   In the pressure-sensitive adhesive composition of the present invention, the number average molecular weight of the acrylic oligomer is in the range of 2,000 to 40,000 because when the number average molecular weight exceeds 40,000, it becomes hard and is in a necessary liquid state. It is based on the knowledge that when it becomes impossible to hold and below 2,000, it easily penetrates into the skin, and as a result, the lipid structure inside the skin is affected and various skin irritation is likely to occur.

アクリル系オリゴマーは、上記のように液状であることの必要性から、一般には、アルキル基の炭素数が4〜10のアクリル酸アルキルエステル又はメタアクリル酸アルキルエステルを用いることが望ましく、例えばアルキル基が、メチル、エチル、プロピル、イソプロピル、2−メトキシエチル、ブチル、イソブチル、ターシャリーブチル、ヘキシル、オクチル、イソオクチル、2−エチルへキシル、ノニル、イソノニル等のものから一種以上を選択して用いることができる。   In general, it is desirable to use an acrylic acid alkyl ester or a methacrylic acid alkyl ester having an alkyl group having 4 to 10 carbon atoms, for example, an alkyl group. Is selected from at least one of methyl, ethyl, propyl, isopropyl, 2-methoxyethyl, butyl, isobutyl, tertiary butyl, hexyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, etc. Can do.

なおアクリル系オリゴマーは、一般には、適当な連鎖移動剤(ラウリルメルカプタンやメルカプトエタノールなど)を用いてアクリル系モノマーを重合(単独重合又は共重合)する通常の方法で製造することができる。   In general, the acrylic oligomer can be produced by an ordinary method in which an acrylic monomer is polymerized (homopolymerized or copolymerized) using an appropriate chain transfer agent (such as lauryl mercaptan or mercaptoethanol).

この発明の粘着剤組成物において用いる粘着剤の粘着ポリマーとしては、特にアルキル基の炭素数が4〜10のアクリル酸アルキルエステル又はメタアクリル酸アルキルエステルと、アクリル酸モノマー、メタクリル酸モノマー、2−ヒドロキシルエチルアクリレート、あるいは2−ヒドロキシエチルメタアクリレートから選択されるモノマーと、を含むモノマー混合液から溶液重合して形成したアクリルポリマーが好適である。 As the pressure-sensitive adhesive polymer used in the pressure-sensitive adhesive composition of the present invention, an acrylic acid alkyl ester or methacrylic acid alkyl ester having an alkyl group having 4 to 10 carbon atoms , an acrylic acid monomer, a methacrylic acid monomer, 2- An acrylic polymer formed by solution polymerization from a monomer mixture containing hydroxylethyl acrylate or a monomer selected from 2-hydroxyethyl methacrylate is preferred.

このアクリルポリマーはアクリル系オリゴマーとの相溶性が良く、粘着層の皮膚への濡れ面積を最も効果的に大きくすることができることを確認している。   This acrylic polymer has good compatibility with acrylic oligomers, and it has been confirmed that the wet area of the adhesive layer on the skin can be most effectively increased.

アクリルポリマーを形成するアルキル基の炭素数が4〜10のアクリル酸アルキルエステル又はメタアクリル酸アルキルエステルとしては、アクリル系オリゴマーについて既述したように、一般には、アルキル基が、メチル、エチル、プロピル、イソプロピル、2−メトキシエチル、ブチル、イソブチル、ターシャリーブチル、ヘキシル、オクチル、イソオクチル、2−エチルへキシル、ノニル、イソノニル等のものを選択して用いることができ、この場合アクリル酸アルキルエステル又はメタクリル酸アルキルエステルは一種の重合の形態でも、或いは特に粘着剤固有の接着力を調整する点から、二種以上混合の共重合の形態でも用いることができる。 As the acrylic acid alkyl ester or methacrylic acid alkyl ester having 4 to 10 carbon atoms of the alkyl group forming the acrylic polymer, as described above for the acrylic oligomer, generally, the alkyl group is methyl, ethyl, propyl. , Isopropyl, 2-methoxyethyl, butyl, isobutyl, tertiary butyl, hexyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, and the like can be used. The methacrylic acid alkyl ester can be used in one form of polymerization or in the form of a copolymerization of two or more kinds, particularly from the viewpoint of adjusting the adhesive strength inherent to the pressure-sensitive adhesive.

この粘着剤としてのアクリルポリマーは、皮膚に対する粘着力を高めるために、アクリルポリマーの1〜15重量%のアクリル酸モノマーやメタクリル酸モノマー或いは2−ヒドロキシルエチルアクリレートや2−ヒドロキシエチルメタアクリレートを共重合させることを特徴とし、又その凝集力を調整するために、アクリルポリマーの0.01〜5重量%の反応型架橋剤、例えば多価エポキシ化合物(エチレングリコール−ジグリシジルエーテル、トリグリシジルイソシアヌレート等)、多価イソシアネート化合物(日本ポリウレタン社製のコロネートL、HL等)、過酸化ベンゾイル(日本油脂社製のナイパーBO等)などの分解してラジカルを発生する過酸化物(過酸化ベンゾイル等)を添加することができる。 Acrylic polymer as an adhesive is a copolymer of acrylic acid monomer, methacrylic acid monomer, 2-hydroxylethyl acrylate or 2-hydroxyethyl methacrylate of 1 to 15% by weight of the acrylic polymer in order to increase adhesion to the skin. characterized in that is also in order to adjust the cohesive force, 0.01 to 5% by weight of the reactive cross-linking agent of an acrylic polymer, for example, polyepoxy compound (ethylene glycol - diglycidyl ether, triglycidyl isocyanurate ), Polyisocyanate compounds (such as Coronate L and HL manufactured by Nippon Polyurethane Co., Ltd.), benzoyl peroxide (Nyper BO manufactured by Nippon Oil & Fats Co., Ltd.) and other peroxides that generate radicals (such as benzoyl peroxide) Can be added.

