JP2008132206A - Skin application adhesive sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a skin application adhesive sheet, causing less stimulation to skin compared to conventional adhesive sheets for skin, and achieving favorable wettability and adaptability to skin, sufficient adhesive force to skin, and excellent long-time adhesion performance to skin. <P>SOLUTION: The skin application adhesive sheet comprises a layer of adhesive agent composition formed on a support. The layer of adhesive agent composition comprises adhesive agent composition formed by hardening (A) a polyether-based polymer having at least one alkenyl group in one molecule, (B) a compound including two or more hydrosilyl groups on average in one molecule, and (C) a hydrosilylation catalyst, in which the compound (B) includes one mol or more hydrosilyl groups per mol of alkenyl groups in total in polyether-based polymer as the polymer (A). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an adhesive sheet for skin application used in the medical field or cosmetic field.

  Adhesive sheets are used in various forms in the medical field, such as surgical tapes, adhesive bandages, wound dressing dressings, or electrocardiographic measurement base materials. As the pressure-sensitive adhesive sheet used for skin application, an acrylic pressure-sensitive adhesive that is excellent in adhesion and moisture permeability and has low irritation to the skin is used. However, since the acrylic adhesive has a strong adhesive force, it may cause pain when it is peeled off from the skin and may damage the stratum corneum of the skin. In addition, the acrylic polymer is generally applied to, for example, a support substrate or release paper after adjusting the viscosity using an organic solvent or the like. The organic solvent used for viscosity adjustment is volatilized and removed after application, but it is difficult to remove completely, and the organic solvent remaining in the adhesive is absorbed into the body from the skin and causes inflammation such as rash. There is.

Silicone pressure-sensitive adhesives have been proposed as pressure-sensitive adhesives that reduce such physical irritation to the skin and do not use organic solvents (for example, Patent Documents 1 and 2). However, the silicone-based pressure-sensitive adhesive does not have sufficient adhesive strength and may not be suitable for long-term skin sticking.
JP 7-216341 JP2005-110875

  The present invention solves the above-mentioned conventional problems, and its purpose is to have less skin irritation compared to conventional adhesive sheets for skin application, and good wettability and familiarity to the skin. Another object of the present invention is to provide a pressure-sensitive adhesive sheet for skin application, which has sufficient adhesive strength to the skin and can be applied to the skin for a long time.

  As a result of intensive studies in view of such problems, the present invention has been completed. That is, the present invention provides a skin adhesive pressure-sensitive adhesive sheet having a pressure-sensitive adhesive composition layer formed on a support, wherein the pressure-sensitive adhesive composition layer comprises a polyether polymer having a siloxane bond. The present invention relates to a pressure-sensitive adhesive sheet.

  In the present invention, the pressure-sensitive adhesive composition layer contains (A) a polyether polymer having at least one alkenyl group in one molecule, and (B) an average of two or more hydrosilyl groups in one molecule. In the pressure-sensitive adhesive composition obtained by curing the compound (C), a hydrosilylation catalyst, the total amount of hydrosilyl groups in the compound (B) is 1 mol or more per 1 mol of the total amount of alkenyl groups in the polymer (A). The present invention relates to a pressure-sensitive adhesive sheet for skin application characterized by having a base weight.

  Further, the present invention is characterized in that in the pressure-sensitive adhesive composition layer, the total amount of hydrosilyl groups of the compound (B) has 1 to 4 mol of hydrosilyl groups per 1 mol of the total amount of alkenyl groups of the polymer (A). The present invention relates to an adhesive sheet for skin application.

  The present invention also relates to a pressure-sensitive adhesive sheet for skin application, wherein the polyether polymer of the polymer (A) is polyoxypropylene.

  The present invention also relates to a pressure-sensitive adhesive sheet for skin application, wherein the hydrosilylation catalyst is a platinum-vinylsiloxane complex.

