JP2002065841A - Skin-stickable adhesive composition, skin-stickable adhesive tape or sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a skin-stickable adhesive composition, and a skin-stickable adhesive tape or sheet which can be appropriately used for an emergency plaster, a large plaster with pad, and a dressing material, and optimally used for external applications such as medical and sanitary fields, sports and cosmetic and health-care fields, and is, in particular, water-proof adhesivity. SOLUTION: This adhesive composition contains 20-120 pts.wt. liquid or paste-like carboxylate at room temperature mixed with 100 pts.wt. acrylic copolymer obtained from a monomer mixture containing, by weight, 40-80% (meta)acrylic alkyl ester, 10-60% ethylenic unsaturated monomer containing alkoxy group and 1-10% ethylenic unsaturated monomer containing carboxylic group. Carboxylate preferably includes glycerin ester of saturated fatty acid, and most preferably, triglyceride of saturated fatty acid such as caprylic acid, capric acid or 2-ethyl hexanoic acid. The skin-stickable tape and sheet are manufactured by forming the adhesive composition on at least one side of a base film in a layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive adhesive composition for skin application used for external applications in the field of medical hygiene and a pressure-sensitive adhesive tape or sheet for skin application using the same. It is suitably used for a bond, a large bandage with a pad, a dressing material and the like.

[0002]

2. Description of the Related Art A pressure-sensitive adhesive tape or sheet to be adhered to a skin surface for use is usually one having a pressure-sensitive adhesive layer provided on one side of a substrate film, and is applied via the pressure-sensitive adhesive layer. It is used by sticking it to the skin surface.

The pressure-sensitive adhesive used for such pressure-sensitive adhesive tapes and sheets for application to the skin is generally roughly classified into a rubber-based pressure-sensitive adhesive and an acrylic pressure-sensitive adhesive.

A rubber-based pressure-sensitive adhesive is a pressure-sensitive adhesive composition obtained by compounding a rubber component such as natural rubber, isoprene rubber, styrene / isoprene / styrene-based rubber, with a tackifier or a softener, etc. It has excellent adhesive strength. However, since this adhesive is usually highly hydrophobic and has low moisture permeability, the skin surface becomes stuffy due to sweating from the skin surface during application, causing skin irritation, and a large amount of sweating during summer or bathing. At times, skin adhesion may drop sharply.

[0005] On the other hand, acrylic pressure-sensitive adhesives have alkylene (meth) acrylate as a main component monomer and are copolymerized with various copolymerizable monomers to balance characteristics according to the purpose. It is possible to prepare an adhesive having good properties, and it is relatively easy to control the adhesive properties. However, the acrylic pressure-sensitive adhesive is relatively easy to impart hydrophilicity or high moisture permeability to the pressure-sensitive adhesive composition, but increases the adhesiveness to the skin surface such as a rubber-based pressure-sensitive adhesive. It is difficult to make the adhesive, and the fact is that it has not yet solved the problem of a decrease in skin adhesion to sweat during summer or bathing as in the case of the rubber-based pressure-sensitive adhesive.

[0006] In other words, currently available adhesives for skin application and adhesive tapes or sheets using the same are:
Although it has excellent adhesion to relatively dry skin, it is not inevitable that the adhesion will decrease significantly due to sweat from the skin, and it can maintain satisfactory skin adhesion to sweat. The fact is that it has not been obtained.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and is intended for practical use even in an environment where there is a lot of sweat from the skin surface, such as during summer, sports, and bathing. As a result of repeated studies to obtain a pressure-sensitive adhesive tape or sheet for skin application that can maintain sufficient skin adhesiveness and that hardly peels or slips even when applied to the skin for several days, It has been found that the above-mentioned problems can be solved by using a pressure-sensitive adhesive composition containing a specific carboxylic acid ester and adjusting the amount of insoluble components to a specific range in the acrylic copolymer of the present invention. Was completed.