しかしこの粘着絆創膏用の粘着剤組成物においては、皮膚に適度に接着(皮膚を傷付けるような接着し過ぎや直ぐに剥離するような接着の不十分さのない状態で接着)するようにするために、一般に、剥離接着力(180°剥離接着力:23℃の雰囲気において、粘着剤塗布面に2kgのロールを往復させて貼り付けた12mm幅のポリエチレンテレフタレート(PET)フイルムを、300mm/minの速度で引き剥がす際の抵抗力)を40〜400gにすることが望ましい。   However, in this pressure-sensitive adhesive composition for adhesive bandages, in order to ensure proper adhesion to the skin (adhesion without over-adhesion that damages the skin or inadequate adhesion that peels off immediately) In general, a peel adhesive strength (180 ° peel adhesive strength: in an atmosphere of 23 ° C., a 12 mm wide polyethylene terephthalate (PET) film attached by reciprocating a 2 kg roll on the pressure-sensitive adhesive application surface is a speed of 300 mm / min. It is desirable to set the resistance when peeling off at 40 to 400 g.

この粘着絆創膏用の粘着剤組成物は、通常は、粘着剤としてのアクリルポリマーを蒸発除去し易い溶剤(トルエン、酢酸エチル、ヘキサンなど)に溶解したアクリルポリマー溶液に、所要量のアクリル系オリゴマーを分散溶解し、必要に応じて反応型架橋剤や接着力調整成分などを添加するという方式でドープの状態に製造することができ、このドープを布、紙、プラスチックフイルムなどに均一に塗布して、粘着絆創膏を形成することができる。   This pressure-sensitive adhesive composition for adhesive bandages is usually prepared by adding a required amount of an acrylic oligomer to an acrylic polymer solution in which an acrylic polymer as a pressure-sensitive adhesive is easily removed by evaporation (toluene, ethyl acetate, hexane, etc.). Dispersed and dissolved, and can be manufactured in a dope state by adding a reactive cross-linking agent or adhesive force adjusting component as necessary. Apply this dope evenly on cloth, paper, plastic film, etc. Can form an adhesive bandage.

なお上記において必要に応じて添加する接着力調整成分は、アクリル系オリゴマーの効果を弱化させないために、粘着剤としてのアクリルポリマーの30重量%以下に留めることが望ましい。   In the above, it is desirable that the adhesive strength adjusting component added as necessary is limited to 30% by weight or less of the acrylic polymer as the pressure-sensitive adhesive so as not to weaken the effect of the acrylic oligomer.

以下この発明の実施例について詳述する。   Examples of the present invention will be described in detail below.

[実施例1]
(1)アクリル系オリゴマーの製造
2−エチルへキシルアクリレート300g(1.63モル)と連鎖移動剤としてのラウリルメルカプタン27.6g(0.136モル)を、溶媒の酢酸エチル82gに溶解して、モノマー混合溶液を形成した。このモノマー混合溶液を、蒸気凝縮還流塔を備えた攪拌機付き重合反応器に仕込み、重合開始剤としてアゾビスイソブチロニトリル0.6gを添加して溶解した後、そのまま湯浴に浸漬して60℃までゆっくり昇温することにより、重合開始剤を分解して、重合反応を開始した。
[Example 1]
(1) Production of acrylic oligomer 300 g (1.63 mol) of 2-ethylhexyl acrylate and 27.6 g (0.136 mol) of lauryl mercaptan as a chain transfer agent were dissolved in 82 g of ethyl acetate as a solvent, A monomer mixed solution was formed. This monomer mixed solution was charged into a polymerization reactor equipped with a stirrer equipped with a vapor condensation reflux tower, and 0.6 g of azobisisobutyronitrile as a polymerization initiator was added and dissolved, and then immersed in a hot water bath as it was. The polymerization initiator was decomposed by slowly raising the temperature to 0 ° C. to initiate the polymerization reaction.

重合反応の開始により発熱が始まり次第、適宜冷却浴に浸漬して冷却することにより、重合反応液の温度を70±3℃に制御しながら、約7時間反応させて、重合反応を終結させた(ここでは重合反応溶液の不揮発残分、すなわち重合反応物であるアクリル系オリゴマーの濃度を測定し、80.4重量%であることを確認して、終結を判定した。なおこの不揮発残分は、約1gの試料溶液を150℃で1時間加熱乾燥した後における不揮発残分の比率である)。このようにして得られたアクリル系オリゴマーの粘ちょうな酢酸エチル溶液は、粘度(B型粘度計による測定、以下同じ)が14ポイズ、アクリル系オリゴマーの数平均分子量(GPC法による測定、以下同じ)が2,200であった。   As soon as heat generation started by the start of the polymerization reaction, the reaction was terminated by appropriately immersing in a cooling bath and cooling to control the temperature of the polymerization reaction solution at 70 ± 3 ° C. for about 7 hours to complete the polymerization reaction. (Here, the non-volatile residue of the polymerization reaction solution, that is, the concentration of the acrylic oligomer as the polymerization reaction product was measured and confirmed to be 80.4% by weight, and the termination was determined. The ratio of non-volatile residue after approximately 1 g of the sample solution was dried by heating at 150 ° C. for 1 hour). The viscous ethyl acetate solution of the acrylic oligomer thus obtained has a viscosity (measured with a B-type viscometer, the same shall apply hereinafter) of 14 poise, and the number average molecular weight of the acrylic oligomer (measured by a GPC method, hereinafter the same shall apply). ) Was 2,200.

(2)アクリルポリマーの製造
アクリル酸モノマー25g(5重量部)と2−エチルへキシルアクリレート500g(100重量部)を酢酸エチル1,575gに溶解して、蒸気凝縮還流塔を備えた攪拌機付き重合反応器に仕込み、重合開始剤のベンゾイルパーオキサイド0.5gを添加した後、そのまま湯浴に浸漬して58℃までゆっくり昇温することにより、重合開始剤を分解して、重合反応を開始した。
(2) Production of Acrylic Polymer 25 g (5 parts by weight) of acrylic acid monomer and 500 g (100 parts by weight) of 2-ethylhexyl acrylate were dissolved in 1,575 g of ethyl acetate and polymerized with a stirrer equipped with a vapor condensation reflux tower. After charging the reactor and adding 0.5 g of benzoyl peroxide as a polymerization initiator, the polymerization initiator was decomposed by slowly immersing it in a hot water bath and slowly raising the temperature to 58 ° C. to initiate the polymerization reaction. .