  The present invention also relates to a pressure-sensitive adhesive sheet for skin application, wherein the ratio of the toluene-insoluble component in the pressure-sensitive adhesive composition layer is 30% to 80%.

  According to the pressure-sensitive adhesive sheet for skin application of the present invention, the skin irritation is small, the wettability to the skin and the familiarity are good compared with the conventional pressure-sensitive adhesive sheet for skin application, sufficient adhesive force and long-lasting skin. Can be obtained.

  The present invention will be described in detail below.

  In the present invention, at least one pressure-sensitive adhesive layer is provided on a support.

  The material of the support is not particularly limited, and usual materials used for skin patches are used. Specifically, urethane polymers such as polyether urethane, amides such as polyether amide, etc. Polymer, acrylic polymer such as polyacrylate, olefin polymer such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ester polymer such as polyether polyester, polyester, nylon, polyethylene, polypropylene, ethylene-vinyl acetate copolymer Examples thereof include films such as coalescence, ethylene-ethyl acrylate copolymer, polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyurethane, polyamide, and polyvinyl alcohol, nonwoven fabric, and metal foil. These may be used singly or in combination of two or more, and moisture-permeable polyurethane films and nonwoven fabrics are preferably used. The thickness of the support is preferably 5 to 200 microns, more preferably 5 to 100 microns in terms of irritation to the skin and durability. If the thickness of the support is more than 200 microns, the followability with respect to the skin is lowered and the film is easily peeled off, which is not preferable because the physical irritation to the skin is increased. If the thickness of the support is less than 5 microns, it is not preferable from the viewpoint of durability.

  The pressure-sensitive adhesive composition laminated on the substrate contains (A) a polyether polymer having at least one alkenyl group in one molecule, and (B) an average of two or more hydrosilyl groups in one molecule. And (C) a mixture comprising a hydrosilylation catalyst is cured.

  The polymer (A) is a polyether polymer having at least one alkenyl group in one molecule. The alkenyl group is not particularly limited as long as it is a group containing a carbon-carbon double bond that is active for hydrosilylation reaction. The alkenyl group is preferably an aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, more preferably 2 to 6 carbon atoms (eg, vinyl group, allyl group, methylvinyl group, propenyl group, butenyl group, pentenyl group). Group, hexenyl group, etc.), preferably a cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, more preferably 3 to 6 carbon atoms (eg, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, etc.) ), A methacryl group and the like.

From the viewpoint of easy synthesis reaction, preferred alkenyl groups include the following (1), (2)
Is mentioned. In the following formula, R ¹ or R ² is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group.
(1) H ₂ C═C (R ¹ ) −
^{(2) HC (R 2)} = CH-
The polymer (A) has an average of at least 1, preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2 alkenyl groups per molecule. Polymer (A) If the average number of alkenyl groups in one molecule is less than 1, the curability will be insufficient, and if the number of alkenyl groups contained in one molecule is too large, the network structure will be dense. For this reason, the adhesive properties tend to decrease.

A typical example of the polyether polymer that is the basic skeleton of the polymer (A) is a polyoxyalkylene polymer composed of a repeating unit represented by the general formula (—R ³ —O—). Here, —R ³ — is a divalent alkylene group. Adhesive properties, skin irritation, the wettability to the skin, the main chain of the preferred polymer (A) is a polyoxypropylene (i.e., the -R ³ - is -CH ₂ CH (CH ₃₎ - is a) . Moreover, it is preferable also from the point of workability | operativity on acquisition. The polyether polymer may be composed of one type of repeating unit or may be composed of a plurality of repeating units. The polyether polymer may be a linear polymer or a branched polymer.

  All the parts other than the alkenyl group of the polymer (A) preferably comprise a polyether skeleton, but may contain other structural units. In that case, the total of the polyether skeleton in the polymer (A) is preferably 80% by weight or more, and more preferably 90% by weight or more.

