KR20160049535A - Bisoprolol-containing patch preparation - Google Patents

Abstract

The present invention provides a pressure sensitive adhesive sheet comprising a support and a pressure sensitive adhesive layer containing a glass type non - soaprolol and a pressure sensitive adhesive laminated on one side of the support, wherein the pressure sensitive adhesive layer has a stress relaxation rate of 20 to 90% And a non-soaprolol-containing adhesive agent having a width of 1.0 to 6.5 N / 30 mm. The non-soaprolol-containing adhesive preparation of the present invention suppresses drying during use, has excellent skin adhesiveness, and suppresses skin irritation upon peeling. As the pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive is suitable, and polyisobutylene and / or styrene-isoprene-styrene block copolymer are more suitable.

Description

[0001] BISOPROLOL-CONTAINING PATCH PREPARATION [0002]

The present invention relates to a non-soaprolol-containing adhesive agent for continuously absorbing non-soaproleol in vivo through the skin surface.

Isoprodol, a highly selective antagonist of the? 1 receptor of the sympathetic nerves, is used for the improvement of essential hypertension, angina pectoris, arrhythmia and the like, and its fumaric acid salt is orally administered as a tablet. On the other hand, in the case of oral administration, there are drawbacks such as insufficient persistence of pharmacological effect and rapid fluctuation of blood concentration after administration, and side effects are easily generated. To improve this, a transdermal preparation has recently been attracting attention .

Such a transdermal preparation can avoid, for example, drug metabolism or various side effects caused by the first passage of the liver, and further, the drug can be continuously administered over a long period of time. Above all, since the dosing operation is easy and the dosage can be strictly controlled, an adhesive preparation containing a drug in a pressure-sensitive adhesive is actively developed. Under such circumstances, various types of percutaneous absorption preparations of nonsofrolol have been recently developed.

The transdermal preparation contains a support including a woven fabric, a nonwoven fabric, a plastic film and the like, and a release liner laminated on the support and having a pressure-sensitive adhesive layer containing a drug and usually laminated on the pressure-sensitive adhesive layer .

As a feature of recent transdermal dosage formulations, it has been proposed that a large amount of a liquid component is contained in a pressure-sensitive adhesive layer and a crosslinking treatment is carried out for the purpose of improving softness upon adhering to the skin or alleviating skin irritation attributable to peeling- To thereby form a gel-like pressure-sensitive adhesive layer (Patent Document 1). Such a gel-like pressure-sensitive adhesive layer makes it possible to relax and disperse the stress provided to the skin surface at the time of peeling, while maintaining high adhesiveness to the skin surface to be adhered. Therefore, these pressure-sensitive adhesive layers are suitably used for percutaneous absorption preparations because they hardly cause physical stimulation to the skin and cause peeling of the stratum corneum and the like.

However, the percutaneous absorption preparation obtained by laminating the gel-like pressure-sensitive adhesive layer on a support may have poor adhesion stability to the skin surface (perspiration sticking resistance) in the summer when sweating is severe, The skin adhesion force at the periphery of the preparation is lowered, and the peripheral edge portion tends to dry easily.

Japanese Patent Application Laid-Open No. 6-23029

The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide a non-soaprol-containing adhesive preparation which suppresses drying during use, has excellent skin adhesiveness and suppresses skin irritation upon peeling, .

DISCLOSURE OF THE INVENTION The inventors of the present invention have made intensive investigations to solve the above problems. As a result, the present inventors found that a pressure-sensitive adhesive layer containing non-soaprolol satisfies a specific stress relaxation rate and a specific shear stress, And it is possible to exert excellent skin adhesiveness and to reduce the irritation upon peeling, and have accomplished the present invention.

That is, the present invention is as follows.

[1] A pressure-sensitive adhesive sheet comprising a support and a pressure-sensitive adhesive layer containing a glass-like non-soeprolol and a pressure-sensitive adhesive layer laminated on one surface of the support, wherein the pressure-sensitive adhesive layer has a stress relaxation rate of 20 to 90% An adhesive formulation containing non-soaprolol having a width of 1.0 to 6.5 N / 30 mm.

[2] The adhesive preparation containing non-soaprolol according to [1], wherein the pressure-sensitive adhesive layer has a stress relaxation rate of 40 to 90% and a shear stress of the pressure-sensitive adhesive layer is 1.0 to 4.0 N / 30 mm.