これにより発熱が始まり次第、適宜冷却浴に浸漬して冷却し、温度を63±3℃に制御しながら、約10時間反応させた。発熱がほぼおさまった段階に、さらにベンゾイルパーオキサイド0.1gを加えた後、温度を70±2℃まで上げて、約5時間加熱重合を行って、重合反応を完結させた。これにより得たアクリルポリマーの酢酸エチル溶液は、粘度が360ポイズ、不揮発残分すなわちアクリルポリマー濃度が25.8重量%、数平均分子量が840,000であった。   As a result, as soon as heat generation started, it was cooled by immersing in a cooling bath as appropriate, and the reaction was carried out for about 10 hours while controlling the temperature at 63 ± 3 ° C. After the exotherm was almost subsided, 0.1 g of benzoyl peroxide was further added, the temperature was raised to 70 ± 2 ° C., and heat polymerization was carried out for about 5 hours to complete the polymerization reaction. The ethyl acetate solution of the acrylic polymer thus obtained had a viscosity of 360 poise, a non-volatile residue, that is, an acrylic polymer concentration of 25.8% by weight, and a number average molecular weight of 840,000.

(3)粘着絆創膏用粘着剤組成物と該組成物を塗布した粘着絆創膏の製造
上記の(1)、(2)で製造したアクリル系オリゴマーの酢酸エチル溶液64.2g(不揮発残分51.6g)と、アクリルポリマーの酢酸エチル溶液200g(不揮発残分51.6g)を混合した溶液に、反応型架橋剤として多価イソシアネート化合物(日本ポリウレタン社製コロネートHL)0.21gを添加した後、酢酸エチル溶剤による調整により、不揮発残分が25重量%の粘着絆創膏用粘着剤組成物の酢酸エチル溶液を製造した。この粘着剤組成物における液状成分としてのアクリル系オリゴマーの含有率は50重量%である。
(3) Adhesive composition for adhesive bandages and manufacture of adhesive bandages coated with the composition
The acrylic oligomer ethyl acetate solution 64.2 g (non-volatile residue 51.6 g) produced in the above (1) and (2) and the acrylic polymer ethyl acetate solution 200 g (non-volatile residue 51.6 g) were mixed. After adding 0.21 g of a polyisocyanate compound (Coronate HL manufactured by Nippon Polyurethane Co., Ltd.) as a reactive crosslinking agent to the solution, the pressure-sensitive adhesive composition for adhesive adhesive plaster having a non-volatile residue of 25% by weight by adjustment with an ethyl acetate solvent Of ethyl acetate was prepared. The content of the acrylic oligomer as a liquid component in this pressure-sensitive adhesive composition is 50% by weight.

この粘着剤組成物の酢酸エチル溶液をポリエステル不織布(200μm厚)に均一に塗布した後、110℃で加熱乾燥して、粘着剤組成物、即ち粘着層の厚さが60μmの粘着絆創膏を製造した。この粘着絆創膏の剥離接着力は321gであった。   The ethyl acetate solution of this pressure-sensitive adhesive composition was uniformly applied to a polyester nonwoven fabric (200 μm thickness) and then dried by heating at 110 ° C. to produce a pressure-sensitive adhesive composition, that is, a pressure-sensitive adhesive bandage having a pressure-sensitive adhesive layer thickness of 60 μm. . The adhesive strength of the adhesive bandage was 321 g.

(4)アクリル系オリゴマーを含まない粘着絆創膏用粘着剤組成物と該組成物を塗布した比較用粘着絆創膏の製造
比較のために、(2)で製造したアクリルポリマーの酢酸エチル溶液200g(不揮発残分51.6g)に、反応型架橋剤の多価イソシアネート化合物(日本ポリウレタン社製コロネートHL)0.21gを加えて混合溶解するとともに、酢酸エチル溶剤による調整によって、不揮発残分が25重量%の粘着絆創膏用粘着剤組成物の酢酸エチル溶液を製造した。
(4) Production of pressure-sensitive adhesive composition for pressure-sensitive adhesive bandages that does not contain an acrylic oligomer and a pressure-sensitive adhesive bandage for comparison with the composition applied
For comparison, 0.21 g of a polyvalent isocyanate compound (Coronate HL manufactured by Nippon Polyurethane Co., Ltd.) as a reactive crosslinking agent was added to 200 g of the acrylic polymer ethyl acetate solution produced in (2) (nonvolatile residue 51.6 g). Then, an ethyl acetate solution of a pressure-sensitive adhesive composition for adhesive bandages with a non-volatile residue of 25% by weight was prepared by mixing and dissolving with an ethyl acetate solvent.

この粘着剤組成物の酢酸エチル溶液を(3)のものと同様に塗布、乾燥して、ポリエステル不織布上における粘着層の厚さが60μmの比較用粘着絆創膏を製造した。この粘着絆創膏の剥離接着力は350gであった。   An ethyl acetate solution of this pressure-sensitive adhesive composition was applied and dried in the same manner as in (3) to produce a comparative adhesive bandage with a pressure-sensitive adhesive layer thickness of 60 μm on the polyester nonwoven fabric. The adhesive strength of the adhesive bandage was 350 g.

