JP6358874B2 - Acrylic adhesive composition and adhesive tape or sheet - Google Patents

Description

  The present invention relates to an acrylic pressure-sensitive adhesive composition, and a pressure-sensitive adhesive tape or sheet in which a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is formed on a base material, particularly a medical pressure-sensitive adhesive tape used by being attached to human skin. Or it relates to a sheet or the like.

  A medical adhesive tape or sheet, a sports adhesive tape or sheet, and an adhesive tape or sheet such as a beauty and health adhesive tape or sheet (hereinafter sometimes collectively referred to as “adhesive tape”) are generally tapes. It has a layer structure in which an adhesive layer is formed on one surface of a substrate, and is used by being attached to human skin for various purposes at medical sites and others. For example, medical adhesive tape is used to fix absorbent cotton, gauze, bandages, catheters, medical tubes, shipping agents, etc. (hereinafter sometimes referred to as “medical tubes”) to human skin. ing. In addition, medical adhesive tapes are used for protecting affected areas, covering surgical sites, suturing, fixing, and the like. The medical pressure-sensitive adhesive tape can also be used as a transdermal absorption patch for absorbing a drug from the skin by containing the drug in the pressure-sensitive adhesive layer. In addition, medical adhesive tapes are also used in emergency adhesive plasters and surgical adhesive tapes that have a specially treated pad. As an adhesive tape for sports, for example, a tape for tape can fix effects such as joints and muscles, and can exert effects such as pain reduction and promotion of treatment by supporting, reinforcing and compressing. .

  The adhesive tape or sheet is designed in consideration of as little skin irritation as possible because it is applied to human skin and is often applied over a long period of time. Specifically, the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer of the medical pressure-sensitive adhesive tape is a rubber-based, acrylic-based, or silicone-based pressure-sensitive adhesive that can fix a medical tube or the like to the skin if desired. There is a demand for a material that has (adhesive strength) and does not sensitize the skin or cause significant skin irritation.

  Further, medical adhesive tapes or sheets and sports adhesive tapes or sheets are required to be excellent in both moisture permeability and flexibility. If the adhesive tape has insufficient moisture permeability, sweat may build up between the skin surface and the adhesive layer due to sweating, causing skin irritation, and when the adhesive tape is peeled off the skin, In some cases, the adhesive force of the pressure-sensitive adhesive layer may decrease during application, and the pressure-sensitive adhesive tape may peel off or the medical tube or the like may not be fixed. In addition, if the adhesive tape for medical use or sports adhesive tape is not flexible enough, it is difficult to apply it to parts with complex shapes such as knee joints. May not be peeled off, may cause wrinkles, and may deteriorate the feeling of use.

  Further, since the adhesive tape or sheet for medical use or the adhesive tape or sheet for sports may be overlaid, self-rear adhesiveness (adhesiveness to the rear surface of the adhesive tape) may be required. In addition, the adhesive tape is also required to have water resistance such that even if it comes into contact with water, the adhesive strength, including the adhesive strength on its back surface, will be reduced, and the adhesive tape will not peel off or the medical tube cannot be fixed. It is done.

  That is, an adhesive tape or sheet having a high adhesive strength generally has high skin irritation. In particular, when a medical tube or the like is fixed, redness or blistering may occur at the applied site, which places a heavy burden on the patient. On the other hand, adhesive tapes with high moisture permeability are generally insufficient in adhesive strength, especially the fixation of medical tubes, etc., and the self-back adhesive strength, and may be peeled off when a strong force is applied. Water resistance may be insufficient.

  Known adhesives that form the adhesive layer of the adhesive tape include rubber adhesives, acrylic adhesives, silicone adhesives, ester adhesives, and the like. For example, rubber adhesives that are widely used contain hydrophobic rubber and tackifier (adhesive resin) as the main components, and vulcanizing agents such as sulfur and crosslinking agents are blended. Each pressure-sensitive adhesive has many points that require improvement, such as insufficient moisture permeability and high skin irritation. Therefore, acrylic pressure-sensitive adhesives are attracting attention because it is easy to adjust the characteristics to obtain a pressure-sensitive adhesive having excellent adhesion and moisture permeability and less skin irritation, and it is easy to obtain raw materials therefor.

  However, an acrylic pressure-sensitive adhesive having a high cohesive acrylic monomer ratio in order to exert high fixability has low moisture permeability, and skin irritation occurs when the pressure-sensitive adhesive has high cohesive strength. It is known that it is easy to come out. If the moisture permeability of the pressure-sensitive adhesive is low, the skin will be stuffy and the skin will be damaged when the pressure-sensitive adhesive tape is peeled off, resulting in increased skin irritation. In addition, when the cohesive strength of the adhesive is high, pain is caused when the adhesive tape is peeled off, and a lot of keratinocytes on the skin surface are peeled off, which easily causes redness and rash. Therefore, it has been desired to develop a pressure-sensitive adhesive composition that has both high fixability and low skin irritation.

  That is, the adhesive tape or sheet for medical use is not only excellent in adhesiveness to the skin and fixing force to the medical tube etc., but also for reducing pain when peeling from the skin surface and reducing the amount of exfoliation. In addition, there is a demand for adjustment so that the adhesiveness to the skin surface does not become excessively high, and high moisture permeability without causing stuffiness. As an attempt to achieve both high fixability and high moisture permeability, generally, a highly cohesive pressure-sensitive adhesive composition is applied by foam coating or pattern (wave type, stripe, lattice type, etc.) coating. There is a method of improving the apparent moisture permeability by working or perforating the tape (Patent Documents 1 to 3, etc.). However, these also have the following problems. In other words, foam coating is a product like a transparent film dressing because sweat may accumulate in unfoamed areas and cause steaming and rash. In some cases, the visibility is poor and the cleanliness may be impaired. In addition to the possibility of sweating and rashes in the area where the adhesive is applied, pattern coating is inevitably caused by areas where the adhesive composition is not applied, Adhesiveness and fixability may deteriorate. In addition to the fact that the tape-piercing process may still cause steaming and rash in areas without holes, the punching process may increase manufacturing costs. On the other hand, since a medical auxiliary pressure-sensitive adhesive tape is often used by being overlaid, it is required that the overlapping portion is not peeled off. For example, in order to fix a medical device such as a gauze, a blood transfusion tube, or an infusion tube to a person's arm, it is necessary to apply a medical auxiliary pressure-sensitive adhesive tape repeatedly and fix them securely. If the overlapped portion is easily peeled off, the fixing function of the medical adhesive tape is hindered. In response to these requirements, for example, various attempts have been made such as adjusting the composition of the acrylic pressure-sensitive adhesive composition (Patent Documents 4 to 7 and the like), but further improvements have been demanded.

  Therefore, as an acrylic pressure-sensitive adhesive composition that forms a pressure-sensitive adhesive layer provided on a pressure-sensitive adhesive tape or sheet, the adhesiveness to the skin, the self-back surface adhesiveness, and the fixability of medical tubes and the like are good, and moisture permeability is provided. Acrylic pressure-sensitive adhesive composition having good skin resistance, low skin irritation, and water resistance, i.e., an acrylic pressure-sensitive adhesive composition having a high level of balanced adhesive properties, particularly at a high level of fixation and moisture permeability. A compatible pressure-sensitive adhesive composition is required. There is also a need for an adhesive tape or sheet comprising an adhesive layer having a high level of balanced adhesive properties.

JP-A-9-506016 JP 2007-215578 A JP 2004-73483 A Japanese Patent Laid-Open No. 4-68074 JP-A-10-158621 JP 2007-338 A International Publication No. 2013/082222

  An object of the present invention is to provide an acrylic pressure-sensitive adhesive composition having good adhesiveness to the skin, self-adhesiveness and fixability of medical tubes, etc., good moisture permeability, low skin irritation, and water resistance. Another object is to provide a pressure-sensitive adhesive tape or sheet having a pressure-sensitive adhesive layer having a high-level balanced adhesive property as described above.

  As a result of earnest research on solving the above-mentioned problems, the present inventors have determined that the acrylic pressure-sensitive adhesive composition contains an acrylic copolymer formed from a predetermined monomer composition. We found that we could solve the problem and completed the invention.