[0008]

That is, the present invention relates to an alkyl (meth) acrylate of 40 to 80% by weight, an alkoxy group-containing ethylenically unsaturated monomer of 10 to 60% by weight, and a carboxyl group-containing ethylenically unsaturated monomer. Saturated monomer 1-1
A pressure-sensitive adhesive composition containing 100 parts by weight of an acrylic copolymer obtained from a monomer mixture containing 0% by weight and 20 to 120 parts by weight of a carboxylic acid ester in a liquid or paste form at room temperature. It is intended to provide a pressure-sensitive adhesive composition for application to the skin, wherein 30 to 80% by weight of the polymer is insoluble.

Further, the present invention is obtained by directly or indirectly forming a pressure-sensitive adhesive composition for skin application according to any one of claims 1 to 4 on at least one surface of a substrate film in a layered form. An object of the present invention is to provide a pressure-sensitive adhesive tape or sheet for application to the skin.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The monomer mixture used in the pressure-sensitive adhesive composition for application to skin of the present invention comprises an alkyl (meth) acrylate, an ethylenically unsaturated monomer containing an alkoxy group, and an ethylene monomer containing a carboxyl group. And an unsaturated monomer as an essential component.

The above-mentioned alkyl (meth) acrylate is a component for imparting tackiness and skin adhesion to the pressure-sensitive adhesive composition and the pressure-sensitive adhesive layer, and particularly has an alkyl group having 2 or more carbon atoms, particularly 6 to 15 carbon atoms. It is effective to use a long-chain alkyl ester. Further, the alkyl (meth) acrylate has an advantage that it has relatively little irritation to the skin and the adhesiveness is hardly reduced even after long-term use.

Specific examples of such alkyl (meth) acrylates include ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, octyl ester, nonyl ester, decyl ester of acrylic acid or methacrylic acid. Ester, dodecyl ester and the like can be used alone or in combination of two or more. Needless to say, these alkyl ester chains may be linear or branched.

The above-mentioned alkyl (meth) acrylate is formed into a pressure-sensitive adhesive composition by copolymerizing with various ethylenically unsaturated monomers described below. In the present invention, the pressure-sensitive adhesive composition is 40 to 80% by weight, preferably 50 to 80% by weight. It is desirable to copolymerize in the range of 70% by weight. If the copolymerization amount of the (meth) acrylic acid alkyl ester is less than 40% by weight, the obtained acrylic copolymer does not have sufficient skin adhesion, and if the amount exceeds 80% by weight. At the copolymerization amount, a decrease in cohesive strength is observed, and an adhesive residue phenomenon may occur at the time of peeling and removal from the skin surface.

On the other hand, the alkoxy group-containing ethylenically unsaturated monomer copolymerized with the alkyl (meth) acrylate ester imparts hydrophilicity to the resulting pressure-sensitive adhesive composition or pressure-sensitive adhesive layer, thereby providing water vapor permeability and moisture absorption. It is a component that imparts properties and is an important component for exhibiting the effects of the present invention. Therefore, 10 to 60 in the acrylic copolymer finally obtained.
It is desirable to copolymerize in an amount of from 20 to 50% by weight, preferably from 20 to 50% by weight. When the copolymerization amount is less than 10% by weight, it is difficult to obtain a sufficient effect for imparting hydrophilicity for maintaining the effects of the present invention and maintaining skin adhesion during sweating, and With a copolymerization amount exceeding 60% by weight,
The adhesiveness to the skin as a pressure-sensitive adhesive decreases, and it becomes difficult to maintain a practical adhesive strength.

Examples of such an ethylenically unsaturated monomer include alkoxy having 1 to 4 carbon atoms such as methoxypolyethylene glycol acrylate, ethoxydiethylene glycol acrylate, butoxydiethylene glycol acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, and butoxyethyl acrylate. It is preferable to use alkoxyalkyl acrylates having groups.

In the present invention, a carboxyl group-containing ethylenically unsaturated monomer is copolymerized with the alkoxy group-containing ethylenically unsaturated monomer. That is, by copolymerizing the carboxyl group-containing ethylenically unsaturated monomer, it is possible to secure a reaction point at the time of crosslinking treatment, and to improve the cohesive force of the obtained acrylic copolymer. It is an important monomer when preparing a product. However, when this monomer is copolymerized in a large amount, it can be expected to improve the cohesion, but the skin irritation gradually increases. Therefore, in the present invention, when a carboxyl group-containing ethylenically unsaturated monomer is copolymerized, it is 1 to 10% by weight, preferably 3 to 10% by weight.
It is desirable to set the copolymerization ratio to about 8% by weight.