  The molecular weight of the polymer (A) is preferably 3,000 to 50,000, more preferably 4,000 to 50,000, and particularly preferably 5,000 to 30,000 from the viewpoint of good workability at room temperature and good adhesive properties. When the number average molecular weight is less than 3,000, the obtained cured product tends to be brittle. Conversely, when the number average molecular weight exceeds 50,000, the viscosity tends to be high and workability tends to be lowered. The molecular weight is a polystyrene equivalent number average molecular weight measured by GPC. The bonding mode of the alkenyl group to the polyether polymer is not particularly limited, and examples thereof include a direct bond of an alkenyl group, an ether bond, an ester bond, a carbonate bond, a urethane bond, and a urea bond.

  The method for producing the polymer (A) is not particularly limited, and examples thereof include a method of introducing an alkenyl group after obtaining a polyether polymer. In this case, various known production methods can be applied to the polyether polymer, and a commercially available polyether polymer may be used. In addition, a method for introducing an alkenyl group into a polyether polymer is also known. For example, a monomer having an alkenyl group (eg, allyl glycidyl ether) and a monomer for synthesizing a polyether polymer are copolymerized. And a functional group that is reactive to the functional group into a polyether polymer in which a functional group (eg, hydroxyl group, alkoxide group) has been previously introduced into a desired portion (end of main chain, etc.) And a method of reacting a compound having both a group and an alkenyl group (eg, acrylic acid, methacrylic acid, vinyl acetate, acrylic acid chloride, etc.).

  The compound (B) is a compound having 1 to 10 hydrosilyl groups in the molecule. The hydrosilyl group means a group having a Si—H bond. In the present invention, when two hydrogen atoms (H) are bonded to the same silicon atom (Si), it is calculated as two hydrosilyl groups. The chemical structure of the compound (B) other than the hydrosilyl group is not particularly limited. The number average molecular weight of the compound (B) calculated from the SiH value obtained by titration is preferably 400 to 3000, more preferably 500 to 1000. This is because if the number average molecular weight is too low, it tends to volatilize at the time of heat-curing, and it tends to be difficult to obtain a sufficient cured product, and if it is too high, the curing rate tends to be slow.

  The number of hydrosilyl groups contained in one molecule of the compound (B) is 1 to 10, preferably 2 to 8. If there are two or more hydrosilyl groups, a plurality of polymer (A) molecules can be cross-linked during curing, exhibiting a preferable cohesive force as an adhesive for skin, and paste when peeled after being applied to the skin. The rest is less likely to occur. However, depending on the number of hydrosilyl groups, the cross-linking becomes too dense, and the adhesive properties such as skin adhesive force and tackiness as a skin pressure-sensitive adhesive tend to be reduced. Incidentally, the density of the cross-linking affects the density between the polyether parts as the main chain of the polymer (A), and further affects the moisture permeability of the entire pressure-sensitive adhesive. Therefore, the number of hydrosilyl groups in the compound (B) should be selected in consideration of the balance with the adhesive properties. Moreover, a compound (B) may be used independently and may be used together 2 or more types. The compound (B) is preferably compatible with the polymer (A). From the viewpoint of easy availability of raw materials and compatibility with the polymer (A), examples of suitable compounds (B) include organohydrogensiloxanes modified with organic groups. A typical example of the organohydrogensiloxane is a compound represented by the following formula (3).