[3] The adhesive agent containing non-soaprolol according to [1] or [2], wherein the adhesive agent comprises a rubber-based adhesive agent.

[4] The adhesive agent according to [3], wherein the rubber-based adhesive is polyisobutylene and / or a styrene-isoprene-styrene block copolymer.

[5] The adhesion preparation containing non-soaprolol according to the above [4], wherein the polyisobutylene is polyisobutylene having a viscosity average molecular weight of 40,000 to 5,500,000.

[6] Polyisobutylene includes a first polyisobutylene (a) having a viscosity average molecular weight of 1,800,000 to 5,500,000 and a second polyisobutylene (b) having a viscosity average molecular weight of 40,000 to 85,000, and the first poly The adhesion agent containing non-soaprolol according to the above [4], wherein the compounding ratio (a: b) of isobutylene (a) and second polyisobutylene (b) is 1: 0.1 to 1: 3 by weight.

[7] The adhesion agent containing non-soaprolol according to [4], wherein the styrene-isoprene-styrene block copolymer has a styrene content of less than 30% by weight.

[8] The adhesive preparation containing non-soaprolol according to [4] or [7], wherein the content of the styrene-isoprene-styrene block copolymer in the pressure-sensitive adhesive layer is 5 to 50% by weight.

The non-soaprolol-containing adhesive preparation of the present invention has an effect of reducing the irritation of the skin caused by peeling of the stratum corneum at the time of peeling, .

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic sectional view showing one embodiment of the adhesive preparation of the present invention. Fig.
Fig. 2 is a schematic plan view showing a state in which a bonding agent, from which the release liner 3 has been peeled off from the adhesive agent of Fig. 1, is installed in a tensile tester.
3 is a sectional view taken along the line III-III in Fig.
Fig. 4 is a schematic plan view when the adhesive preparation provided in the tensile tester of Fig. 2 is deformed in the shearing direction. Fig.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view showing an embodiment of the non-soaprolol-containing adhesive preparation of the present invention (hereinafter abbreviated as "adhesive preparation"). 1 comprises a support 1, a pressure-sensitive adhesive layer 2 laminated on one side of the support 1, and a release liner 3 laminated on the pressure-sensitive adhesive layer 2, Respectively. Further, the release liner 3 may be omitted. The pressure-sensitive adhesive layer (2) contains glass-type non-soaprolol and a pressure-sensitive adhesive.

&Quot; Free-form non-soaprolol " means free base of non-soaprolol. In order to incorporate the glass-like non-soaproleol in the pressure-sensitive adhesive layer, the glass-like nonsofrolol may be blended as it is, or a pharmaceutically acceptable salt of nonsofrolol may be desalted at the time of blending, Soaprolol may be used. That is, the pressure-sensitive adhesive layer may contain free-form non-soaproleol at the time of using the adhesive preparation. Pharmaceutically acceptable salts of nonsofrolol include, for example, fumaric acid salts and hydrochloric acid salts. Since the free-form non-soaproleol used in the present invention is a drug which is in a liquid phase at room temperature (for example, 25 DEG C), it is contained in the pressure-sensitive adhesive layer, so that not only the pharmacological action as nonsofrolol but also the plasticizing action Shows a tendency that the pressure-sensitive adhesive layer tends to soften, and has the effect of improving the soft feeling when adhering to the skin or alleviating the skin irritation caused by peeling of the stratum corneum of the skin at the time of detachment.

The content of the free-form non-soaproleol can be appropriately set as required, but is generally 0.5 to 40% by weight, preferably 0.5 to 30% by weight, in the pressure-sensitive adhesive layer. When the content is 0.5% by weight or more, release of a drug in an amount effective for treatment can be expected. When the amount is 40% by weight or less, a sufficient therapeutic effect can be exhibited and economically advantageous, and when it is 30% by weight or less, it is more economically advantageous.