(5)アクリル系オリゴマーによる皮膚角質層の剥離損傷防止効果の測定
上記の(3)、(4)で製造した粘着絆創膏の短冊状(幅12mm、長さ40mm)試験片(粘着層有効面積:480mm)のそれぞれについて、人の後腕部内側皮膚に24時間貼り付けた後剥がして、粘着層表面をニンヒドリン溶液で染色し、剥離破壊により粘着層表面に付着した角質細胞を暗紫色に発色させ、顕微鏡写真の画像解析により角質細胞の発色面積比率(暗紫色に発色した面積の総和/粘着層面積×100)を測定したところ、(4)の粘着絆創膏の場合には92%であったのに対し、(3)の粘着絆創膏の場合には8%で、アクリル系オリゴマーの存在により、皮膚角質の剥離損傷が大幅に改善されることが判明した。
(5) Measurement of peeling damage prevention effect of skin stratum corneum by acrylic oligomer
For each of the strip-like (width 12 mm, length 40 mm) test pieces (adhesive layer effective area: 480 mm 2 ) of the adhesive adhesive plaster produced in the above (3) and (4), 24 hours on the inner skin of the human forearm After pasting, peeling off, staining the surface of the adhesive layer with ninhydrin solution, coloring the corneocytes attached to the surface of the adhesive layer due to peeling failure, and developing the color area ratio of the corneocytes (coloring in dark purple) by analyzing the photomicrograph Total area / adhesive layer area × 100) was 92% in the case of the adhesive bandage of (4), whereas it was 8% in the case of the adhesive bandage of (3). It was found that the exfoliation damage of the skin keratin was greatly improved by the presence of the system oligomer.

[実施例2]
(1)アクリル系オリゴマーの製造
メチルメタアクリレート75g(0.749モル)、2−エチルへキシルアクリレート225g(1.221モル)とラウリルメルカプタン2.6g(0.013モル)を、酢酸エチル溶液76gに溶解して、モノマー混合溶液を形成した。このモノマー混合溶液を実施例1の(1)と同じ条件、方式で重合反応させて、アクリル系オリゴマーの酢酸エチル溶液を製造した。この溶液は、不揮発残分(アクリル系オリゴマーの濃度)が80.0重量%、粘度が28ポイズ、アクリル系オリゴマーの数平均分子量が24,000であった。
[Example 2]
(1) Production of acrylic oligomer 75 g (0.749 mol) of methyl methacrylate, 225 g (1.221 mol) of 2-ethylhexyl acrylate and 2.6 g (0.013 mol) of lauryl mercaptan were added to 76 g of ethyl acetate solution. To form a monomer mixed solution. This monomer mixed solution was subjected to a polymerization reaction under the same conditions and method as in (1) of Example 1 to produce an ethyl acetate solution of an acrylic oligomer. This solution had a non-volatile residue (concentration of acrylic oligomer) of 80.0% by weight, a viscosity of 28 poise, and the number average molecular weight of the acrylic oligomer was 24,000.

(2)アクリルポリマーの製造
アクリル酸モノマー25g(5重量部)、メチルメタアクリレート125g(25重量部)と2−エチルへキシルアクリレート375g(75重量部)を酢酸エチル1,575gに溶解したモノマー混合溶液を、実施例1の(2)と同じ条件、方式で重合反応させて、アクリルポリマーの酢酸エチル溶液を製造した。この溶液は、粘度が344ポイズ、不揮発残分(アクリルポリマーの濃度)が25.9重量%、数平均分子量が980,000であった。
(2) Production of acrylic polymer
A monomer mixed solution in which 25 g (5 parts by weight) of an acrylic acid monomer, 125 g (25 parts by weight) of methyl methacrylate and 375 g (75 parts by weight) of 2-ethylhexyl acrylate were dissolved in 1,575 g of ethyl acetate was used. A polymerization reaction was carried out under the same conditions and method as in (2) to produce an ethyl acetate solution of an acrylic polymer. This solution had a viscosity of 344 poise, a non-volatile residue (acrylic polymer concentration) of 25.9% by weight, and a number average molecular weight of 980,000.

(3)粘着絆創膏用粘着剤組成物と該組成物を塗布した粘着絆創膏の製造
上記の(1)、(2)で製造したアクリル系オリゴマーの酢酸エチル溶液11.5g(不揮発残分9.2g)と、アクリルポリマーの酢酸エチル溶液200g(不揮発残分51.8g)を混合し、酢酸エチル溶剤による調整によって、不揮発残分が25重量%の粘着絆創膏用粘着剤組成物の酢酸エチル溶液を製造した。この組成物におけるアクリル系オリゴマーの含有率は15重量%である。
(3) Adhesive composition for adhesive bandages and manufacture of adhesive bandages coated with the composition
Mix 11.5 g (nonvolatile residue 9.2 g) of the acrylic oligomer ethyl acetate solution prepared in (1) and (2) above and 200 g of acrylic polymer ethyl acetate solution (nonvolatile residue 51.8 g). By adjusting with an ethyl acetate solvent, an ethyl acetate solution of a pressure-sensitive adhesive composition for adhesive bandages with a non-volatile residue of 25% by weight was produced. The acrylic oligomer content in the composition is 15% by weight.

この粘着剤組成物の酢酸エチル溶液を、ポリエステル不織布(200μm厚)に均一に塗布した後、110℃で加熱乾燥して、粘着層の厚さが60μmの粘着絆創膏を製造した。この粘着絆創膏の剥離接着力は328gであった。   The ethyl acetate solution of the pressure-sensitive adhesive composition was uniformly applied to a polyester nonwoven fabric (thickness: 200 μm), and then heated and dried at 110 ° C. to produce a pressure-sensitive adhesive bandage having a pressure-sensitive adhesive layer thickness of 60 μm. The adhesive strength of the adhesive bandage was 328 g.

(4)アクリル系オリゴマーを含まない粘着絆創膏用粘着剤組成物と該組成物を塗布した比較用粘着絆創膏の製造
上記の(2)で製造したアクリルポリマーの酢酸エチル溶液を(3)のものと同様に塗布、乾燥して、ポリエステル不織布上における粘着層の厚さが60μmのアクリル系オリゴマーを含まない比較用粘着絆創膏を製造した。この粘着絆創膏の剥離接着力は341gであった。
(4) Production of pressure-sensitive adhesive composition for pressure-sensitive adhesive bandages that does not contain an acrylic oligomer and a pressure-sensitive adhesive bandage for comparison with the composition applied
The acrylic polymer ethyl acetate solution prepared in (2) above was applied and dried in the same manner as in (3), and the comparative adhesive without the acrylic oligomer having an adhesive layer thickness of 60 μm on the polyester nonwoven fabric. A bandage was produced. The adhesive strength of the adhesive bandage was 341 g.