Representative examples of such monomers include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, and the like. Among these, acrylic acid and methacrylic acid are preferred as monomers in view of copolymerizability and handleability.

The copolymer contained in the pressure-sensitive adhesive composition for application to the skin of the present invention may be a copolymer obtained by using a mixture of the above monomers as an essential component. Styrene, vinyl acetate, N-vinyl-2
-Pyrrolidone, 2-hydroxyethyl acrylate, 2
A monomer such as -hydroxypropyl acrylate may be appropriately copolymerized as necessary.

The acrylic copolymer in the pressure-sensitive adhesive composition for application to the skin of the present invention preferably has a glass transition temperature of 250 ° K or lower. That is, the glass transition temperature is 2
By setting the temperature to 50 ° K or lower, the skin adhesive force important as a pressure-sensitive adhesive tape or sheet for skin application can be sufficiently exhibited.

It is desirable that the weight average molecular weight of the acrylic copolymer is adjusted to 1,000,000 or less, preferably about 500,000 to 900,000. In other words, the acrylic copolymer of the present invention is subjected to a cross-linking treatment or the like in order to exhibit sufficient cohesiveness even when plasticized by a compatible carboxylic acid ester, so that the insoluble content is in the range of 30 to 80% by weight. Although it is necessary to adjust, if the weight average molecular weight of the acrylic copolymer is too large, when the pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive composition, the internal cohesive force of the pressure-sensitive adhesive layer is excessively increased, and the skin adhesive strength is increased. You may run into shortages. Therefore, in the present invention, it is desirable to adjust the weight average molecular weight of the acrylic copolymer used to 1,000,000 or less.

The polymerization method for obtaining the acrylic copolymer is not particularly limited, such as solution polymerization, emulsion polymerization, and suspension polymerization, and may be any of ordinary polymerization methods such as peroxide compounds and azo compounds. Copolymerization can be performed by radical polymerization using a radical polymerization initiator.

The adhesive composition for adhering to skin of the present invention is used in an amount of 20 to 12 parts by weight based on 100 parts by weight of the acrylic copolymer.
It contains 0 parts by weight of a carboxylic acid ester.
The carboxylic acid ester used in the present invention exhibits a liquid or paste-like property at room temperature. When the pressure-sensitive adhesive composition is used, the adhesiveness is reduced to an unacceptable range. Shaped shapes cannot be used.

In the present invention, when the carboxylic acid ester is formed into an adhesive layer by making it compatible with the acrylic copolymer, the elastic modulus in the micro-deformation region can be reduced, and the skin surface to be adhered can be reduced. By improving the adhesiveness (wetting property) of the surface of the pressure-sensitive adhesive layer to the irregularities of the surface, good skin adhesion can be exhibited, and further excellent sweat resistance can be exhibited. The reason for this is not clear, but at the time of perspiration, the water at the interface between the skin surface and the pressure-sensitive adhesive layer is absorbed into the pressure-sensitive adhesive layer by a carboxylic acid ester acting as a surfactant, and furthermore, the water absorbed at the interface causes adhesion. It is estimated that the moisture permeability of the agent layer is also improved, and as a result, skin adhesion can be maintained even during sweating.

The carboxylic acid ester that can be used is one that has an affinity and compatibility with the acrylic copolymer and also has an affinity for water during sweating. , Ethyl myristate, isopropyl myristate, isopropyl palmitate, butyl stearate, isopropyl isostearate, hexyl laurate, cetyl lactate, myristyl lactate, diethyl phthalate, octyldodecyl myristate, octyldodecyl oleate, hexyldecyl dimethyloctanoate ,
Carboxylic esters using monohydric alcohols such as cetyl 2-ethylhexanoate, isocetyl 2-ethylhexanoate, stearyl 2-ethylhexanoate, dioctyl succinate, propylene glycol dicaprylate, propylene glycol dicaprate, and propylene diisostearate Divalents such as glycol, glyceryl monocaprylate, glyceryl tricaprylate, glyceryl tri-2-ethylhexanoate, glyceryl tricaprate, glyceryl trilaurate, glyceryl triisostearate, glyceryl trioleate, and trimethylolpropane tri-2-ethylhexanoate Carboxylic esters using the above polyhydric alcohols can be used.