That is, according to the present invention,
The following components (a) to (d);
(A) hydrophilic (meth) acrylic acid ester 20-60 mass%,
(B) Long-chain hydrophobic (meth) acrylic acid alkyl ester 1-60% by mass, (c) 0.01-15% by mass of an acrylic monomer having a functional group, and (d) (a), ( Other monomers copolymerizable with b) and (c) Acrylic copolymer formed from 5 to 40% by mass [however, the sum of (a), (b), (c) and (d) is 100 Mass%. An acrylic pressure-sensitive adhesive composition containing
(C) The acrylic pressure-sensitive adhesive composition is characterized in that the acrylic monomer having a functional group contains a (poly) lactone ring-opening adduct of (meth) acrylic acid. “(Meth) acrylic acid” is a general term for “acrylic acid” and “methacrylic acid” as well known to those skilled in the art, and is used in the same meaning in the present invention. Similarly, in the present invention, “(meth) acrylate” may be used as a general term for “acrylate” and “methacrylate”.

Moreover, according to this invention, the acrylic adhesive composition of the following (1)-(5) is provided as an aspect.
(1) (a) hydrophilic (meth) acrylic acid ester is (meth) acrylic acid alkoxyalkyl ester, (meth) acrylic acid polyalkylene glycol ester, (meth) acrylic acid hydroxyalkyl ester, and (meth) acrylic acid The acrylic pressure-sensitive adhesive composition as described above, which is at least one selected from the group consisting of hydroxyaralkyl esters.
(2) The acrylic pressure-sensitive adhesive composition as described above, wherein (b) the long-chain hydrophobic (meth) acrylic acid alkyl ester is a (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms.
(3) The acrylic pressure-sensitive adhesive composition as described above, wherein the acrylic monomer having a functional group (c) further contains (meth) acrylic acid.
(4) The acrylic pressure-sensitive adhesive composition according to (c), wherein the acrylic monomer having a functional group further contains β-carboxyethyl (meth) acrylate.
(5) (d) Other monomers copolymerizable with the above (a), (b) and (c) are alicyclic alcohols or aromatic alcohols (including heterocyclic aromatic alcohols). The said acrylic adhesive composition containing (meth) acrylic acid ester of this.

  Moreover, according to this invention, an adhesive tape or sheet provided with the adhesive layer and base material which consist of said acrylic adhesive composition is provided.

According to the invention, the following components (a) to (d):
(A) hydrophilic (meth) acrylic acid ester 20-60 mass%,
(B) 1-60 mass% of long-chain hydrophobic (meth) acrylic acid alkyl ester,
(C) Acrylic monomer having a functional group 0.01 to 15% by mass, and (d) Other monomer copolymerizable with the above (a), (b) and (c) 5 to 40% % Of an acrylic copolymer [however, the sum of (a), (b), (c) and (d) is 100% by mass. An acrylic pressure-sensitive adhesive composition containing
(C) The acrylic monomer having a functional group contains the (poly) lactone ring-opening adduct of (meth) acrylic acid, whereby the above-mentioned acrylic pressure-sensitive adhesive composition is used. Acrylic pressure-sensitive adhesive composition having good adhesiveness to the skin, self-back-side adhesiveness and fixability of medical tubes, etc., good moisture permeability, low skin irritation, and water resistance, that is, at a high level There is an effect that it is possible to provide an acrylic pressure-sensitive adhesive composition having balanced pressure-sensitive adhesive properties, in particular, a pressure-sensitive adhesive composition having both high fixability and moisture permeability.

  Moreover, according to the present invention, the pressure-sensitive adhesive layer having a high-level balanced adhesive property can be obtained by being a pressure-sensitive adhesive tape or sheet comprising a pressure-sensitive adhesive layer comprising the acrylic pressure-sensitive adhesive composition and a substrate. The effect that the adhesive tape or sheet | seat with which it is provided can be provided is show | played.

I. Acrylic pressure-sensitive adhesive composition The acrylic pressure-sensitive adhesive composition of the present invention comprises the following components (a) to (d);
(A) hydrophilic (meth) acrylic acid ester 20-60 mass%,
(B) 1-60 mass% of long-chain hydrophobic (meth) acrylic acid alkyl ester,
(C) Acrylic monomer having a functional group 0.01 to 15% by mass, and (d) Other monomer copolymerizable with the above (a), (b) and (c) 5 to 40% % Of an acrylic copolymer [however, the sum of (a), (b), (c) and (d) is 100% by mass. An acrylic pressure-sensitive adhesive composition containing
(C) The acrylic monomer having a functional group contains a (poly) lactone ring-opening adduct of (meth) acrylic acid.

1. Acrylic copolymer The acrylic copolymer contained in the acrylic pressure-sensitive adhesive composition of the present invention comprises the following components (a) to (d);
(A) hydrophilic (meth) acrylic acid ester 20-60 mass%,
(B) 1-60 mass% of long-chain hydrophobic (meth) acrylic acid alkyl ester,
(C) Acrylic monomer having a functional group 0.01 to 15% by mass, and (d) Other monomer copolymerizable with the above (a), (b) and (c) 5 to 40% % Of an acrylic copolymer [however, the sum of (a), (b), (c) and (d) is 100% by mass. ]. That is, as a monomer for forming an acrylic copolymer, (a) a hydrophilic (meth) acrylic acid ester, (b) a long-chain hydrophobic (meth) acrylic acid alkyl ester, and (c) an acrylic having a functional group And (d) an acrylic monomer containing a functional group (c) containing (d) another monomer copolymerizable with (a), (b) and (c) It contains a (poly) lactone ring-opening adduct of (meth) acrylic acid.

2. (A) Hydrophilic (meth) acrylic acid ester (a) Hydrophilic (meth) acrylic acid ester forming an acrylic copolymer in the present invention is a (meth) acrylic acid ester having a hydrophilic ester residue. Yes, it may be used alone or in combination of two or more. (A) Hydrophilic (meth) acrylic acid esters include (meth) acrylic acid alkoxyalkyl esters, (meth) acrylic acid polyalkylene glycol esters, (meth) acrylic acid hydroxyalkyl esters, and (meth) acrylic acid hydroxyaralkyls. It is preferably at least one selected from the group consisting of esters. Specifically, ethoxyethoxyethyl (meth) acrylate such as ethoxyethoxyethyl acrylate (EEEA), 2-hydroxyethyl (meth) acrylate such as 2-hydroxyethyl acrylate (2-HEA), acrylic acid 4 Examples include 4-hydroxybutyl (meth) acrylate such as -hydroxybutyl (4-HBA). As the (meth) acrylic acid polyalkylene glycol ester of the _formula: in _{^{CH 2 = CR 1 -CO- (O}} -CH 2 CHR 2) n -OR 3 ( wherein, ^{R 1} and ^{R 2:} each independently (Meth) acrylic acid methoxypolyethylene glycol or (meth) acrylic acid methoxypolypropylene glycol represented by a hydrogen atom or a methyl group, R ³ : an alkyl group having 1 to 20 carbon atoms, and n: an integer of 1 to 12. Can be mentioned. More preferable (a) hydrophilic (meth) acrylic acid ester is (meth) acrylic acid alkoxyalkyl ester having an alkoxy group having 1 to 4 carbon atoms such as EEEA, or (meth) acrylic acid methoxypolyethylene glycol.

  The proportion of the (a) hydrophilic (meth) acrylic acid ester forming the acrylic copolymer is in the range of 20 to 60% by mass, preferably 25 to 58% by mass, more preferably 30 to 56% by mass [ However, the sum of (a), (b), (c) and (d) is 100% by mass. ]. In the acrylic pressure-sensitive adhesive composition of the present invention, if the proportion of (a) hydrophilic (meth) acrylic acid ester is too small, the moisture permeability is lowered, and the skin may be stuffed at the time of pasting for a long time. Adhesive strength and fixing strength may be significantly reduced.

3. (B) Long-chain hydrophobic (meth) acrylic acid alkyl ester In the present invention, (b) long-chain hydrophobic (meth) acrylic acid alkyl ester that forms an acrylic copolymer is hydrophobic having a long-chain alkyl residue. (Meth) acrylic acid ester, which may be used alone or in combination of two or more. (B) The long-chain hydrophobic (meth) acrylic acid alkyl ester is a (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms (which may be linear or branched). Preferably, for example, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, (Meth) acrylic acid dodecyl etc. are mentioned. (B) The long-chain hydrophobic (meth) acrylic acid alkyl ester is more preferably isononyl acrylate, 2-ethylhexyl acrylate (2-EHA), or isooctyl acrylate.

  The proportion of (b) long-chain hydrophobic (meth) acrylic acid alkyl ester forming the acrylic copolymer is in the range of 1 to 60% by mass, preferably 2 to 55% by mass, more preferably 5 to 50% by mass. [However, the sum of (a), (b), (c) and (d) is 100% by mass. ]. The acrylic pressure-sensitive adhesive composition of the present invention (b) long-chain hydrophobic (meth) acrylic acid alkyl ester with a too small proportion is likely to be peeled off due to a decrease in skin adhesive strength, and may be particularly noticeable during water immersion. If the amount is too large, the moisture permeability may be reduced, and the skin may be stuffed when applied for a long time, or the fixation may be lowered.