The pressure-sensitive adhesive is not particularly limited and includes, for example, an acrylic pressure-sensitive adhesive such as an acrylic polymer; Rubber-based pressure-sensitive adhesives such as styrene-diene-styrene block copolymer (for example, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer), polyisoprene, polyisobutylene and polybutadiene; Silicone type pressure-sensitive adhesives such as silicone rubber, dimethylsiloxane base and diphenylsiloxane base; Vinyl ether-based pressure-sensitive adhesives such as polyvinyl methyl ether, polyvinyl ethyl ether, and polyvinyl isobutyl ether; Vinyl acetate-based pressure-sensitive adhesives such as vinyl acetate-ethylene copolymer; And polyester-based pressure sensitive adhesives such as polyesters containing carboxylic acid components such as dimethyl terephthalate, dimethyl isophthalate and dimethyl phthalate and polyhydric alcohol components such as ethylene glycol. Among them, a rubber adhesive is preferred.

Examples of the rubber-based pressure-sensitive adhesive include rubber-based pressure-sensitive adhesives composed mainly of at least one selected from polyisobutylene, polyisoprene, butyl rubber, styrene-isoprene-styrene block copolymer and styrene-butadiene-styrene block copolymer. Of these, polyisobutylene and / or styrene-isoprene-styrene block copolymers are suitably used in view of high drug stability, required adhesion and cohesive strength. In the present invention, the term "styrene-isoprene-styrene block copolymer" means a triblock (a polymer chain having polystyrene blocks bonded to both ends of the polyisoprene block) alone or a block copolymer of triblock and diblock A polymer chain in which one end of a polyisoprene block is bonded to one end of a polystyrene block), and is preferably a block copolymer comprising a mixture of a triblock and a diblock.

When polyisobutylene is used as the rubber-based pressure-sensitive adhesive, it may contain one kind of polyisobutylene alone or two or more kinds of polyisobutylene having different molecular weights.

When the polyisobutylene is contained alone, the content of polyisobutylene in the pressure-sensitive adhesive layer is preferably 15 to 60% by weight, and more preferably 15 to 55% by weight. If the content of polyisobutylene is less than 15% by weight, it may be difficult to impart the necessary internal cohesive force to the pressure-sensitive adhesive layer. On the other hand, if the content is more than 60% by weight, the skin adhesiveness and tackiness of the pressure- have.

In the case where polyisobutylene is contained alone as a single species, the molecular weight of polyisobutylene is not particularly limited, and the viscosity average molecular weight is preferably 40,000 to 5,500,000, more preferably 45,000 to 5,000,000. If the viscosity average molecular weight is less than 40,000, it may be difficult to impart the necessary internal cohesive force to the pressure-sensitive adhesive layer. On the other hand, when the viscosity average molecular weight exceeds 5,500,000, the skin adhesiveness and tack of the pressure-

It is preferable to contain two or more kinds of polyisobutylenes having different molecular weights in order to easily balance the proper cohesion force of the pressure-sensitive adhesive layer, proper flexibility and skin adhesiveness. In the present specification, " two or more kinds of polyisobutylene having different molecular weights " refers to polyisobutylene having a peak of molecular weight distribution measured by gel permeation chromatography (GPC) in two or more independent regions. Further, the peak of the molecular weight distribution of each polyisobutylene is generally one. Examples of the " two or more kinds of polyisobutylene having different molecular weights " include two or more kinds of polyisobutylene having different viscosity average molecular weights.

As the two or more kinds of polyisobutylene having different molecular weights, for example, a mixture of a first polyisobutylene and a second polyisobutylene having a relatively smaller molecular weight than the first polyisobutylene is preferable. The first polyisobutylene imparts a suitable cohesive force to the pressure-sensitive adhesive layer, and the second polyisobutylene can impart appropriate flexibility and skin adhesiveness to the pressure-sensitive adhesive layer. The molecular weights of the first polyisobutylene and the second polyisobutylene are not particularly limited. However, in order to obtain good adhesiveness and sufficient releasability of nonsofrolol, the viscosity average molecular weight of the first polyisobutylene is preferably , Preferably from 1,800,000 to 5,500,000, more preferably from 2,000,000 to 5,000,000, and the viscosity average molecular weight of the second polyisobutylene is preferably from 40,000 to 85,000, more preferably from 45,000 to 65,000. If the viscosity average molecular weight of the first polyisobutylene is less than 1,800,000, it may be difficult to impart the necessary internal cohesive force to the pressure-sensitive adhesive layer. On the other hand, if the viscosity average molecular weight exceeds 5,500,000, the skin adhesiveness and tack of the pressure- have. If the viscosity average molecular weight of the second polyisobutylene is less than 40,000, stickiness is caused in the pressure-sensitive adhesive layer and the skin surface may be contaminated. On the other hand, if the viscosity average molecular weight is more than 85,000, There is a possibility that the tag is lowered. The first and second polyisobutylenes may be used in combination of two or more kinds within the respective molecular weight distribution ranges.