Among the above carboxylic esters, a saturated fatty acid having no unsaturated double bond is used from the viewpoint of preventing oxidative deterioration, and a glycerin ester is used from the viewpoint of low skin irritation and economy. It is desirable. Therefore, as the saturated fatty acids, caprylic acid, capric acid,
-It is preferable to use an esterified product of a saturated fatty acid such as ethylhexanoic acid and a monohydric or polyhydric alcohol, and most preferably to use triglyceryl caprylate, triglyceryl caprate, or triglyceryl 2-ethylhexanoate. Is desirable.

In the case where a carboxylic acid ester having an unsaturated bond is used, the carboxylic acid ester may be oxidized and degraded by oxygen in the atmosphere to cause a change in physical properties, thereby failing to exhibit desired characteristics. In such a case, it is preferable that an antioxidant known per se is incorporated into the pressure-sensitive adhesive layer.

One or more of the above-mentioned carboxylic acid esters are blended in the acrylic copolymer. The amount of the carboxylic acid ester is 20 to 120 parts by weight based on 100 parts by weight of the acrylic polymer. , Preferably 30 to
It is adjusted to be in the range of 100 parts by weight. If the amount of the carboxylic acid ester is less than 20 parts by weight, the skin adhesive property is greatly reduced when the skin surface to be stuck is sweated, and it is difficult to obtain the effects intended by the present invention.
If the amount is more than 0 parts by weight, the carboxylic acid ester blooms from the pressure-sensitive adhesive layer, and the skin adhesion may be reduced even when sweating is not preferred, which is not preferable.

The pressure-sensitive adhesive composition of the present invention has at least the above components. In the present invention, 30 to 80% by weight, preferably 35 to 70% by weight of the acrylic copolymer is insoluble. It is characterized by. In the present invention, “insolubilized” means not dissolved in an organic solvent, but specifically means not dissolved in toluene. The insolubilization rate was determined by immersing the dried sample in toluene at room temperature for 7 days, filtering the insoluble matter through a polytetrafluoroethylene membrane (NTF membrane, manufactured by Nitto Denko Corporation) having an average pore diameter of 0.2 μm, and drying. Is a value calculated by the ratio to the dry sample weight before immersion.

In the present invention, when the insolubilization ratio is less than 30% by weight, the internal cohesive force of the formed pressure-sensitive adhesive layer becomes insufficient, causing a shift during application to the skin surface,
When peeled from the skin surface, the adhesive remains on the skin surface,
There is a possibility that a so-called adhesive residue phenomenon may occur. On the other hand, when the insolubilization rate exceeds 80% by weight, skin adhesion is extremely reduced, and there is a possibility that edge peeling or peeling-off phenomenon may occur during application.

In the present invention, as a method of insolubilizing the acrylic copolymer, a method of generally performing a crosslinking treatment can be adopted. The cross-linking treatment includes chemical cross-linking using a cross-linking agent such as an organic peroxide, an isocyanate compound, an organic metal salt, a metal alcoholate, a metal chelate, an epoxy compound, or a primary amino compound, or physical irradiation with ionizing radiation. Of these, from the viewpoints of easy adjustment of the degree of crosslinking, ease of compounding, and pot life, chemical crosslinking using metal chelates, metal alcoholates, and polyfunctional isocyanates, and ionization. It is preferable to perform physical crosslinking treatment by irradiation with sexual radiation.