4). (C) Acrylic monomer having a functional group In the present invention, the acrylic monomer having a functional group (c) that forms an acrylic copolymer is an acrylic copolymer contained in the acrylic pressure-sensitive adhesive composition. It is contained in order to improve the crosslinkability of the polymer, and one kind thereof may be used alone, or two or more kinds thereof may be contained. (C) As a functional group in an acrylic monomer having a functional group, a monofunctional acrylic monomer having a polar group such as a carboxyl group, an amide group, an amino group, or an epoxy group, or a polyfunctional acrylic monomer Monomers, that is, acrylic monomers having a plurality, for example, 2 to 4 functional groups, are conventionally known. Specifically, monofunctional acrylic monomers include acrylic monocarboxylic acids such as (meth) acrylic acid, and terminal carboxyalkyl esters of (meth) acrylic acid such as (meth) acrylic acid β-carboxyethyl. , Acrylic monomers having a carboxyl group such as (poly) lactone ring-opening adducts of (meth) acrylic acid such as (meth) acrylic acid ω-carboxypolycaprolactone; (meth) acrylamide; (meth) acrylic acid N , N-dimethylaminoethyl, acrylic monomers having an amino group such as N, N-diethylaminoethyl (meth) acrylate; and the like. As acrylic monomers having two or more functional groups, that is, polyfunctional acrylic monomers, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, ethylene Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol Examples include tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, and the like.

  In the acrylic copolymer contained in the acrylic pressure-sensitive adhesive composition of the present invention, (c) the acrylic monomer having a functional group contains a (poly) lactone ring-opening adduct of (meth) acrylic acid. It is possible to obtain an acrylic pressure-sensitive adhesive composition having good adhesion to the skin, good self-back adhesion, good moisture permeability, low skin irritation, and water resistance. it can. Examples of the (poly) lactone ring-opening adduct of (meth) acrylic acid include (meth) acrylic acid ω-carboxypolycaprolactone, (meth) acrylic acid ω-carboxycaprolactone, and preferably (meth) acrylic acid. It is omega-carboxypolycaprolactone.

  The proportion of the acrylic monomer having a functional group (c) that forms the acrylic copolymer is 0.01 to 15% by mass, preferably 0.5 to 12% by mass, more preferably 1 to 10% by mass. [However, the sum of (a), (b), (c) and (d) is 100% by mass. ]. In the acrylic pressure-sensitive adhesive composition of the present invention, when the proportion of the acrylic monomer having a functional group (c) is too small, the adhesive strength is reduced, or the pressure-sensitive adhesive is applied to the adherend such as skin or medical tube. In some cases, it may remain, and if it is too much, the moisture permeability may be lowered or the adhesion to the skin may be significantly deteriorated.

  The acrylic copolymer contained in the acrylic pressure-sensitive adhesive composition of the present invention is more preferably such that (c) an acrylic monomer having a functional group further contains (meth) acrylic acid. Can do. (C) The content ratio of (meth) acrylic acid in the acrylic monomer having a functional group is usually 0.05 to 9% by mass, preferably 0.1 to 7% by mass [however, (a) (b) The total of (c) and (d) is 100% by mass. ].

  Further, in the acrylic copolymer contained in the acrylic pressure-sensitive adhesive composition of the present invention, (c) an acrylic monomer having a functional group further contains β-carboxyethyl (meth) acrylate. Can be used more preferably. (C) The content ratio of β-carboxyethyl (meth) acrylate in the acrylic monomer having a functional group is usually 0.05 to 10% by mass, preferably 0.1 to 8% by mass [where (a ) (B) The sum of (c) and (d) is 100% by mass. ].

  In addition, the acrylic copolymer contained in the acrylic pressure-sensitive adhesive composition of the present invention may further comprise (c) an acrylic monomer having a functional group further comprising a polyfunctional acrylic monomer. What is contained can also be used. Examples of the polyfunctional acrylic monomer include 1,6-hexanediol di (meth) acrylate. (C) The content ratio of the polyfunctional acrylic monomer in the acrylic monomer having a functional group is usually 0.005 to 1% by mass, preferably 0.01 to 0.5% by mass. The sum of a), (b), (c) and (d) is 100% by mass. ].

5). (D) Other monomer copolymerizable with the above (a), (b) and (c) In the present invention, an acrylic copolymer is formed. (D) The above (a), (b) and (c Other monomers copolymerizable with (a), (b) and (c) are not particularly limited as long as they can be copolymerized with (a), (b) and (c), and are conventionally used to form an acrylic copolymer. Monomers may be used, one of which may be used alone, or two or more of them may be contained. Examples of the other monomer (d) include vinyl acetate, short-chain hydrophobic (meth) acrylic acid alkyl esters, and (meth) acrylic acid esters of cyclic alcohols. For example, the other monomer of (d) can contain a (meth) acrylic acid alkyl ester having a C 1-7 alkyl group as a short-chain hydrophobic (meth) acrylic acid alkyl ester, Specifically, as (meth) acrylic acid alkyl ester having an alkyl group having 1 to 7 carbon atoms (which may be linear, branched or cyclic), methyl (meth) acrylate, (meth) acrylic Ethyl acetate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acryl Examples include isobutyl acid, n-hexyl (meth) acrylate, and cyclohexyl (meth) acrylate. Further, as the other monomer of (d), (meth) acrylic of alicyclic alcohol or aromatic alcohol (including heterocyclic aromatic alcohol) which is (meth) acrylic acid ester of cyclic alcohol. From the viewpoint of the balance between moisture permeability and adhesive strength of the acrylic pressure-sensitive adhesive composition of the present invention, it is preferable to contain and use the acid ester. Specifically, cyclohexyl (meth) acrylate [first The (meth) acrylic acid alkyl ester having an alkyl group having 1 to 7 carbon atoms is also included. ], Benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like.

  (D) The proportion of the other monomer copolymerizable with (a), (b) and (c) is 5 to 40% by mass, preferably 7 to 37% by mass, which forms an acrylic copolymer. More preferably, it is the range of 10-35 mass% [However, the sum total of (a) (b) (c) and (d) shall be 100 mass%. ]. The acrylic pressure-sensitive adhesive composition of the present invention has a high level of balance when (d) the other monomer copolymerizable with (a), (b) and (c) is outside the above range. In some cases, a pressure-sensitive adhesive layer having a sticky adhesive property cannot be obtained. For example, when the acrylic copolymer does not contain (d) the other monomer copolymerizable with (a), (b) and (c), the medical tube cannot be fixed securely. There is a risk.

6). Formation of Acrylic Copolymer The acrylic copolymer contained in the acrylic pressure-sensitive adhesive composition of the present invention uses the monomers (a) to (d) described above at a predetermined ratio. It can be formed by copolymerizing by a usual method. Acrylic copolymers can generally be synthesized by radical polymerization, and examples of polymerization methods include solution polymerization, emulsion polymerization, bulk polymerization, etc. The solution polymerization method is preferable. Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide and lauroyl peroxide; azo initiators such as azobisisobutyronitrile; and the like. For example, a radical polymerization initiator is added at a ratio of about 0.01 to 2% by mass with respect to all monomers, and the mixture is stirred for several hours to several tens of hours at a temperature of about 40 to 90 ° C. in a nitrogen stream. Let In the solution polymerization method, ethyl acetate, acetone, toluene, a mixture thereof or the like is generally used as a solvent. Also, using water as a medium, one or more general-purpose surfactants and a monomer component are added and emulsified, heated, then added with an initiator and stirred to effect acrylic polymerization by emulsion polymerization. A system copolymer can also be formed.

  In order to increase the cohesiveness of the acrylic pressure-sensitive adhesive composition, various cross-linking agents can be used as desired. Examples of the crosslinking agent include substances having two or more reactive functional groups such as an epoxy group, an isocyanate group, a hydrazide group, and a carbodiimide group. As a commercially available crosslinking agent, TETRAD (registered trademark) as an epoxy crosslinking agent can be used. ) -X, Coronate (registered trademark) L and the like can be mentioned as the isocyanate crosslinking agent. When the acrylic pressure-sensitive adhesive composition has sufficient cohesiveness, the use of a cross-linking agent is unnecessary, but when a cross-linking agent is added to the acrylic copolymer, the use ratio thereof is the acrylic copolymer 100. Preferably it is 0.005-3 mass parts with respect to a mass part, More preferably, it is 0.01-2 mass parts, Most preferably, it is 0.02-1.5 mass parts. If the use ratio of the crosslinking agent is too small, the effect of improving the cohesiveness may be reduced or the adhesive may remain on the adherend, and if it is excessive, the cohesiveness is too large or peels off when adhering to the skin. It may be easier.