(5)アクリル系オリゴマーの皮膚角質層の剥離損傷防止効果の測定
上記の(3)、(4)で製造した粘着絆創膏のそれぞれについて、実施例1の場合と同じ条件、方式で、付着した皮膚の角質細胞による発色面積比率を測定したところ、(4)の粘着絆創膏では94%であったのに対し、(3)の粘着絆創膏では21%で、アクリル系オリゴマーの存在によって、皮膚角質の剥離損傷が大きく改善されることが確認された。
(5) Measurement of peeling damage prevention effect of acrylic oligomer on skin stratum corneum
For each of the adhesive bandages produced in the above (3) and (4), the ratio of the color development area by the keratinocytes of the attached skin was measured under the same conditions and method as in Example 1, and the adhesive of (4) The adhesive bandage was 94%, while the adhesive bandage of (3) was 21%. It was confirmed that the exfoliation damage of the skin keratin was greatly improved by the presence of the acrylic oligomer.

[実施例3]
(1)アクリル系オリゴマーの製造
2−メトキシエチルアクリレート120g(0.922モル)、2−エチルへキシルアクリレート180g(0.977モル)とラウリルメルカプタン17.4g(0.086モル)を、酢酸エチル80gに溶解して、モノマー混合溶液を形成した。このモノマー混合溶液を、実施例1の(1)と同じ条件、方式で、重合反応させて、アクリル系オリゴマーの酢酸エチル溶液を製造した。この溶液は、不揮発残分(アクリル系オリゴマーの濃度)が80.2重量%、アクリル系オリゴマーの数平均分子量が3,100であった。
[Example 3]
(1) Production of acrylic oligomer
A monomer mixture was prepared by dissolving 120 g (0.922 mol) of 2-methoxyethyl acrylate, 180 g (0.977 mol) of 2-ethylhexyl acrylate and 17.4 g (0.086 mol) of lauryl mercaptan in 80 g of ethyl acetate. A solution was formed. This monomer mixed solution was subjected to a polymerization reaction under the same conditions and method as in (1) of Example 1 to produce an ethyl acetate solution of an acrylic oligomer. This solution had a non-volatile residue (concentration of acrylic oligomer) of 80.2% by weight, and the acrylic oligomer had a number average molecular weight of 3,100.

(2)粘着絆創膏用粘着剤組成物と該組成物を塗布した粘着絆創膏の製造
上記の(1)で製造したアクリル系オリゴマーの酢酸エチル溶液78.7g(不揮発残分63.1g)と、実施例1の(2)で製造したアクリルポリマーの酢酸エチル溶液200g(不揮発残分51.6g)を混合した溶液に、反応型架橋剤として多価イソシアネート化合物(日本ポリウレタン社製コロネートHL)0.21gを添加した後、酢酸エチル溶剤による調整により、不揮発残分が25重量%の粘着絆創膏用粘着剤組成物の酢酸エチル溶液を製造した。この粘着剤組成物におけるアクリル系オリゴマーの含有率は55重量%である。
(2) Adhesive composition for adhesive bandages and manufacture of adhesive bandages coated with the composition
78.7 g (nonvolatile residue 63.1 g) of the ethyl acetate solution of the acrylic oligomer produced in the above (1) and 200 g (nonvolatile residue 51) of the ethyl acetate solution of the acrylic polymer produced in (2) of Example 1 .6 g) was added as a reactive crosslinking agent 0.21 g of a polyisocyanate compound (Coronate HL, manufactured by Nippon Polyurethane Co., Ltd.), and then adjusted with an ethyl acetate solvent to give a non-volatile residue of 25 wt% An ethyl acetate solution of the adhesive composition for adhesive bandages was produced. The content of the acrylic oligomer in this pressure-sensitive adhesive composition is 55% by weight.

この粘着剤組成物の酢酸エチル溶液をポリエステル不織布(200μm厚)に均一に塗布した後、110℃で乾燥加熱して、粘着層の厚さが60μmの粘着絆創膏を製造した。この粘着絆創膏の剥離接着力は324gであった。   An ethyl acetate solution of this pressure-sensitive adhesive composition was uniformly applied to a polyester nonwoven fabric (200 μm thickness), and then dried and heated at 110 ° C. to produce a pressure-sensitive adhesive bandage with a pressure-sensitive adhesive layer thickness of 60 μm. The adhesive strength of the adhesive bandage was 324 g.

(3)アクリル系オリゴマーの皮膚角質層の剥離損傷防止効果の測定
上記の(2)及び実施例1の(4)で製造した粘着絆創膏のそれぞれについて、実施例1の場合と同じ条件、方式で、付着した皮膚の角質細胞による発色面積比率を測定したところ、後者の粘着絆創膏の場合には92%であったのに対し、前者の上記(2)の粘着絆創膏の場合には7%で、アクリル系オリゴマーによって、皮膚角質の剥離損傷効果が大幅に改善されることが判明した。
(3) Measurement of peeling damage prevention effect of acrylic oligomer on skin stratum corneum
For each of the adhesive bandages produced in the above (2) and Example 1 (4), the ratio of the color development area by the keratinocytes of the attached skin was measured under the same conditions and method as in Example 1. In the case of the adhesive adhesive bandage of 92%, it was 7% in the case of the former adhesive bandage of the above (2), and the acrylic oligomer significantly improves the peeling damage effect of the skin keratin. It has been found.