The pressure-sensitive adhesive composition for application to the skin of the present invention has the above constitution. If necessary, a plasticizer represented by a polyhydric alcohol such as glycerin, polyethylene glycol or polypropylene glycol, or a polyacrylic resin may be used. Acid, cross-linked polyacrylic acid, water-soluble or water-absorbing resin represented by polyvinylpyrrolidone, rosin-based resin, terpene-based resin, tackifying resin represented by petroleum-based resin, various softeners, various fillers, Various additives such as pigments may be blended.

The pressure-sensitive adhesive composition for skin application having the above constitution can be directly or indirectly formed into a layer on one surface of a base film to form a pressure-sensitive adhesive tape or sheet for skin application. Here, "indirectly" does not directly contact the pressure-sensitive adhesive layer on the base material film, but, for example, applies a primer to the surface of the base material film to improve the anchoring property with the pressure-sensitive adhesive layer. To form a pressure-sensitive adhesive layer.

The substrate film constituting the pressure-sensitive adhesive tape or sheet for application to the skin of the present invention is not particularly limited as long as it indicates the pressure-sensitive adhesive layer, but is applied to the skin surface as a pressure-sensitive adhesive tape or sheet. In order to remarkably improve the prevention of stuffiness on the skin surface and the reduction of skin adhesion during perspiration, it is preferable to use a base film having moisture permeability.

Examples of such a base film include urethane polymers such as polyether urethane and polyester urethane, amide polymers such as polyether polyamide block polymer, acrylic polymers such as polyacrylate, polyethylene and polypropylene, and ethylene / acetic acid. It can be obtained from materials such as polyolefin polymers such as vinyl copolymers and polyester polymers such as polyether polyesters. In addition, these base films are preferably selected from materials having water vapor permeability in order to prevent stuffiness and whitening when applied to the skin surface, for example, using a urethane-based or amide-based film. Is preferred. The base film may be made of any one of the above materials, or may be a laminated film in which a plurality of films made of any material are laminated.

When the above substrate film is applied to the skin surface
In order to avoid discomfort, the thickness should be 1
0 to 100 μm, preferably about 20 to 40 μm
Good. In addition, the ability to follow the skin when affixed to the skin surface
In order to improve the tensile strength, a tensile strength of 100 to 900 kg /
cm^Two, 100% modulus from 10 to 100 kg / cm
^TwoIt is preferable to adjust to the extent. Adjusted to this range
When a base film is used, the magnitude of movement like joints
It is effective when affixed to the skin surface. Base material fill
Not only non-porous film but also water vapor permeable
It is also possible to use a porous film that is permeable,
It is effective in preventing stuffiness. Such a film
In the case of, there is no particular limitation on the material, and a known porous material is used.
It can be easily obtained by applying technology. Non-porous
In the case of a conductive film, the larger the film thickness, the
The air permeability tends to decrease, but the porous filter
In the case of lum, a decrease in water vapor permeability is observed in proportion to the thickness.
It is useful because it does not appear in the book.

The adhesive tape or sheet of the present invention can be suitably used for an emergency bandage, a large bandage, a dressing material, a drape material and the like. Is usually
(About 100 μm), it is preferable to use a porous film. As the base film suitable for the porous film, a porous plastic film made of a polyolefin resin is preferable, and for example, resins such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer can be used. In particular, it is preferable to use a linear low-density polyethylene resin from the viewpoint of productivity and workability. The linear low-density polyethylene resin is a copolymer of ethylene and an α-olefin, and examples of the α-olefin include butene, hexene, and octene.

On the other hand, the pressure-sensitive adhesive layer formed on at least one surface of the base film preferably has a thickness of about 10 to 80 μm. When the thickness is less than 10 μm, sufficient skin adhesion may not be exhibited when applied to the skin, and when the thickness exceeds 80 μm, sufficient water vapor permeability is obtained as an adhesive tape or sheet as a whole. It is difficult to impart sweat resistance because it cannot be applied, and skin irritation may be manifested by long-term application.