  The weight average molecular weight of the acrylic copolymer is preferably 200,000 to 1,000,000, more preferably 300,000 to 900,000. By setting the weight average molecular weight of the acrylic copolymer within the above range, it is possible to balance cohesion, adhesiveness, mixing workability with other components described later, affinity, and the like. The weight average molecular weight of the acrylic copolymer is a value obtained as a standard polystyrene equivalent value by gel permeation chromatography (GPC).

7). Acrylic adhesive composition (Preparation of acrylic adhesive composition)
In addition to the acrylic copolymer described above, the acrylic pressure-sensitive adhesive composition of the present invention may contain one or more other compounding agents depending on the purpose and for improving the adhesive properties and handleability. It can prepare by containing 2 or more types. In addition, another compounding agent can be mixed and contained when forming an acrylic copolymer or in the formed acrylic copolymer. The acrylic pressure-sensitive adhesive composition of the present invention can be prepared by a method known per se as a liquid material such as a heat-meltable solid, solution, suspension or emulsion.

[Other ingredients]
Examples of other compounding agents include, in addition to the crosslinking agent described above, tackifiers, fillers, softeners, antioxidants, ultraviolet absorbers, and drugs and drug absorption accelerators as required. As these other compounding agents, conventionally, other compounding agents contained in the acrylic pressure-sensitive adhesive composition may be appropriately selected and contained in a normal range depending on the type of the compounding agent. it can. Examples of tackifiers include rosin resins, terpene resins, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, coumarone indene resins, styrene resins, phenolic resins, xylene resins. And the like. Examples of the filler include calcium carbonate, zinc white (zinc oxide), silica, titanium oxide, and synthetic aluminum silicate. Further, as a drug that can be optionally contained, as a drug that can be absorbed transdermally, for example, an angina pectoris, corticosteroid agent, analgesic / anti-inflammatory agent, hypnotic analgesic agent, anti-inflammatory agent, antiallergic agent, antihistamine agent, Examples thereof include coronary vasodilators, antibacterial agents, moisturizers, vitamins, antitussives, anesthetics, antitumor agents, fragrances and the like, and contain an effective amount as necessary.

  The acrylic pressure-sensitive adhesive composition of the present invention further has hydrophilic additives for promoting moisture permeability, such as polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (PVP), as long as the adhesive properties and stability over time are not impaired. , Polycarboxymethylcellulose (CMC), polyethylene glycol (PEG), polypropylene glycol (PPG), diglycerin, polyglycerin, polyacrylate, polyethylene oxide (PEO), polyvinyl butyral, polyoxyethylene nonylphenyl ether, karaya gum and pectin Natural polysaccharides such as these may be contained, and one or more of these may be mixed as appropriate.

8). Applications of acrylic pressure-sensitive adhesive composition The acrylic pressure-sensitive adhesive composition of the present invention has a well-balanced pressure-sensitive adhesive property, so that it is a pressure-sensitive adhesive product comprising a pressure-sensitive adhesive layer made of an acrylic pressure-sensitive adhesive composition, usually a base It can be widely used as a pressure-sensitive adhesive tape or sheet laminated with a material. For example, it can be used for paper, plastic, metal pressure-sensitive adhesive tapes and the like. The acrylic pressure-sensitive adhesive composition of the present invention has good adhesiveness to the skin, self-adhesiveness, and fixability of medical tubes, etc., good moisture permeability, low skin irritation, and water resistance. Therefore, it is suitable as a medical adhesive tape or sheet, a sports adhesive tape or sheet, and a beauty and health adhesive tape or sheet.

II. The pressure-sensitive adhesive tape or sheet The pressure-sensitive adhesive tape or sheet of the present invention comprises a pressure-sensitive adhesive layer and a substrate made of the acrylic pressure-sensitive adhesive composition, and particularly a medical pressure-sensitive adhesive tape or sheet or a sports pressure-sensitive adhesive tape or sheet, Furthermore, it is suitable for an adhesive tape or sheet for beauty and health.

1. Adhesive layer The adhesive layer provided in the adhesive tape or sheet of the present invention is an adhesive layer comprising the acrylic adhesive composition described above. The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is usually in the range of 10 to 400 μm, preferably 20 to 300 μm, from the viewpoint of securing the fixation to the skin and the balance with the thickness of the base material described later. Moreover, the fabric weight of an adhesive layer is 10-400 g / m < ² > normally, Preferably it is the range of 20-300 g / m < ² >. In addition, although an adhesive layer has a uniform thickness normally, you may provide a difference in thickness partially. The thickness of the pressure-sensitive adhesive layer can be measured with a dial gauge.

2. The base material provided in the pressure-sensitive adhesive tape or sheet of the present invention is conventionally provided in a pressure-sensitive adhesive tape or sheet that is used by being attached to the skin, in particular, a medical pressure-sensitive adhesive tape or sheet or a sports pressure-sensitive adhesive tape or sheet. Although it is not particularly limited, it is usually preferable to have appropriate stretchability, flexibility, strength, and appropriate air permeability. For example, plastic films such as polyester film, polyethylene film, polypropylene film, polyvinyl chloride film, polycarbonate film, polyurethane film, polyvinyl alcohol film, ethylene vinyl acetate copolymer film and cellophane film; foam; cotton yarn, silk thread, polyester fiber , Nylon fibers, polyethylene fibers, polypropylene fibers and the like, that is, fiber substrates such as woven fabrics, knitted fabrics and nonwoven fabrics; papers; laminates thereof; and the like. From the viewpoint of followability to skin and stretchability, the base material is preferably an elastic base material, specifically, a fiber base material such as woven fabric, knitted fabric or non-woven fabric is preferably selected, and more specifically, Cotton cloth is desirable. The thickness of the substrate is usually 20 to 800 μm, preferably 50 to 700 μm, and the basis weight is usually 10 to 400 g / m ² , preferably 20 to 300 g / m ² . If desired, a primer or the like may be treated or processed for the purpose of improving the water-repellent treatment or the adhesiveness with the pressure-sensitive adhesive layer.

3. Release sheet The adhesive tape or sheet of the present invention can be used, for example, as a wound adhesive bandage in which an adhesive tape or sheet comprising an adhesive layer and a substrate is wound around a roll core material. From a viewpoint, it is good also as a thing provided with a peeling sheet other than an adhesive layer and a base material. When the pressure-sensitive adhesive tape or sheet of the present invention includes a release sheet, the release sheet is usually provided on the surface of the pressure-sensitive adhesive layer opposite to the base material. The release sheet protects the pressure-sensitive adhesive layer until the pressure-sensitive adhesive tape or sheet provided with the pressure-sensitive adhesive layer made of the acrylic pressure-sensitive adhesive composition is attached to the adherend, and on the upper surface thereof, It can also be used as an alternative to the release sheet used to apply the acrylic pressure-sensitive adhesive composition to form the pressure-sensitive adhesive layer. As the release sheet, those conventionally used in the field of patches can be used. For example, a high-quality paper subjected to silicone surface treatment (release treatment), a paper substrate such as glassine paper, a polyester film, or the like can be used. The thickness of the release sheet is usually 20 to 300 μm, preferably 30 to 200 μm, more preferably 50 to 100 μm. Also, the basis weight of the release sheet is not particularly limited, but is usually 50 to 150 g / ^{m 2,} preferably from 60 to 100 / ^{m 2.} Although one release sheet may be used, even if one release sheet is peeled off by providing one or two or more linear release sheet dividing portions that divide the outer shape at substantially the center of the release sheet. Alternatively, the other peeled body may remain, and a sticking operation can be performed without touching the pressure-sensitive adhesive layer to improve workability. For example, in the case where a pressure-sensitive adhesive tape or sheet comprising a pressure-sensitive adhesive layer made of an acrylic pressure-sensitive adhesive composition is made into a roll, it is particularly effective for making the release sheet easy to peel off and improving the handleability. In addition, two or more release sheets may be arranged so that one release sheet is covered with the other release sheet or folded so that the release sheet is easily peeled off from the pressure-sensitive adhesive layer. Moreover, the width | variety of a peeling sheet is 0.2 mm or more from the viewpoint of the flow-out prevention of adhesive composition, productivity, handleability, economical efficiency, the ease of a manufacturing method, etc. from the application area | region of an adhesive, especially 1 It is preferable to increase it by -5 mm.