[実施例4]
(1)アクリル系オリゴマーの製造
2−エチルヘキシルアクリレート300g(1.63モル)、ラウレルメルカプタン13.8g(0.068モル)を用いる以外は、実施例1の(1)と同じ条件、方式で、アクリル系オリゴマーの酢酸エチル溶液を製造した。この溶液は、不揮発残分が82.3重量%、アクリル系オリゴマーの数平均分子量が4,400であった。
[Example 4]
(1) Production of acrylic oligomer
Except for using 300 g (1.63 mol) of 2-ethylhexyl acrylate and 13.8 g (0.068 mol) of laurel mercaptan, an ethyl acetate solution of an acrylic oligomer was used under the same conditions and method as in (1) of Example 1. Manufactured. This solution had a non-volatile residue of 82.3% by weight and an acrylic oligomer having a number average molecular weight of 4,400.

(2)アクリルポリマーの製造
2−ヒドロキシエチルアクリレート50g(10重量部)と、2−エチルへキシルアクリレート500g(100重量部)を用いる以外は実施例1の(2)と同様の条件、方式で重合反応させて、アクリルポリマーの粘ちょうな酢酸エチル溶液を製造した。この溶液は、粘度が274ポイズ、不揮発残分(アクリルポリマーの濃度)が22.5重量%、数平均分子量が710,000であった。
(2) Production of acrylic polymer
An acrylic polymer was polymerized by the same conditions and method as in (2) of Example 1 except that 50 g (10 parts by weight) of 2-hydroxyethyl acrylate and 500 g (100 parts by weight) of 2-ethylhexyl acrylate were used. A viscous ethyl acetate solution was prepared. This solution had a viscosity of 274 poise, a non-volatile residue (acrylic polymer concentration) of 22.5% by weight, and a number average molecular weight of 710,000.

(3)粘着絆創膏用粘着剤組成物と該組成物を塗布した粘着絆創膏の製造
上記の(1)で製造したアクリル系オリゴマーの酢酸エチル溶液36.5g(不揮発残分30.0g)と、(2)で製造したアクリルポリマーの酢酸エチル溶液200g(不揮発残分45.0g)を混合した溶液に、反応型架橋剤として多価イソシアネート化合物(日本ポリウレタン社製コロネートL)0.3gを添加した後、酢酸エチル溶剤による調整により、不揮発残分が25重量%の粘着絆創膏用粘着剤組成物の酢酸エチル溶液を製造した。この粘着剤組成物におけるアクリル系オリゴマーの含有率は40重量%である。
(3) Adhesive composition for adhesive bandages and manufacture of adhesive bandages coated with the composition
Acrylic oligomer ethyl acetate solution 36.5 g (non-volatile residue 30.0 g) produced in (1) above and 200 g acrylic polymer ethyl acetate solution (non-volatile residue 45.0 g) produced in (2) After adding 0.3 g of a polyisocyanate compound (Coronate L manufactured by Nippon Polyurethane Co., Ltd.) as a reactive crosslinking agent to the mixed solution, the pressure-sensitive adhesive for adhesive adhesive plaster having a non-volatile residue of 25% by weight by adjustment with an ethyl acetate solvent An ethyl acetate solution of the composition was prepared. The content of the acrylic oligomer in this pressure-sensitive adhesive composition is 40% by weight.

この粘着剤組成物の酢酸エチル溶液をポリエステル不織布(200μm厚)に均一に塗布した後、110℃で加熱乾燥して、粘着層の厚さが60μmの粘着絆創膏を製造した。この粘着絆創膏の剥離接着力は336gであった。   The ethyl acetate solution of this pressure-sensitive adhesive composition was uniformly applied to a polyester non-woven fabric (thickness: 200 μm) and then dried by heating at 110 ° C. to produce a pressure-sensitive adhesive bandage having a pressure-sensitive adhesive layer thickness of 60 μm. The adhesive strength of the adhesive bandage was 336 g.

(4)アクリル系オリゴマーを含まない粘着絆創膏用粘着剤組成物と該組成物を塗布した比較用粘着絆創膏の製造
上記の(2)で製造したアクリルポリマーの酢酸エチル溶液を上記の(3)と同様に塗布、乾燥して、ポリエステル不織布上における粘着層の厚さが60μmの比較用粘着絆創膏を製造した。この粘着絆創膏の剥離接着力は340gであった。
(4) Production of pressure-sensitive adhesive composition for pressure-sensitive adhesive bandages that does not contain an acrylic oligomer and a pressure-sensitive adhesive bandage for comparison with the composition applied
The acrylic polymer ethyl acetate solution produced in the above (2) was applied and dried in the same manner as in the above (3) to produce a comparative adhesive bandage with an adhesive layer thickness of 60 μm on the polyester nonwoven fabric. The adhesive strength of the adhesive bandage was 340 g.

(5)アクリル系オリゴマーの皮膚角質層の剥離損傷防止効果の測定
上記の(3)、(4)で製造した粘着伴創膏のそれぞれについて、実施例1の場合と同じ条件、方式で、付着した皮膚の角質細胞による発色面積比率を測定したところ、(4)の粘着絆創膏の場合には86%であったのに対し、(3)の粘着絆創膏の場合には11%で、アクリル系オリゴマーによって、皮膚角質の剥離損傷が大きく改善されることが判明した。
(5) Measurement of peeling damage prevention effect of acrylic oligomer on skin stratum corneum
For each of the adhesive bandages produced in the above (3) and (4), the ratio of the color development area by the corneocytes of the attached skin was measured under the same conditions and method as in Example 1, and (4) In the case of the adhesive adhesive bandage, it was 86%, whereas in the case of the adhesive adhesive bandage of (3), it was found that the acrylic oligomer significantly improved the exfoliation damage of the skin keratin.

以上説明したように、この発明に係る粘着絆創膏用粘着剤組成物の製造方法によれば、皮膚接着性ととともに剥離性(皮膚の剥離損傷防止性)が優れた粘着絆創膏を提供することができる。 As described above, according to the method for producing a pressure-sensitive adhesive composition for a pressure-sensitive adhesive bandage according to the present invention, it is possible to provide a pressure-sensitive adhesive bandage having excellent skin peelability and peelability (skin peeling damage prevention). .