The pressure-sensitive adhesive tape or sheet for application to the skin of the present invention preferably has water vapor permeability.
The moisture permeability of the entire adhesive material is 300 g / m ² · 24 h ·
40 ° C, 30% R. H. Above, preferably 300 to 24
^{00g / m 2 · 24h · 40} ℃ · 30% R. H. And more preferably 800 to 2400 g / m ² · 24h · 40
℃ 30% R.C. H. Set to the range. When a patch is applied to the skin surface of a person, the minimum is 300 g / m ² · 24 h · 40 ° C. · 30%, depending on individual differences and the site of application.
R. H. This is because if it does not have such a moisture permeability, when it is attached to a site where the amount of perspiration is large, sufficient moisture permeability cannot be exhibited, which may cause stuffiness.

The pressure-sensitive adhesive tape or sheet of the present invention has the above-mentioned structure. Usually, on the exposed surface of the pressure-sensitive adhesive layer, a release sheet whose surface has been subjected to a release treatment such as silicone treatment is temporarily attached. It is common to keep.

[0040]

EFFECT OF THE INVENTION Since the pressure-sensitive adhesive composition for application to the skin of the present invention has the above constitution, it is less irritating to the skin and is useful for long-term application. In particular, it does not cause a significant decrease in skin adhesion even when moisture is released due to sweating on the skin surface, and has excellent sweat resistance, which causes inconvenience even when used in summer, sports, bathing. No effect is exhibited.

[0041]

EXAMPLES Examples of the present invention will be described below in more detail, but the present invention is not limited thereto, and various applications can be made without departing from the technical idea of the present invention. It is possible. In the following text, “parts” means “parts by weight”, and “%” means “% by weight”.

Example 1 Isononyl acrylate 65 under an inert gas atmosphere
, 30 parts of 2-methoxyethyl acrylate and 5 parts of acrylic acid are uniformly dissolved and mixed in 80 parts of toluene, and 0.3 part of azobisisobutyronitrile as a polymerization initiator is added. To carry out a copolymerization reaction to obtain an acrylic copolymer.

Next, 60 parts of triglyceryl caprylate and 0.1 part of a trifunctional isocyanate compound (manufactured by Nippon Polyurethane Co., Coronate HL) as a crosslinking agent were mixed with 100 parts of this copolymer in a toluene solvent. This is applied to the treated surface of a release sheet having one side subjected to silicone treatment so that the thickness after drying is 40 μm, and is heated and dried at 110 ° C. for 3 minutes to form a crosslinked skin-applied pressure-sensitive adhesive layer. did.

Next, on the surface of the obtained pressure-sensitive adhesive layer, a polyester-based nonwoven fabric (Sontara 8010, manufactured by DuPont)
And then aged at 60 ° C. for 72 hours to produce a pressure-sensitive adhesive sheet for skin application of the present invention.

Example 2 In Example 1, the amount of triglyceryl caprylate was changed to 3
A pressure-sensitive adhesive sheet for applying to the skin of the present invention was prepared in the same manner as in Example 1 except that 0 part was used.

Example 3 In Example 1, the amount of triglyceryl caprylate was changed to 1
A pressure-sensitive adhesive sheet for application to the skin of the present invention was prepared in the same manner as in Example 1, except that the amount of the trifunctional isocyanate compound as a crosslinking agent was 0.14 parts.

Comparative Example 1 A pressure-sensitive adhesive sheet for application to skin was prepared in the same manner as in Example 1, except that triglyceryl caprylate as a carboxylic acid ester was not used.

Comparative Example 2 The acrylic copolymer obtained in Example 1 was obtained by copolymerizing a monomer mixture comprising 92 parts of 2-ethylhexyl acrylate and 8 parts of acrylic acid, and was used as a crosslinking agent. 0.11 of the trifunctional isocyanate compound
A pressure-sensitive adhesive sheet for sticking to skin was prepared in the same manner as in Example 1 except that the above-mentioned parts were used.

Comparative Example 3 In Example 1, the acrylic copolymer was used as a copolymer obtained by copolymerizing a monomer mixture consisting of 70 parts of 2-ethylhexyl acrylate and 30 parts of 2-methoxyethyl acrylate. An adhesive sheet for applying to skin was prepared in the same manner as in Example 1 except that the crosslinking agent was not blended.