上記式（３）のａの値が分子中のヒドロシリル基の数の数と一致する。ａ＋ｂの値は特に限定はないが好ましくは２〜５０である。Ｒ⁴は主鎖の炭素数が２〜２０の炭化水素基である。上記式（３）の化合物は、未変性のメチルハイドロジェンシリコーンを変性してＲを導入することにより得ることができる。未変性のメチルハイドロジェンシリコーンとは、上記（３）においてＲ⁴が全てＨである化合物に相当し、株式会社シーエムシー発行（１９９０．１．３１）の「シリコーンの市場展望−メーカー戦略と応用展開−」にも記載されているように、各種変性シリコーンの原料として用いられている。Ｒ⁴の導入のための有機化合物としては、α−オレフィン、スチレン、α−メチルスチレン、アリルアルキルエーテル、アリルアルキルエステル、アリルフェニルエーテル、アリルフェニルエステル等が挙げられる。変性のために加える上述の有機化合物の量によって、分子中のヒドロシリル基の数を調節することができる。

The value of a in the above formula (3) matches the number of hydrosilyl groups in the molecule. The value of a + b is not particularly limited but is preferably 2-50. R ⁴ is a hydrocarbon group having 2 to 20 carbon atoms in the main chain. The compound of the above formula (3) can be obtained by modifying an unmodified methyl hydrogen silicone and introducing R. Unmodified methylhydrogen silicone corresponds to the compound in which R ⁴ is all H in the above (3), and “Silicon Market Outlook-Manufacturer Strategy and Application” issued by CMC Co., Ltd. (1990.1.31). As described in "Development-", it is used as a raw material for various modified silicones. Examples of the organic compound for introducing R ⁴ include α-olefin, styrene, α-methylstyrene, allyl alkyl ether, allyl alkyl ester, allyl phenyl ether, allyl phenyl ester, and the like. The number of hydrosilyl groups in the molecule can be adjusted by the amount of the above-mentioned organic compound added for modification.

  The ratio of the amount of the polymer (A) and the compound (B) in the pressure-sensitive adhesive composition laminated on the substrate is derived from the compound (B) with respect to the number of alkenyl groups derived from the polymer (A). Expressed by the number of hydrosilyl groups. The degree of crosslinking density after curing is determined by the number of hydrosilyl groups relative to the number of alkenyl groups in the pressure-sensitive adhesive composition. In consideration of appropriate tackiness and fixing ability to the skin, the preferred amount ratio of the pressure-sensitive adhesive composition is 1 hydrosilyl group derived from the compound (B) per 1 mol of the total amount of alkenyl groups derived from the polymer (A). More preferable molar ratio is 1 mol to 4 mol of hydrosilyl groups derived from the compound (B) per 1 mol of the total amount of alkenyl groups derived from the polymer (A).

  It does not specifically limit as a hydrosilylation catalyst which is a catalyst (C) component, Arbitrary things can be used if a hydrosilylation reaction is accelerated | stimulated. Specifically, chloroplatinic acid, a platinum-vinylsiloxane complex (for example, platinum-1,3-divinyl-1,1,3,3, -tetramethyldisiloxane complex or platinum-1,3,5,7- Tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane complex), platinum-olefin complex (for example, Ptx (ViMe2SiOSiMe2Vi) y, Pt [(MeViSiO) 4] z (where x, y, and z are positive) )) And the like are exemplified. Among these, from the viewpoint of the activity of the catalyst, a platinum complex catalyst not containing a strong acid conjugate base as a ligand is preferable, a platinum-vinylsiloxane complex is more preferable, and platinum-1,3-divinyl-1,1 is preferable. 3,3, -tetramethyldisiloxane complex or platinum-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane complex is particularly preferred.

The amount of the catalyst (C) is not particularly limited, but is preferably 10 ⁻⁸ to 10 ⁻¹ mol, more preferably 10 ⁻⁶ to 10 ⁻¹⁰ mol, based on 1 mol of the total amount of alkenyl groups by the polymer (A). ^-3 mol. If it is in the said range, it will become easy to achieve appropriate hardening rate, stable sclerosis | hardenability, ensuring of a required pot life, etc.

  The pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer may contain components other than the above (A) to (C). These components include tackifiers, adhesion promoters, storage stabilizers for compound (B), and other components.