Claims (7)

アクリルポリマーの溶液に、所定量のアクリル系オリゴマーの溶液を溶解させた後、所定量の反応性架橋剤を添加してなる粘着絆創膏用粘着剤組成物の製造方法であって、
(1)アルキル基の炭素数が4〜10のアクリル酸アルキルエステル又はメタアクリル酸アルキルエステルの一種以上を溶液重合して形成したアクリル系オリゴマーの溶液を製造する工程
(2)アルキル基の炭素数が4〜10のアクリル酸アルキルエステル又はメタアクリル酸アルキルエステルと、アクリル酸モノマー、メタクリル酸モノマー、2−ヒドロキシルエチルアクリレート、あるいは2−ヒドロキシエチルメタアクリレートから選択されるモノマーと、を含むモノマー混合液を溶液重合して形成したアクリルポリマーを含んでなるアクリルポリマーの溶液を製造する工程
(3)前記アクリル系オリゴマーの溶液およびアクリルポリマーの溶液を混合してなる溶液に対して、前記反応性架橋剤を、前記アクリルポリマーの0.01〜5重量%の範囲内の値となるように添加する工程と、
を含むことを特徴とする粘着絆創膏用粘着剤組成物の製造方法。
A method for producing a pressure-sensitive adhesive composition for an adhesive bandage comprising dissolving a predetermined amount of an acrylic oligomer solution in an acrylic polymer solution and then adding a predetermined amount of a reactive crosslinking agent,
(1) A step of producing a solution of an acrylic oligomer formed by solution polymerization of one or more of alkyl alkyl ester or alkyl methacrylate having 4 to 10 carbon atoms of alkyl group (2) carbon number of alkyl group Is a monomer mixed solution containing an alkyl ester of acrylic acid or methacrylic acid alkyl ester of 4 to 10 and a monomer selected from acrylic acid monomer, methacrylic acid monomer, 2-hydroxylethyl acrylate, or 2-hydroxyethyl methacrylate Step (3) for producing an acrylic polymer solution comprising an acrylic polymer formed by solution polymerization of the above-mentioned reactive crosslinking agent with respect to a solution obtained by mixing the acrylic oligomer solution and the acrylic polymer solution 0.01 ~ of the acrylic polymer A step of adding to a value within a range of% by weight,
The manufacturing method of the adhesive composition for adhesive adhesive plaster characterized by including.
前記アクリル系オリゴマーの溶液が、数平均分子量が2,000〜4,400であるアクリル系オリゴマーを含むことを特徴とする請求項1に記載の粘着絆創膏用粘着剤組成物の製造方法。   The method for producing a pressure-sensitive adhesive composition for adhesive bandages according to claim 1, wherein the acrylic oligomer solution comprises an acrylic oligomer having a number average molecular weight of 2,000 to 4,400. 前記反応性架橋剤が、多価エポキシ化合物または多価イソシアネート化合物であることを特徴とする請求項1または2に記載の粘着絆創膏用粘着剤組成物の製造方法。   The said reactive crosslinking agent is a polyhydric epoxy compound or a polyvalent isocyanate compound, The manufacturing method of the adhesive composition for adhesive bandages of Claim 1 or 2 characterized by the above-mentioned. アクリルポリマーの溶液に、所定量のアクリル系オリゴマーの溶液を溶解させた後、所定量の反応性架橋剤を添加して粘着絆創膏用粘着剤組成物とし、さらに、ベースシートの片面に、前記粘着絆創膏用粘着剤組成物からなる粘着層を設けてなる粘着絆創膏の製造方法であって、
(1)アルキル基の炭素数が4〜10のアクリル酸アルキルエステル又はメタアクリル酸アルキルエステルの一種以上を溶液重合して形成したアクリル系オリゴマーの溶液を製造する工程
(2)アルキル基の炭素数が4〜10のアクリル酸アルキルエステル又はメタアクリル酸アルキルエステルと、アクリル酸モノマー、メタクリル酸モノマー、2−ヒドロキシルエチルアクリレート、あるいは2−ヒドロキシエチルメタアクリレートから選択されるモノマーと、を含むモノマー混合液を溶液重合して形成したアクリルポリマーを含んでなるアクリルポリマーの溶液を製造する工程
(3)前記アクリル系オリゴマーの溶液およびアクリルポリマーの溶液を混合してなる溶液に対して、前記反応性架橋剤を、前記アクリルポリマーの0.01〜5重量%の範囲内の値となるように添加する工程と、
(4)ベースシートの片面に、前記粘着絆創膏用粘着剤組成物からなる粘着層を設けて、粘着絆創膏とする工程と、
を含むことを特徴とする粘着絆創膏の製造方法。
A predetermined amount of an acrylic oligomer solution is dissolved in an acrylic polymer solution, and then a predetermined amount of a reactive crosslinking agent is added to form an adhesive composition for an adhesive bandage. A method for producing an adhesive bandage comprising an adhesive layer comprising an adhesive composition for an adhesive bandage,
(1) A step of producing a solution of an acrylic oligomer formed by solution polymerization of one or more of alkyl alkyl ester or alkyl methacrylate having 4 to 10 carbon atoms of alkyl group (2) carbon number of alkyl group Is a monomer mixed solution containing an alkyl ester of acrylic acid or methacrylic acid alkyl ester of 4 to 10 and a monomer selected from acrylic acid monomer, methacrylic acid monomer, 2-hydroxylethyl acrylate, or 2-hydroxyethyl methacrylate Step (3) for producing an acrylic polymer solution comprising an acrylic polymer formed by solution polymerization of the above-mentioned reactive crosslinking agent with respect to a solution obtained by mixing the acrylic oligomer solution and the acrylic polymer solution 0.01 ~ of the acrylic polymer A step of adding to a value within a range of% by weight,
(4) providing a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for the pressure-sensitive adhesive bandage on one side of the base sheet to form a pressure-sensitive adhesive bandage;
The manufacturing method of the adhesive adhesive bandage characterized by including.
前記アクリル系オリゴマーの溶液が、数平均分子量が2,000〜4,400であるアクリル系オリゴマーを含むことを特徴とする請求項4に記載の粘着絆創膏の製造方法。   The method for producing an adhesive bandage according to claim 4, wherein the acrylic oligomer solution comprises an acrylic oligomer having a number average molecular weight of 2,000 to 4,400. 前記反応性架橋剤が、多価エポキシ化合物または多価イソシアネート化合物であることを特徴とする請求項4または5に記載の粘着絆創膏の製造方法。   The method for producing an adhesive bandage according to claim 4 or 5, wherein the reactive crosslinking agent is a polyvalent epoxy compound or a polyvalent isocyanate compound. 前記粘着絆創膏の剥離接着力が40〜400gfの範囲内の値であることを特徴とする請求項4〜6のいずれか一項に記載の粘着絆創膏の製造方法。   The method for producing a pressure-sensitive adhesive bandage according to any one of claims 4 to 6, wherein the adhesive strength of the adhesive bandage is within a range of 40 to 400 gf.
JP2011000019A 2011-01-04 2011-01-04 Method for producing pressure-sensitive adhesive composition for adhesive bandage Expired - Fee Related JP5337172B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2011000019A JP5337172B2 (en) 2011-01-04 2011-01-04 Method for producing pressure-sensitive adhesive composition for adhesive bandage