4). Adhesive Tape or Sheet The form, shape, and size of the adhesive tape or sheet of the present invention are not particularly limited, and can be appropriately selected depending on the application, purpose of use, and the like. Since the pressure-sensitive adhesive tape or sheet of the present invention is a pressure-sensitive adhesive tape or sheet having a pressure-sensitive adhesive layer having balanced pressure-sensitive adhesive properties, as described above, a medical pressure-sensitive adhesive tape or sheet, or a sports pressure-sensitive adhesive tape or sheet. Is suitable. Therefore, depending on the application tape or the like (which may or may not be provided with a release sheet) in the form of an adhesive tape or sheet wound around a roll core material, the shape such as an oval, a circle, a square, a rectangle, etc. It can be set as a pressure-sensitive adhesive tape or sheet having a predetermined size. The thickness of the pressure-sensitive adhesive tape or sheet (referring to the total thickness of the pressure-sensitive adhesive layer and the substrate) is usually 30 to 1200 μm, preferably 70 to 1000 μm, more preferably 130 to 800 μm.

5). Manufacturing method of pressure-sensitive adhesive tape or sheet A method of manufacturing a pressure-sensitive adhesive tape or sheet comprising a pressure-sensitive adhesive layer and a base material comprising the acrylic pressure-sensitive adhesive composition of the present invention is a base material using the acrylic pressure-sensitive adhesive composition of the present invention. There is no particular limitation as long as the pressure-sensitive adhesive layer can be formed thereon. For example, a method in which an acrylic pressure-sensitive adhesive composition is applied to the upper surface of a base material to form a pressure-sensitive adhesive layer, and a release sheet is laminated on the upper surface of the pressure-sensitive adhesive layer as desired. Or a method of forming the pressure-sensitive adhesive layer on the substrate by melting and supplying the acrylic pressure-sensitive adhesive composition, or on the upper surface of the release sheet (may be a release sheet). A molten acrylic pressure-sensitive adhesive composition or a liquid (solution, suspension, emulsion, etc.) acrylic pressure-sensitive adhesive composition is applied to form a pressure-sensitive adhesive layer, and a substrate is laminated on the top surface of the pressure-sensitive adhesive layer There are methods. From the viewpoint of efficiently forming a pressure-sensitive adhesive layer having a stable thickness, an acrylic pressure-sensitive adhesive composition is continuously supplied to the upper surface of a release sheet (which may be a release sheet) that is continuously supplied and traveled. A pressure-sensitive adhesive tape or sheet comprising a base material, a pressure-sensitive adhesive layer, and a release sheet in this order by laminating the base material on the top surface of the pressure-sensitive adhesive layer Is preferably employed. The pressure-sensitive adhesive tape or sheet provided with the pressure-sensitive adhesive layer and the base material obtained by the above method is usually a pressure-sensitive adhesive tape or sheet that is slit into a predetermined width and wound around a roll core material (not provided with a release sheet). However, depending on the application, etc., the adhesive is formed from an acrylic pressure-sensitive adhesive composition by cutting into an oval, circular, square, rectangular or other shape and a predetermined size. You may manufacture the adhesive tape or sheet | seat provided with an agent layer and a base material.

III. Acrylic pressure-sensitive adhesive composition and properties of pressure-sensitive adhesive tape or sheet The acrylic pressure-sensitive adhesive composition of the present invention has good adhesiveness to the skin, self-rear-sided adhesiveness, and fixing properties such as medical tubes, and An acrylic pressure-sensitive adhesive composition having good moisture permeability, low skin irritation, and water resistance, that is, an acrylic pressure-sensitive adhesive composition having balanced pressure-sensitive adhesive properties. The pressure-sensitive adhesive tape or sheet of the present invention is a pressure-sensitive adhesive tape or sheet provided with a pressure-sensitive adhesive layer having high-level balanced adhesive properties. The excellent adhesive properties of the acrylic adhesive composition of the present invention and the adhesive tape or sheet can be confirmed by the properties shown below.

[Overlapping 180 ° adhesive strength]
The acrylic pressure-sensitive adhesive composition of the present invention is excellent in self-back adhesiveness. For example, the adhesive property of the overlapped portion when the adhesive tape is wrapped around a fingertip and attached, two medical tubes, etc. Adhesiveness of the overlapped portion when the adhesive tape is applied to the skin in an X-shape or when partially overlapped and fixed in parallel is excellent. The self-adhesiveness is confirmed by confirming that the 180 ° adhesive strength described below is in the range of usually 6 to 15 N / 25 mm, preferably 7 to 14 N / 25 mm, more preferably 8 to 13 N / 25 mm. Can do. If the adhesive force of the overlapped 180 ° adhesive is too small, the adhesive tape at the overlapped portion described above may be peeled off, and as a result, the medical tube or the like cannot be reliably fixed and may come off. If the adhesive strength is too large, when the adhesive tape or sheet is peeled off, the adhesive tape or sheet will be peeled off from the skin with the overlapping part remaining, causing pain or redness on the skin. Sometimes.

  The 180 ° adhesive strength of the acrylic adhesive composition is measured by the following method. That is, a test piece (hereinafter, also referred to as “test piece A”) cut out from an adhesive tape or sheet into a width of 25 mm and a length of about 90 mm and a test piece B larger than the test piece A are prepared. Under an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, the test piece B is previously attached to the bakelite plate, and then the test piece is provided on the back surface of the test piece B (the surface opposite to the adhesive layer of the substrate). A is pasted and pressure pasted by reciprocating a 2 kg rubber roll once at a speed of 600 mm / min. After 20 minutes, the test piece A is peeled off at a peeling speed of 300 mm / min, and the peeling force is measured to obtain a 180 ° adhesive strength (unit: N / 25 mm, average value of n = 5).

[Shearing force (vs bakelite plate)]
The acrylic pressure-sensitive adhesive composition of the present invention is excellent in adhesiveness when a force in the displacement direction is applied to the pressure-sensitive adhesive tape or sheet, and the shearing force (to the bakelite plate) is usually 35 N / 25 · 25 mm or more, Preferably it is 40 N / 25 * 25 mm or more, More preferably, it is 45 N / 25 * 25 mm or more. If the shearing force (with respect to the bakelite plate) is too small, the adhesive tape or sheet may be peeled off due to changes in body posture or exercise. In addition, although there is no upper limit in particular for a shear force (vs bakelite board), the adhesive composition which usually exceeds 100 N / 25 * 25 mm is not used.

  The shearing force (to the bakelite plate) of the acrylic pressure-sensitive adhesive composition is measured by the following method. That is, in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, a test piece cut out from an adhesive tape or sheet to a width of 25 mm × a length of about 90 mm is attached to one end of a bakelite plate so that the application area is 25 mm × 25 mm. A 2 kg rubber roll is reciprocated once at a speed of 600 mm / min for pressure sticking. After 20 minutes, the test piece is pulled in the shear direction (0 ° direction) at a tensile speed of 300 mm / min, and the shear force is measured. The maximum load at the time of measurement is defined as shear force (vs. bakelite plate) (unit: N / 25 · 25 mm, average value of n = 5).

[Overlap shear force (vs bakelite plate)]
The acrylic pressure-sensitive adhesive composition of the present invention has excellent self-back adhesiveness, and has excellent adhesiveness when a force in the shifting direction is applied to the overlapped portion of the pressure-sensitive adhesive tape or sheet. The shearing force (to the bakelite plate) is usually 30 N / 25 · 25 mm or more, preferably 35 N / 25 · 25 mm or more, more preferably 40 N / 25 · 25 mm or more. There is no particular upper limit on the lap-bonding shear force (to the bakelite plate), but it is usually less than 80 N / 25 · 25 mm. If the lap-bonding shear force (to the bakelite plate) is too small, the adhesive tape on the lap-bonded part will be peeled off when a force in the displacement direction is applied to the lap-bonded part of the adhesive tape or sheet, resulting in a medical tube, etc. May not be securely fixed and may come off.

  The lap-bonding shear force (vs. bakelite plate) of the acrylic pressure-sensitive adhesive composition is measured by the following method. That is, a test piece (hereinafter, also referred to as “test piece A”) cut out from an adhesive tape or sheet into a width of 25 mm and a length of about 90 mm and a test piece B larger than the test piece A are prepared. In an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, the test piece B is pasted on one end of the bakelite plate in advance, and then the test piece A is pasted on the back surface of the test piece B so that the pasting area is 25 mm × 25 mm. A 2 kg rubber roll is reciprocated once at a speed of 600 mm / min to apply pressure. After 20 minutes, the test piece A is pulled in the shearing direction (0 ° direction) at a tensile speed of 300 mm / min, and the shearing force is measured. The maximum load at the time of measurement is defined as the lap-bonding shear force (vs. bakelite plate) (unit: N / 25 · 25 mm, average value of n = 5).