Comparative Example 4 In Example 1, 60 parts of triglyceryl caprylate as a carboxylic acid ester was replaced with polyethylene glycol (molecular weight: 400), and the amount of a trifunctional isocyanate compound as a crosslinking agent was changed to 0.16 part. A pressure-sensitive adhesive sheet for application to the skin was prepared in the same manner as in Example 1 except that the procedure was repeated.

Comparative Example 5 Example 1 was repeated except that the amount of the trifunctional isocyanate compound as a crosslinking agent was changed to 0.05 part.
In the same manner as in the above, a pressure-sensitive adhesive sheet for sticking to skin was prepared.

Comparative Example 6 Example 1 was repeated except that the amount of the trifunctional isocyanate compound as a crosslinking agent was changed to 0.40 part.
In the same manner as in the above, a pressure-sensitive adhesive sheet for sticking to skin was prepared.

Comparative Example 7 30 parts of styrene / isoprene / styrene block copolymer (styrene content 15%), liquid polyisoprene 30
Parts, and 40 parts of a β-pinene-based polymer (softening point 115 ° C.) were uniformly mixed in toluene, and the mixture was applied to the treated surface of a release sheet having one surface subjected to silicone treatment in the same manner as in Example 1.
After drying, a pressure-sensitive adhesive sheet for applying to the skin was prepared.

Comparative Example 8 In Example 1, the amount of triglyceryl caprylate was changed to 1
An adhesive sheet for applying to skin was prepared in the same manner as in Example 1 except that the amount was 5 parts.

Comparative Example 9 In Example 1, the amount of triglyceryl caprylate was changed to 1
A pressure-sensitive adhesive sheet for application to skin was prepared in the same manner as in Example 1, except that the amount was 40 parts and the amount of the trifunctional isocyanate compound as a crosslinking agent was 0.12 parts.

Example 4 Example 4 was repeated except that triglyceryl caprylate (60 parts) was replaced with isopropyl myristate (50 parts) and the amount of the trifunctional isocyanate compound as a crosslinking agent was 0.12 parts. In the same manner as in Example 1, a skin pressure-sensitive adhesive sheet of the present invention was produced.

Example 5 The skin of the present invention was prepared in the same manner as in Example 1 except that the adhesive composition was changed to 70 parts of isononyl acrylate, 25 parts of 2-ethoxyethyl acrylate, and 5 parts of acrylic acid. A pressure-sensitive adhesive sheet was prepared.

The following tests were carried out on the pressure-sensitive adhesive sheets for application to skin obtained in the above Examples and Comparative Examples, and the results are shown in Table 1.

<Measurement of Insoluble Content> A predetermined amount (approximately 0.2 g) of the pressure-sensitive adhesive was collected from each pressure-sensitive adhesive sheet and weighed to determine the weight (W1). Next, this adhesive was immersed in toluene at room temperature for 7 days to extract soluble components. Insoluble matter (residue) is converted to a polytetrafluoroethylene membrane (average pore size 0.2
μm, NTF membrane, manufactured by Nitto Denko Corporation), filtered, dried and weighed to determine the weight (W2). The ratio of insoluble matter (gel fraction) was calculated by the following equation.

[0060]

(Equation 1)

<Moisture Permeability> 10 ml of distilled water with an inner diameter of 40 m
m, put in a glass container of height 40mm, diameter 50mm
The skin-adhesive pressure-sensitive adhesive sheet cut into a circle was adhered to the mouth of the container with the pressure-sensitive adhesive layer facing downward, and fixed. After measuring the weight (W4) of the whole container to which the pressure-sensitive adhesive sheet was stuck, this was measured at 40 ° C. and a relative humidity of 30% RH. H. And the weight (W4) after standing for 24 hours was measured. The moisture permeability was calculated by the following equation.