  Tackifiers and tackifiers include phenol resins, modified phenol resins, terpene phenol resins, xylene phenol resins, cyclopentadiene-phenol resins, xylene resins, petroleum resins, phenol-modified petroleum resins, rosin ester resins, low molecular weight polystyrene Resin, terpene resin and the like. When these are used to improve the adhesive properties, they may be used alone or in combination of two or more. The amount of the tackifier and the adhesion promoter used is preferably 10 to 100 parts by weight, more preferably 15 to 50 parts per 100 parts by weight of the total amount of the polymer (A) and the compound (B). Parts by weight. If the amount used is too large, the moisture permeability of the pressure-sensitive adhesive layer decreases, which is not preferable.

Examples of the storage stabilizer for the compound (B) include compounds containing an aliphatic unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds, and organic peroxides. The storage stabilizer suppresses the conversion of hydrosilyl groups (Si-H groups) to Si-OH groups in the compound (B) (due to standing for a long time or mixing of moisture), thereby reducing the pot life of coating. Can be improved. The blending amount of the storage stabilizer is preferably 10 ⁻⁶ to 10 ⁻¹ mol with respect to 1 mol of the total amount of hydrosilyl groups contained in the pressure-sensitive adhesive composition due to the compound (B).

  The pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer may contain a water-soluble organic polymer or a water-absorbing polymer for improving the water resistance, sweat resistance, water absorption, etc. of the pressure-sensitive adhesive layer. Furthermore, other plasticizers, softeners, fillers, pigments, surfactants, ultraviolet absorbers, antioxidants, antibacterial agents, and the like may be blended. At this time, it is preferable not to use an organic solvent, but the use thereof is not denied.

  The pressure-sensitive adhesive sheet for skin application of the present invention is obtained by curing the above-mentioned pressure-sensitive adhesive composition. Here, the curing means that a hydrosilylation reaction is performed between the polymer (A) and the compound (B) by heating. Examples of the curing conditions include leaving at 40 to 180 ° C. for 1 to 60 minutes. If it is desired to complete the curing, it may be further left at 40 to 80 ° C. for several days. The degree of curing can be expressed by the proportion (% by weight) of toluene insoluble components in the pressure-sensitive adhesive layer. The toluene-insoluble component is a component that does not dissolve even when immersed in toluene for 7 days. Preferably, the proportion of the toluene insoluble component in the pressure-sensitive adhesive layer is 30 to 80% by weight. Within this range, the pressure-sensitive adhesive composition exhibits a sufficient fixing force for long-time skin patching, and when the resulting pressure-sensitive adhesive sheet for skin patching is peeled off after skin patching, the pressure-sensitive adhesive remains on the skin. Cohesive failure is less likely to occur. The ratio of the toluene-insoluble component can be controlled by the ratio of the amount of the polymer (A) and the compound (B) (the ratio of the total amount of alkenyl groups to the total amount of hydrosilyl groups) and the curing conditions. The viscosity at the time of curing is preferably 10 to 1000 Pa · s. This viscosity can be controlled by the ratio of the amounts of the components (A) to (C) and the kind and amount of the storage stabilizer for the compound (B) described above.

  The thickness of the pressure-sensitive adhesive layer is not particularly limited, and may be, for example, 10 to 5000 μm.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples, and various applications are possible without departing from the technical idea of the present invention. is there.

(Synthesis of polymer (A))
An oxypropylene polymer glycol having a number average molecular weight of 3000 was obtained by a polymerization method using caustic alkali. According to the method of Synthesis Example 1 of JP-A-5-117521, propylene oxide was polymerized using a double metal cyanide complex catalyst (zinc hexacyanocobaltate) using the oxypropylene polymer glycol as an initiator, and the number average molecular weight 28,000 polymers were obtained. The polymer is converted to an allyl group using a 28% methanol solution of sodium methylate and allyl chloride, and then desalted and purified to have approximately two allyl group ends in one molecule. A polyoxyalkylene polymer (polymer (A)) was obtained. The allyl terminal group amount of the obtained polymer was 0.12 mmol / g.