[Skin adhesive strength]
The acrylic pressure-sensitive adhesive composition of the present invention has moderate adhesive strength to the skin, and the skin adhesive strength described below is usually 0.7 to 3 N / 15 mm, preferably 0.8 to 2. 0.5 N / 15 mm, more preferably in the range of 0.9 to 2 N / 15 mm. If the skin adhesive strength is too small, the adhesive tape or sheet may be peeled off due to body movement, arm bending or stretching, rubbing of clothing, etc., and as a result, medical tubes etc. cannot be fixed stably or fall off. There is a risk. If the skin adhesive strength is too high, skin irritation or sensitization may occur, and when the adhesive tape or sheet is peeled off, pain may be felt, the amount of exfoliated keratin may increase, or redness may remain on the skin. There is.

  The skin adhesive strength of the acrylic pressure-sensitive adhesive composition is measured by the following method. That is, a test piece cut out from an adhesive tape or sheet to a width of 15 mm and a length of about 90 mm in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% is affixed to the inner side of the human forearm (palm side) and applied with a palm for 10 seconds. Crimp and press. After 20 minutes, the test piece is peeled off in the 90 ° direction at a peeling rate of 100 mm / min, and the skin adhesive strength is measured (unit: N / 15 mm, average value of n = 5).

[Simple fixability test]
The fixing force of a medical tube or the like of the acrylic pressure-sensitive adhesive composition of the present invention can be confirmed by a simple fixability test measured by the following method. That is, a test piece cut out from an adhesive tape or sheet to a width of 12 mm and a length of about 50 mm is attached to a portion from the fingertip to the first joint of the index finger so that the application area is 12 mm wide and 25 mm long. After pressure bonding with a finger for 10 seconds, the film was pulled in the shear direction (0 ° direction) at a pulling speed of 300 mm / min, and the maximum load was measured to obtain the shear adhesive force by a simple fixability test (unit: N / 12 × 25 mm. average value of n = 5). The acrylic pressure-sensitive adhesive composition of the present invention has a shear adhesive strength of 10N / 12 × 25 mm or more, preferably 12N / 12 × 25 mm or more, more preferably 14N / 12 × 25 mm or more, as determined by a simple fixability test. Although there is no upper limit in particular for the shear adhesive force by a simple fixability test, it is usually 40 N / 12 × 25 mm or less, and in many cases 30 N / 12 × 25 mm or less from the viewpoint of not having an excessively large adhesive force.

[Moisture permeability]
The acrylic pressure-sensitive adhesive composition of the present invention has excellent moisture permeability, and the moisture permeability described below is usually 2,000 g / m ² · 24 hours or more, preferably 2,200 g / m ² · 24 hours. More preferably, it is 2,400 g / m ² · 24 hours or more. Due to the high moisture permeability of the acrylic pressure-sensitive adhesive composition, when sticking adhesive tape or sheet to the skin, it prevents steam and sweat from accumulating, prevents a decrease in adhesive strength due to sweating, and prevents rashes. Become. Moisture permeability, but there is no particular upper limit, from the viewpoint of water resistance, etc., usually 10,000g ^{/ m} 2 · 24 hours or less, or less often 5,000g ^{/ m} 2 · 24 hours.

The moisture permeability of the acrylic pressure-sensitive adhesive composition is measured according to JIS L1099 A-1 method (calcium chloride method), and is put in a moisture permeable cup in an atmosphere of a temperature of 40 ° C. and a relative humidity of 90%. The amount of calcium chloride is measured as 15 g (unit: g / m ² · 24 hours).

[Tube extraction force]
The acrylic pressure-sensitive adhesive composition of the present invention has a practicality that, for example, when a patient carelessly pulls out or hooks a medical tube or the like, the medical tube is fixed without being pulled out. It has a certain tube fixing force. As for the tube fixing force, the tube pulling force measured by the tube pulling test described below is usually 14 N / 25 × 70 mm × 1 or more, preferably 15 N / 25 × 70 mm × 1 or more, more preferably 16 N / 25. × 70 mm × 1 or more. If the tube pulling force is too small, the medical tube or the like may be easily pulled out if the patient carelessly pulls out or hooks the medical tube or the like. The tube pulling force does not have an upper limit, but is usually 50 N / 25 × 70 mm × 1 or less.

  The tube pulling force of the acrylic pressure-sensitive adhesive composition is measured by the following method. That is, in an atmosphere with a temperature of 23 ° C. and a relative humidity of 50%, one dialysis tube (from Nikkiso Co., Ltd., product number NV-Y030P, in which only a part with an inner diameter of 4 mm and an outer diameter of 6.5 mm was cut into a 180 mm length) The test piece cut out from the adhesive tape or sheet to a width of 25 mm and a length of 70 mm is placed in the center of the human forearm so that it is parallel to the length direction of Affix one tube and fix the tube and the forearm (compressing with a fingertip). After 20 minutes, the tube was pulled in the fingertip direction (perpendicular to the attached adhesive tape or sheet test piece) at a pulling speed of 300 mm / min, and the maximum load was defined as the tube pulling force (unit: N / 25 × 70 mm × 1 (average value of n = 3). Since there is a possibility that the subject may be painful during the test, the test may be interrupted with 30N / 25 × 70 mm × 1 as a target.

[Immersion shear force (vs bakelite plate)]
The acrylic pressure-sensitive adhesive composition of the present invention has a submerged shearing force (to bakelite plate) of usually 20 N / 25 · 25 mm or more, preferably 25 N / 25 · 25 mm or more, more preferably 30 N / 25 · 25 mm or more. Thus, even when the adhesive tape or sheet affixed to the skin comes into contact with water by hand washing or bathing, and a force is applied in the direction of displacement, the decrease in adhesion is at a level that is practically not problematic.

  The immersion shearing force (vs. bakelite plate) of the acrylic pressure-sensitive adhesive composition is measured by the following method. That is, in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, a test piece cut out from an adhesive tape or sheet to a width of 25 mm × a length of about 90 mm is attached to one end of a bakelite plate so that the application area is 25 mm × 25 mm. A 2 kg rubber roll is reciprocated once at a speed of 600 mm / min for pressure sticking. After 20 minutes, the bakelite plate with the test piece attached was immersed in water at a temperature of 20 ° C. for 20 minutes and allowed to stand. Then, the bakelite plate was taken out of the water and wiped off lightly, and immediately after that, tested at a tensile rate of 300 mm / min. Pull the piece in the shear direction (0 ° direction) and measure the shear force. The maximum load at the time of measurement is the immersion shear force (vs. bakelite plate) (unit: N / 25 · 25 mm, average value of n = 5).

[Submerged shearing force (vs. bakelite plate)]
The acrylic pressure-sensitive adhesive composition of the present invention has a submerged layered shear force (vs. bakelite plate) of usually 1.5 N / 25 · 25 mm or more, preferably 2N / 25 · 25 mm or more, more preferably 2.5 N / 25.・ Because the adhesive tape or sheet affixed to the skin is in contact with water by hand washing or bathing due to being 25 mm or more, even if a force is applied in the direction of displacement, the adhesiveness of the overlapped part is practically reduced. There is no problem.

  The submerged shear strength (to bakelite plate) of the acrylic pressure-sensitive adhesive composition is measured by the following method. That is, a test piece (hereinafter, also referred to as “test piece A”) cut out from an adhesive tape or sheet into a width of 25 mm and a length of about 90 mm and a test piece B larger than the test piece A are prepared. In an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, the test piece B is pasted on one end of the bakelite plate in advance, and then the test piece A is pasted on the back surface of the test piece B so that the pasting area is 25 mm × 25 mm. A 2 kg rubber roll is reciprocated once at a speed of 600 mm / min to apply pressure. After the lapse of 20 minutes, the bakelite plate on which the test pieces A and B were pasted was immersed in water at a temperature of 20 ° C. for 20 minutes and allowed to stand. Then, the bakelite plate was taken out of the water and lightly wiped off moisture. The test piece A is pulled in the shear direction (0 ° direction) in minutes, and the shear force is measured. The maximum load at the time of measurement is defined as the submerged piled shear force (vs. bakelite plate) (unit: N / 25 · 25 mm, average value of n = 5).

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these examples. The method for measuring the characteristics or physical properties of the acrylic pressure-sensitive adhesive composition of the present invention and the pressure-sensitive adhesive tape or sheet is based on the method already described.