[0062]

(Equation 2) Moisture permeability ^{(g / m 2 · 24h ·} 40 ℃ · 30% RH) = (W3-W4) / (0.02
× 0.02 × π)

<Skin Adhesive Strength (Normal Condition)> 23 ° C., 30% R.H. H. In a test room under constant temperature and humidity conditions of 20 mm × 60 mm
The skin-adhesive pressure-sensitive adhesive sheet cut into a rectangular shape is pressure-bonded by reciprocating once with a 2 kg roller, and after 20 minutes, the pressure-sensitive adhesive sheet is peeled in a direction of 180 degrees at a peeling speed of 300 mm / min. The peel resistance stress at that time was defined as the skin adhesive strength (normal state).

<Skin Adhesion (Sweating)> 23 ° C., 30% R.H. H. 20mm x 60m on the back of a volunteer who rested for more than 30 minutes in a test room under constant temperature and humidity conditions
2 kg of the skin-adhesive pressure-sensitive adhesive sheet cut into a rectangular shape
The roller is reciprocated one time with a roller, and the entire area of the adhesive sheet is adhered to a polyester film (10% moisture permeability).
g / m · 24h · 40 ° C. · 30% R. H. After the elapse of 6 hours, the polyester film is removed, and the adhesive sheet is peeled in a direction of 180 degrees at a peeling speed of 300 mm / min. ).

<Glue Remaining During Peeling> As described above, the skin surface after the measurement of the skin adhesive force in the normal state and during sweating is visually observed, and the presence or absence of the glue residue on the skin surface is determined according to the following criteria. Was determined. ：: No adhesive residue is observed on the skin surface. Δ: Adhesive residue was observed on a part of the skin surface. ×: Adhesive residue was observed on the entire surface.

<Skin maceration at the time of peeling> After the skin adhesion test at the time of sweating, the skin surface was visually observed, and the degree of maceration of the skin surface was determined according to the following criteria. ：: maceration was observed and the nest was in the same state as the surrounding skin. Δ: slightly whitish and slightly different from the surrounding skin. ×: Obvious white maceration.

[0067]

[Table 1]

As is evident from the results shown in Table 1, the difference between the skin adhesive strength under normal conditions and the skin adhesive strength during perspiration is smaller in the example product than in the comparative example product, and the product is excellent in perspiration resistance. It is an adhesive sheet. Also, the example product has no adhesive residue at the time of peeling,
It does not cause skin maceration.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C081 AA03 AA12 BB04 CA081 CC01 CE11 DA02 DC03 4J002 BG041 BG051 BG061 BG071 EH046 EH056 GB01 GF00 GJ01 4J100 AJ02R AJ08R AJ09R AL03P AL04 BA05Q08 JA08 BA08

Claims (7)

[Claims] 1. An alkyl (meth) acrylate 4
Acrylic copolymer obtained from a monomer mixture containing 0 to 80% by weight, 10 to 60% by weight of an alkoxy group-containing ethylenically unsaturated monomer, and 1 to 10% by weight of a carboxyl group-containing ethylenically unsaturated monomer. A pressure-sensitive adhesive composition containing 100 parts by weight of coalesced and 20 to 120 parts by weight of a carboxylic acid ester in a liquid or paste form at room temperature, wherein 30 to 80% by weight of an acrylic copolymer is insoluble. An adhesive composition for adhering to skin. 2. The pressure-sensitive adhesive composition for application to skin according to claim 1, wherein the carboxylic acid ester is a glycerin ester of a saturated fatty acid. 3. The method according to claim 1, wherein the saturated fatty acid is caprylic acid, capric acid,
The pressure-sensitive adhesive composition for application to the skin according to claim 2, which is any one of 2-ethylhexanoic acid. 4. The pressure-sensitive adhesive composition for application to skin according to claim 2, wherein the glycerin ester is a triglycerin ester. 5. A pressure-sensitive adhesive for skin application, wherein the pressure-sensitive adhesive composition for skin application according to any one of claims 1 to 4 is directly or indirectly formed in a layer on at least one surface of a substrate film. Tape or sheet. 6. The pressure-sensitive adhesive tape or sheet according to claim 5, wherein the base film is a base film having moisture permeability. 7. The total moisture permeability is from 300 to 2400 g /
^{m 2 · 24h · 40 ℃ ·} 30% R. H. Claim 5
Or a pressure-sensitive adhesive tape or sheet for adhering to skin according to item 6.