(Synthesis of Compound (B))
In the presence of a platinum catalyst, 0.5 equivalent of α-methylstyrene of the total hydrosilyl group amount is added to methyl hydrogen silicone represented by the following formula (4) (wherein x is an average of 5), and 1 molecule A compound (compound (B)) having an average of 2.5 hydrosilyl groups therein was obtained. The hydrosilyl group content of this compound was 3.2 mmol / g.

（実施例１）
重合体（Ａ）１００重量部に対して、化合物（Ｂ）を７．２重量部、ヒドロシリル化触媒である白金−１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン錯体（３重量％白金イソプロパノール溶液）０．１重量部、マレイン酸ジメチル０．０３重量部を十分に混合して粘着剤組成物を得た。この粘着剤組成物を室温にしてシリコーン剥離処理を施した剥離紙の処理面上に、硬化後の厚みが５０μｍになるように塗工して、１３０℃で３分間硬化させて粘着剤層を形成した。次に硬化した粘着剤層の上に、支持体としてポリエステルフィルム（厚さ２５μｍ）を速度２ｍ／ｍｉｎの条件にて重さ２Ｋｇのゴムローラーを用いてラミネートした。

(Example 1)
7.2 parts by weight of compound (B) with respect to 100 parts by weight of polymer (A), platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (hydrosilylation catalyst) 3 wt% platinum isopropanol solution) 0.1 parts by weight and 0.03 parts by weight of dimethyl maleate were sufficiently mixed to obtain an adhesive composition. The pressure-sensitive adhesive composition was coated on the treated surface of release paper that had been subjected to silicone release treatment at room temperature so that the thickness after curing was 50 μm, and cured at 130 ° C. for 3 minutes to form a pressure-sensitive adhesive layer. Formed. Next, a polyester film (thickness: 25 μm) as a support was laminated on the cured pressure-sensitive adhesive layer under the condition of a speed of 2 m / min using a rubber roller weighing 2 kg.

(Example 2)
9.2 parts by weight of compound (B) with respect to 100 parts by weight of polymer (A), platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (hydrosilylation catalyst) 3 wt% platinum isopropanol solution) 0.1 parts by weight and 0.03 parts by weight of dimethyl maleate were sufficiently mixed to obtain an adhesive composition. The pressure-sensitive adhesive composition was coated on the treated surface of release paper that had been subjected to silicone release treatment at room temperature so that the thickness after curing was 50 μm, and cured at 130 ° C. for 3 minutes to form a pressure-sensitive adhesive layer. Formed. Next, a polyester film (thickness: 25 μm) as a support was laminated on the cured pressure-sensitive adhesive layer under the condition of a speed of 2 m / min using a rubber roller weighing 2 kg.

(Example 3)
10.7 parts by weight of compound (B) with respect to 100 parts by weight of polymer (A), platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (hydrosilylation catalyst) 3 wt% platinum isopropanol solution) 0.1 parts by weight and 0.03 parts by weight of dimethyl maleate were sufficiently mixed to obtain an adhesive composition. The pressure-sensitive adhesive composition was coated on the treated surface of release paper that had been subjected to silicone release treatment at room temperature so that the thickness after curing was 50 μm, and cured at 130 ° C. for 3 minutes to form a pressure-sensitive adhesive layer. Formed. Next, a polyester film (thickness: 25 μm) as a support was laminated on the cured pressure-sensitive adhesive layer under the condition of a speed of 2 m / min using a rubber roller weighing 2 kg.