[Example 1]
[Preparation of acrylic pressure-sensitive adhesive composition]
The monomers shown in the following (a) to (d) are dissolved and mixed in ethyl acetate under an inert gas atmosphere to obtain a monomer mixture, and then a copolymerization reaction is performed to produce an acrylic copolymer. did. Next, 0.03 parts by mass of a tetrafunctional epoxy crosslinker [TETRAD-X manufactured by Mitsubishi Gas Chemical Co., Ltd.] is used to crosslink 100 parts by mass of the acrylic copolymer, and the acrylic adhesive having the composition shown in Table 1 is used. An agent composition was prepared.
(A) Hydrophilic (meth) acrylic acid ester: 40% by mass of ethoxyethoxyethyl acrylate,
(B) Long-chain hydrophobic (meth) acrylic acid alkyl ester: isononyl acrylate 20.9% by mass,
(C) Acrylic monomer having a functional group:
Acrylic acid ω-carboxypolycaprolactone 4.5% by mass,
Acrylic acid 4.5% by mass,
1,6-hexanediol dimethacrylate 0.1% by mass, and (d) other monomer copolymerizable with the above (a), (b) and (c) [hereinafter referred to as “(d) other monomer Sometimes referred to as a “mer.” ]:
20% by mass of vinyl acetate,
Cyclohexyl acrylate 10% by mass
[The sum of (a), (b), (c) and (d) is 100% by mass. ]

[Manufacture of adhesive tape]
The obtained acrylic pressure-sensitive adhesive composition was applied to the upper surface of the film so as to have a thickness of 40 μm after drying while running a polyester film (release sheet) having a thickness of 75 μm subjected to silicone surface treatment, and then dried and adhered. An agent layer was formed. Next, a pressure-sensitive adhesive tape provided with a pressure-sensitive adhesive layer comprising a base material and an acrylic pressure-sensitive adhesive composition by laminating a cotton cloth (thickness: 550 μm, basis weight: 150 g / m ² ) as a base material on the upper surface of the pressure-sensitive adhesive layer. (Raw material) was obtained.

[Properties of acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive tape]
With respect to the obtained adhesive tape, various properties shown in Table 2 (hereinafter sometimes collectively referred to as “adhesive properties”) such as 180 ° adhesive strength, shear strength, skin adhesive strength, moisture permeability, and the like were measured. . The measurement results are shown in Table 2.

[Example 2]
An acrylic copolymer was formed from a mixture of monomers having the composition shown in Table 1 [0.2 parts by mass of a trifunctional epoxy crosslinking agent (manufactured by Kyoeisha Chemical Co., Ltd. with respect to 100 parts by mass of the acrylic copolymer). Cross-linked using Epolite 100MF). In the same manner as in Example 1, an acrylic pressure-sensitive adhesive composition was prepared to obtain a pressure-sensitive adhesive tape. The adhesive property was measured about the obtained adhesive tape. The measurement results are shown in Table 2.

[Example 3]
An acrylic copolymer was formed from a mixture of monomers having the composition shown in Table 1 [crosslinked with 0.02 parts by mass of a tetrafunctional epoxy crosslinking agent (TETRAD-X) to 100 parts by mass of the acrylic copolymer. I let you. In the same manner as in Example 1, an acrylic pressure-sensitive adhesive composition was prepared to obtain a pressure-sensitive adhesive tape. The adhesive property was measured about the obtained adhesive tape. The measurement results are shown in Table 2.

[Comparative Example 1]
An acrylic copolymer was formed from a mixture of monomers having the composition shown in Table 1 [1.0 mass part of an isocyanate-based cross-linking agent (manufactured by Nippon Polyurethane Industry Co., Ltd. Coronate (R) L) was used for crosslinking. In the same manner as in Example 1, an acrylic pressure-sensitive adhesive composition was prepared to obtain a pressure-sensitive adhesive tape. The adhesive property was measured about the obtained adhesive tape. The measurement results are shown in Table 2.

[Comparative Example 2]
An acrylic copolymer was formed from a mixture of monomers having the composition shown in Table 1 [0.2 parts by mass of an isocyanate cross-linking agent [Coronate (registered trademark) L] with respect to 100 parts by mass of the acrylic copolymer). Was used to crosslink. In the same manner as in Example 1, an acrylic pressure-sensitive adhesive composition was prepared to obtain a pressure-sensitive adhesive tape. The adhesive property was measured about the obtained adhesive tape. The measurement results are shown in Table 2. In the measurement of skin adhesive strength, the test piece was affixed to the inner side of the human forearm, and after 20 minutes, the tape end was peeled off by about 5% in the area ratio before measurement (hereinafter referred to as “5% peeling”). This is not preferable because it not only looks good, but also may lead to tape dropping. Moreover, in the measurement of the submerged superposed shear force (to the bakelite plate), when the adhesive tape was immersed in water, the superposed part was immediately peeled off in water.

[Comparative Example 3]
An acrylic copolymer was formed from a mixture of monomers having the composition shown in Table 1 [0.03 parts by mass of a tetrafunctional epoxy crosslinking agent (TETRAD-X) was used with respect to 100 parts by mass of the acrylic copolymer. And crosslinked. In the same manner as in Example 1, an acrylic pressure-sensitive adhesive composition was prepared to obtain a pressure-sensitive adhesive tape. The adhesive property was measured about the obtained adhesive tape. The measurement results are shown in Table 2.

[Comparative Example 4]
An acrylic copolymer was formed from a mixture of monomers having the composition shown in Table 1 [1.7 parts by mass of an isocyanate crosslinking agent [Coronate (registered trademark) L] with respect to 100 parts by mass of the acrylic copolymer). Was used to crosslink. In the same manner as in Example 1, an acrylic pressure-sensitive adhesive composition was prepared to obtain a pressure-sensitive adhesive tape. The adhesive property was measured about the obtained adhesive tape. The measurement results are shown in Table 2. In the measurement of the submerged shear force (vs. bakelite plate), the adhesive tape was immersed in water, and almost no force was applied and it was immediately peeled off from the bakelite plate.

[Comparative Example 5]
An acrylic copolymer was formed from a mixture of monomers having the composition shown in Table 1 [0.5 parts by mass of an isocyanate cross-linking agent [Coronate (registered trademark) L] with respect to 100 parts by mass of the acrylic copolymer). Was used to crosslink. In the same manner as in Example 1, an acrylic pressure-sensitive adhesive composition was prepared to obtain a pressure-sensitive adhesive tape. The adhesive property was measured about the obtained adhesive tape. The measurement results are shown in Table 2.

[Comparative Example 6]
An acrylic copolymer was formed from a mixture of monomers having the composition shown in Table 1 [1.5 parts by mass of an isocyanate crosslinking agent [Coronate (registered trademark) L] with respect to 100 parts by mass of the acrylic copolymer). Was used to crosslink. In the same manner as in Example 1, an acrylic pressure-sensitive adhesive composition was prepared to obtain a pressure-sensitive adhesive tape. The adhesive property was measured about the obtained adhesive tape. The measurement results are shown in Table 2.

[Comparative Examples 7 and 8]
An acrylic copolymer was formed from a mixture of monomers having the composition shown in Table 1. [0.06 parts by mass of tetrafunctional epoxy cross-linking agent (TETRAD-X) was used with respect to 100 parts by mass of the acrylic copolymer. And crosslinked. In the same manner as in Example 1, an acrylic pressure-sensitive adhesive composition was prepared to obtain a pressure-sensitive adhesive tape. The adhesive property was measured about the obtained adhesive tape. The measurement results are shown in Table 2.