In the present specification, the viscosity average molecular weight is calculated by the following equation (1) (Schulz-Blaschke equation) from the flow time of the capillary of the Ubbelode viscometer at 20 ° C, (2) using the J value.

_{J 0 = η SP /c(1+0.31 ηSP)} (cm 3 / g) (Schulz-Blaschke equation) (1)

η _SP = t / t _o -1

t: the flow time of the solution (according to the Hagenbach-Couette formula)

t ₀ : the flow time of the solvent (according to the Hagenbach-Couette formula)

c: concentration (g / cm ³⁾ was added

J₀= 3.06 x 10^{- 2}Mv^{0 . 65} (2)

M _v : viscosity average molecular weight

When two or more kinds of polyisobutylenes having different molecular weights are used as the rubber pressure-sensitive adhesive, the total content of polyisobutylene in the pressure-sensitive adhesive layer is preferably 15 to 70 wt%, more preferably 30 to 65 wt% Preferably 50 to 65% by weight. If the total content of polyisobutylene is less than 15% by weight, it may be difficult to impart the necessary internal cohesive force to the pressure-sensitive adhesive layer. On the other hand, if the content exceeds 70% by weight, skin adhesiveness and tackiness of the pressure- .

In the case of using two kinds of polyisobutylene having different molecular weights as the rubber-based pressure-sensitive adhesive, in the embodiment using the first polyisobutylene (a) and the second polyisobutylene (b), the first polyisobutylene The blend ratio (a: b) of the first polyisobutylene (a) and the second polyisobutylene (b) is preferably 1: 0.1 to 1: 3, more preferably 1: 0.5 to 1: 2, 1: 0.65 to 1: 0.97, and most preferably 1: 0.77 to 1: 0.97. If the compounding ratio of the second polyisobutylene (b) in the two types of polyisobutylene exceeds the above upper limit, the internal cohesive force of the pressure-sensitive adhesive layer may be lowered. On the other hand, The lowering of the skin adhesion force of the skin may be increased.

When a styrene-isoprene-styrene block copolymer is used as a rubber-based pressure-sensitive adhesive, the styrene-isoprene-styrene block copolymer preferably has a styrene content of less than 30% by weight. The diblock ratio is preferably 0 to 80 wt%, and more preferably 10 to 50 wt%. The content of the styrene-isoprene-styrene block copolymer in the pressure-sensitive adhesive layer is preferably 5 to 50% by weight, and more preferably 10 to 30% by weight. If the content of the styrene-isoprene-styrene block copolymer is less than 5% by weight, it may be difficult to impart the necessary internal cohesion to the pressure-sensitive adhesive layer. On the other hand, if the content exceeds 50% by weight, There is a risk of degradation.

Further, by changing the styrene content of the styrene-isoprene-styrene block copolymer and the content of the styrene-isoprene-styrene block copolymer in the pressure-sensitive adhesive layer, a desired stress relaxation rate and shear stress are easily obtained.

For example, when the styrene-isoprene-styrene block copolymer is used alone as the rubber-based pressure-sensitive adhesive, the styrene content is preferably 10 to 24 wt%, and more preferably 15 to 24 wt%. When the styrene content of the styrene-isoprene-styrene block copolymer is 10 wt% or more and less than 15 wt%, the content of the styrene-isoprene-styrene block copolymer in the pressure-sensitive adhesive layer is preferably 10 to 30 wt% When the styrene content of the isoprene-styrene block copolymer is 15 to 24% by weight, the content of the styrene-isoprene-styrene block copolymer in the pressure-sensitive adhesive layer is preferably 17.5 to 22.5% by weight.

When a styrene-isoprene-styrene block copolymer and polyisobutylene are used as a rubber-based pressure-sensitive adhesive, the styrene content of the styrene-isoprene-styrene block copolymer is preferably greater than 24% by weight and less than 30% by weight. The total content of the styrene-isoprene-styrene block copolymer and polyisobutylene in the pressure-sensitive adhesive layer is preferably 5 to 50% by weight. The blend weight ratio (l / m) of polyisobutylene (l) and styrene-isoprene-styrene block copolymer (m) is preferably 0.20 to 0.80, more preferably 0.30 to 0.70, and most preferably 0.40 to 0.60 Is most preferable.