(Comparative Example 1)
For 100 parts by weight of the polymer (A), 3.2 parts by weight of the compound (B) and platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (hydrosilylation catalyst) 3 wt% platinum isopropanol solution) 0.1 parts by weight and 0.03 parts by weight of dimethyl maleate were sufficiently mixed to obtain an adhesive composition. The pressure-sensitive adhesive composition was coated on the treated surface of release paper that had been subjected to silicone release treatment at room temperature so that the thickness after curing was 50 μm, and cured at 130 ° C. for 3 minutes to form a pressure-sensitive adhesive layer. Formed. Next, a polyester film (thickness: 25 μm) as a support was laminated on the cured pressure-sensitive adhesive layer under the condition of a speed of 2 m / min using a rubber roller weighing 2 kg.

(Adhesive strength)
On top of that, the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive composition was cut into a width of 25 mm, a rubber roller having a weight of 2 kg was attached to a SUS304 plate at a speed of 2 m / min, and left for 1 hour. The stress at the time of peeling each tape from the SUS304 plate at an angle of 180 ° at a speed of 300 mm / min was used as a measurement value of the adhesive strength.

(Ratio of toluene insoluble components)
The weight (W1) of a 200 mesh wire mesh cut in about 5 cm square was accurately weighed. Next, about 0.5 g of the pressure-sensitive adhesive was collected from each pressure-sensitive adhesive sheet, wrapped with the wire mesh, and accurately weighed (W2). This was immersed in 50 g of toluene at room temperature for 7 days. Thereafter, the wire mesh was taken out and dried, and the weight (W3) was precisely weighed. The ratio of toluene insoluble components was calculated according to the following formula.
Toluene insoluble component (%) = (W3-W1) × 100 / (W2-W1)
(Skin fixation)
A tape having the pressure-sensitive adhesive composition cut to a 50 mm square was affixed to the back of the volunteer, and a roller having a weight of 2 kg was reciprocated once to cause pressure bonding. After 6 hours, the degree of peeling was determined. Those that did not peel were marked with ◯, those that were partially peeled were marked with Δ, and those that were completely peeled were marked with ×.

(Skin irritation)
A tape having the pressure-sensitive adhesive composition cut to a width of 20 mm was affixed to the back of the volunteer, and a roller having a weight of 2 kg was reciprocated once for pressure bonding. After 2 hours, the pain when the tape having the pressure-sensitive adhesive composition was peeled was subjected to sensory evaluation. The case where there was no pain was rated as ◯, the case where there was pain but no redness of the skin, etc. was marked as Δ, and the case where pain was strong and the skin was inflamed was marked as x.

Claims (6)

  A pressure-sensitive adhesive sheet for skin patch, wherein the pressure-sensitive adhesive composition layer is formed of a polyether polymer having a siloxane bond in a patch having a pressure-sensitive adhesive composition layer formed on a support. In a patch having a pressure-sensitive adhesive composition layer formed on a support, the pressure-sensitive adhesive composition layer is (A) a polyether polymer having at least one alkenyl group in one molecule, and (B) one molecule. A pressure-sensitive adhesive composition obtained by curing a compound containing an average of two or more hydrosilyl groups therein, (C) a hydrosilylation catalyst, wherein the total amount of hydrosilyl groups in the compound (B) is the polymer (A). 2. The pressure-sensitive adhesive sheet according to claim 1, wherein the pressure-sensitive adhesive sheet has 1 mol or more of hydrosilyl group per 1 mol of the total amount of alkenyl groups.   3. The pressure-sensitive adhesive composition layer according to claim 2, wherein the total amount of hydrosilyl groups in the compound (B) has 1 to 4 moles of hydrosilyl groups per mole of the total amount of alkenyl groups in the polymer (A). The adhesive sheet as described.   The pressure-sensitive adhesive sheet according to claim 2 or 3, wherein the polyether polymer of the polymer (A) is polyoxypropylene.   The pressure-sensitive adhesive sheet according to any one of claims 2 to 4, wherein the hydrosilylation catalyst is a platinum-vinylsiloxane complex.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 5, wherein the proportion of the toluene-insoluble component in the pressure-sensitive adhesive composition layer is 30% to 80%.