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2011000019A JP5337172B2 (en) 2011-01-04 2011-01-04 Method for producing pressure-sensitive adhesive composition for adhesive bandage

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
JP2001235912A Division JP4688364B2 (en) 2001-08-03 2001-08-03 Adhesive composition for adhesive bandages

Publications (2)

Publication Number Publication Date
JP2011080088A true JP2011080088A (en) 2011-04-21
JP5337172B2 JP5337172B2 (en) 2013-11-06

Family

ID=44074427

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2011000019A Expired - Fee Related JP5337172B2 (en) 2011-01-04 2011-01-04 Method for producing pressure-sensitive adhesive composition for adhesive bandage

Country Status (1)

Country Link
JP (1) JP5337172B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021176641A1 (en) * 2020-03-05 2021-09-10 株式会社寺岡製作所 Adhesive tape

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09249855A (en) * 1996-03-18 1997-09-22 Nitto Denko Corp Tacky agent and tape or sheet for medical application using the same
JPH09301853A (en) * 1996-05-14 1997-11-25 Nitto Denko Corp Plaster and plaster preparation
JP2003049142A (en) * 2001-08-03 2003-02-21 K & I Medical Research:Kk Adhesive composition for adhesive plaster

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09249855A (en) * 1996-03-18 1997-09-22 Nitto Denko Corp Tacky agent and tape or sheet for medical application using the same
JPH09301853A (en) * 1996-05-14 1997-11-25 Nitto Denko Corp Plaster and plaster preparation
JP2003049142A (en) * 2001-08-03 2003-02-21 K & I Medical Research:Kk Adhesive composition for adhesive plaster

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021176641A1 (en) * 2020-03-05 2021-09-10 株式会社寺岡製作所 Adhesive tape
JPWO2021176641A1 (en) * 2020-03-05 2021-09-10
CN115244151A (en) * 2020-03-05 2022-10-25 株式会社寺冈制作所 Adhesive tape
JP7395709B2 (en) 2020-03-05 2023-12-11 株式会社寺岡製作所 Adhesive tape
CN115244151B (en) * 2020-03-05 2023-12-12 株式会社寺冈制作所 Adhesive tape

Also Published As

Publication number Publication date
JP5337172B2 (en) 2013-11-06

Similar Documents

Publication Publication Date Title
US7431985B2 (en) Medical pressure-sensitive adhesive composition, process for producing the same, and medical tape
US6441092B1 (en) Wet-stick adhesives
TWI352727B (en)
JP6023407B2 (en) Manufacturing method of medical adhesive tape or sheet
KR20150108771A (en) Adhesive tape or sheet for skin
TW201217490A (en) Acrylic adhesive tape and method for manufacturing same
JP4108499B2 (en) Water-dispersed pressure-sensitive adhesive composition and pressure-sensitive adhesive product
JP5334374B2 (en) Self-wearing adhesive and self-wearing adhesive tape using the same
EP1194496B1 (en) Wet-stick adhesives
JP2003049128A (en) Method for producing acrylic adhesive sheet for optical member and acrylic adhesive sheet for optical member
JP4688364B2 (en) Adhesive composition for adhesive bandages
JP2007314584A (en) Adhesive tape
JP2007031672A (en) Pressure-sensitive adhesive tape having not been subjected to release treatment and manufacturing method thereof
JP5337172B2 (en) Method for producing pressure-sensitive adhesive composition for adhesive bandage
JP2009261727A (en) Medical self-adhesive composite and self-adhesive tape or sheet
JP2003049129A (en) Method for producing acrylic adhesive tape and acrylic adhesive tape
JP2002053461A (en) Medical adhesive composition, method for producing the same and adhesive tape or sheet using the composition
KR102068595B1 (en) Skin Temperature Sensitive Adhesive Composition Comprising Biomedical Polymer and Adhesive Sheet Thereof
JP2018131584A (en) Skin adhesive tape and method for producing the same
JPS5814471B2 (en) Removable adhesive composition
JP4679852B2 (en) Adhesive composition for medical and sanitary materials, and adhesive tape or sheet using the same
JP7387216B1 (en) Removable adhesive composition and adhesive sheet
JP4914590B2 (en) Copolymer emulsion for adhesive for human body sticking, adhesive composition for human body sticking, and patch for human body sticking.
JP5596365B2 (en) Exfoliating adhesive sheet
KR102207590B1 (en) Adhesive Composition for Anti-Irritation of Skin Comprising Biomedical Polymer and Adhesive Sheet Thereof

Legal Events

Date Code Title Description
A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20130625

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20130712

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20130730

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20130802

R150 Certificate of patent or registration of utility model

Ref document number: 5337172

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

LAPS Cancellation because of no payment of annual fees