From Table 2, the following components (a) to (d);
(A) hydrophilic (meth) acrylic acid ester 20-60 mass%,
(B) 1-60 mass% of long-chain hydrophobic (meth) acrylic acid alkyl ester,
(C) Acrylic monomer having a functional group 0.01 to 15% by mass, and (d) Other monomer copolymerizable with the above (a), (b) and (c) 5 to 40% % Of an acrylic copolymer [however, the sum of (a), (b), (c) and (d) is 100% by mass. An acrylic pressure-sensitive adhesive composition containing
(C) The acrylic pressure-sensitive adhesive composition according to Examples 1 to 3, wherein the acrylic monomer having a functional group contains a (poly) lactone ring-opening adduct of (meth) acrylic acid. In addition, the pressure-sensitive adhesive tape or sheet of Examples 1 to 3 provided with a pressure-sensitive adhesive layer and a base material made of an acrylic pressure-sensitive adhesive composition has an overlap strength of 180 ° adhesive strength of 6 to 15 N / 25 mm, shear force (relative to Bakelite plate) is 35 N / 25 · 25 mm or more, Overlap shear force (against bakelite plate) is 30 N / 25 · 25 mm or more, Skin adhesive strength is 0.7 to 3 N / 15 mm, and moisture permeability is 2,000 g / m ² · 24 hours or more, the tube pulling force is 14N / 25 × 70mm × 1 or more, submerged shear force (vs Bakelite plate) is 20 N / 25-25 mm or more, and flooded lap bonding shear ( Bakelite plate) is 1.5N / 25 · 25mm or more, so it has good adhesiveness to the skin, self-adhesiveness, and fixing of medical tubes, etc., and has good moisture permeability and low skin irritation. Further, it was found to be a pressure-sensitive adhesive tape or sheet comprising an acrylic pressure-sensitive adhesive composition having water resistance; and a pressure-sensitive adhesive layer having a high level of balanced pressure-sensitive adhesive properties. Therefore, according to the acrylic pressure-sensitive adhesive composition of the present invention; and the pressure-sensitive adhesive tape or sheet, a medical tube or the like can be reliably fixed, so that the possibility of causing a medical accident can be avoided.

  On the other hand, (c) the acrylic monomer having a functional group for forming an acrylic copolymer does not contain a (poly) lactone ring-opening adduct of (meth) acrylic acid. The adhesive tape or sheet of Comparative Examples 1 to 5 comprising the acrylic adhesive composition of Comparative Example 5 and the adhesive layer and substrate made of the acrylic adhesive composition are all overlaid 180 ° adhesive. The force was less than 6 N / 25 mm, and the lap-bonding shear force (against the bakelite plate) was less than 30 N / 25 · 25 m. In these comparative examples, the skin adhesive force and tube pull-out force are too small (Comparative Example 1), skin adhesive force, moisture permeability, tube pull-out force, submerged shear force (vs. bakelite plate) and submerged layered shear force (To bakelite plate) is too small (Comparative Example 2), Submerged shear force (to bakelite plate) or Submerged layered shear force (to bakelite plate) is too small (Comparative Example 3), Shear force (to bakelite plate) ), Tube pulling force, submerged shearing force (for bakelite plate) and submerged shearing force (for bakelite plate) are too small (Comparative Example 4 and Comparative Example 5). It cannot be said to be an acrylic pressure-sensitive adhesive composition having all the desired properties such as water resistance, low skin irritation due to high moisture permeability, and property such as medical properties, And it was found to not be a pressure-sensitive adhesive tape or sheet comprising a pressure-sensitive adhesive layer having a balanced adhesive properties of the balance at a high level.

  Moreover, the acrylic adhesive composition of the comparative example 6 which does not contain the other monomer which can be copolymerized with (d) said (a), (b) and (c) for forming an acrylic copolymer Comparative Examples 6 to 8 provided with an acrylic pressure-sensitive adhesive composition of Comparative Examples 7 and 8 having a content of (d) of less than 5% by mass, and a pressure-sensitive adhesive layer made of the acrylic pressure-sensitive adhesive composition. The adhesive tape or sheet of No. 8 has an overlap strength of 180 ° less than 6N / 25mm, an overlap shear force (to bakelite plate) of less than 30N / 25 · 25mm, and a tube pulling force of 14N / 25 × 70mm × 1. It was less than the book. In these comparative examples, the shear force (to the bakelite plate) is too small (Comparative Examples 6 and 7), the skin adhesive force is too small (Comparative Examples 7 and 8), and the immersion shear force (to the bakelite plate). And the soaking and laminating shear force (to the bakelite plate) is too small (Comparative Examples 6 and 7). Adhesion to the skin, self-adhesiveness and fixation of medical tubes, moisture permeability, low skin irritation Furthermore, it cannot be said that it is an acrylic pressure-sensitive adhesive composition having all desired properties such as water resistance, and it cannot be said to be a pressure-sensitive adhesive tape or sheet having a pressure-sensitive adhesive layer having a high level of balanced pressure-sensitive adhesive properties. I understood.

[Examples 4 to 6]
[(D) Study of other monomers]
(D) The other monomer copolymerizable with said (a), (b) and (c) which is a monomer component contained in the acrylic adhesive composition of this invention was further examined. That is, (d) the other monomer copolymerizable with the (a), (b) and (c) is an alicyclic alcohol or an aromatic alcohol (including a heterocyclic aromatic alcohol). An acrylic copolymer was formed from a mixture of monomers having the composition shown in Table 3 and containing (meth) acrylic acid ester [1.3 parts by mass of isocyanate based on 100 parts by mass of acrylic copolymer Crosslinking was performed using a crosslinker [Coronate® L]. In the same manner as in Example 1, an acrylic pressure-sensitive adhesive composition was prepared to obtain a pressure-sensitive adhesive tape. About the obtained adhesive tape, the measurement of skin adhesive force and the simple fixation test were done. The results are shown in Table 4.

  From Table 4, (d) the other monomer copolymerizable with (a), (b) and (c), which is a monomer component contained in the acrylic pressure-sensitive adhesive composition, is an alicyclic group. Acrylic adhesives of Examples 4 to 6 containing (meth) acrylic acid esters of alcohol (Example 4), aromatic alcohol (Example 5) or heterocyclic aromatic alcohol (Example 6), respectively. The adhesive tapes or sheets of Examples 4 to 6 including the adhesive composition and the adhesive layer and the base material made of the acrylic adhesive composition are more preferably such that the skin adhesive strength is 0.9 to 2 N / 15 mm. Since the shear adhesive strength by the simple fixing test is a preferable range of 12 N / 12 × 25 mm or more, it has excellent characteristics as an adhesive, and as an adhesive tape or sheet. There could be confirmed.

The present invention provides the following components (a) to (d):
(A) hydrophilic (meth) acrylic acid ester 20-60 mass%,
(B) 1-60 mass% of long-chain hydrophobic (meth) acrylic acid alkyl ester,
(C) Acrylic monomer having a functional group 0.01 to 15% by mass, and (d) Other monomer copolymerizable with the above (a), (b) and (c) 5 to 40% % Of an acrylic copolymer [however, the sum of (a), (b), (c) and (d) is 100% by mass. An acrylic pressure-sensitive adhesive composition containing
(C) The acrylic monomer having a functional group contains the (poly) lactone ring-opening adduct of (meth) acrylic acid, whereby the above-mentioned acrylic pressure-sensitive adhesive composition is used. Acrylic pressure-sensitive adhesive composition having good adhesiveness to the skin, self-back-side adhesiveness and fixability of medical tubes, etc., good moisture permeability, low skin irritation, and water resistance, that is, at a high level Since an acrylic pressure-sensitive adhesive composition having balanced pressure-sensitive adhesive properties, in particular, a pressure-sensitive adhesive composition having both high fixability and moisture permeability, can be provided, the industrial applicability is high.

  Moreover, this invention is an adhesive provided with the adhesive layer which has the adhesive characteristic which was balanced at a high level by being an adhesive tape or a sheet | seat provided with the adhesive layer which consists of said acrylic adhesive composition, and a base material. Since a tape or a sheet can be provided, the industrial applicability is high.

Claims (3)

The following components (a) to (d);
(A) (meth) acrylic acid polyethylene glycol ester 20-60% by mass,
(B) 1 to 60 mass% of (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms,
(C) Monocarboxylic acid of (meth) acrylic acid, terminal carboxyalkyl ester of (meth) acrylic acid, (poly) lactone ring-opening adduct of (meth) acrylic acid, or 1,6-hexanediol di (meth) One or two or more acrylates, 0.01 to 15% by mass, and (d) other monomers copolymerizable with (a), (b) and (c) 5 to 40% by mass
Acrylic copolymer formed from [wherein the total of (a), (b), (c) and (d) is 100% by mass. An acrylic pressure-sensitive adhesive composition containing
Component (c) contains 3.5% by mass or more of a (poly) lactone ring-opening adduct of (meth) acrylic acid based on the entire acrylic pressure-sensitive adhesive composition , and
The acrylic pressure-sensitive adhesive composition as described above, wherein the component (d) contains a (meth) acrylic acid ester of an alicyclic alcohol or an aromatic alcohol (including a heterocyclic aromatic alcohol). The acrylic pressure-sensitive adhesive composition according to claim 1, wherein the component (c) contains (meth) acrylic acid β-carboxyethyl as a terminal carboxyalkyl ester of (meth) acrylic acid. An adhesive tape or sheet provided with the adhesive layer and base material which consist of an acrylic adhesive composition of Claim 1 or Claim 2 .