When an acrylic pressure-sensitive adhesive is used as the pressure-sensitive adhesive, a preferable acrylic pressure-sensitive adhesive is an acrylic ester pressure-sensitive adhesive containing as a main component a polymer containing an alkyl (meth) acrylate as an essential monomer (hereinafter abbreviated as "acrylic polymer"). Examples of the acrylic polymer include a homopolymer or a copolymer containing a (meth) acrylic acid alkyl ester as a monomer. Here, the number of carbon atoms of the alkyl group in the alkyl (meth) acrylate is preferably 4 to 12. The alkyl group may be linear or branched. Examples of the alkyl group include butyl, t-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isonyl, decyl, undecyl and dodecyl. 2-ethylhexyl is preferred. (Meth) acrylic acid alkyl ester may be used alone or in combination of two or more. The content of the acrylic polymer in the acrylic ester pressure-sensitive adhesive is preferably 50% by weight or more, and more preferably 60% by weight or more.

The acrylic polymer may contain a copolymer of the alkyl (meth) acrylate and other monomers copolymerizable therewith. Examples of such other monomers include monomers having a carboxyl group such as (meth) acrylic acid, itaconic acid, maleic acid, and maleic anhydride; Monomers having a sulfo group such as styrenesulfonic acid, allylsulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalenesulfonic acid and acrylamidomethylsulfonic acid; Monomers having a hydroxyl group such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; (Meth) acrylic acid derivatives having an amide group such as (meth) acrylamide, dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide and hydroxyethyl ; (Meth) acrylic acid aminoalkyl esters such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; (Meth) acrylic acid alkoxy esters such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate; (Meth) acrylic acid alkoxyalkylene glycol esters such as (meth) acrylic acid methoxyethylene glycol, (meth) acrylic acid methoxyethyleneglycol, (meth) acrylic acid methoxypolyethylene glycol and (meth) acrylic acid methoxypolypropylene glycol; (Meth) acrylonitrile; Vinyl pyrrolidone, vinyl pyrrolidone, vinyl pyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrrole, vinylimidazole, vinylcaprolactam, vinyloxazole, vinylmorpholine, And vinyl compounds such as polynein. The (meth) acrylic acid alkyl ester and other monomers which are monomer units of the copolymer may be used alone or in combination of two or more.

In the case of using an acrylic pressure-sensitive adhesive, the content of the acrylic pressure-sensitive adhesive in the pressure-sensitive adhesive layer is preferably 30 to 75% by weight, more preferably 35 to 70% by weight, Is from 40 to 65% by weight.

In the case where the pressure-sensitive adhesive layer contains a rubber-based pressure-sensitive adhesive, for example, a resin such as a rosin resin, a polyterpene resin, a coumarone-indene resin, a petroleum resin, a terpene- Of a tackifier is preferably used. The tackifier may be used alone, or two or more tackifiers may be used in combination. As the tackifier, a petroleum resin is preferable. Examples of the petroleum resin include an aliphatic (C5) petroleum resin, an aromatic (C9) petroleum resin, a copolymerization system (C5-C9) petroleum resin, and an aromatic And an alicyclic saturated hydrocarbon resin obtained by adding an alicyclic saturated hydrocarbon resin.

The softening point of the tackifier is preferably 90 to 150 占 폚, more preferably 95 to 145 占 폚. When the softening point is from 90 to 150 캜, it tends to be easily compatible with each component of the pressure-sensitive adhesive layer and easily mixed uniformly. The softening point in the present invention is a value measured by the ring method.

The content of the tackifier in the pressure-sensitive adhesive layer is preferably 10 to 55% by weight, more preferably 10 to 50% by weight, and particularly preferably 10 to 45% by weight. When the content of the tackifier is less than 10% by weight, the tack and cohesive strength may be insufficient. On the other hand, when the content exceeds 55% by weight, the pressure-sensitive adhesive layer becomes hard and the skin adhesiveness tends to deteriorate.

Further, various liquid or paste-like organic components may be further added to these pressure-sensitive adhesive layers from the viewpoint of imparting a soft feeling upon adhering the skin. Here, the term "liquid or paste-like organic component" means that the viscosity at 25 ° C is in the range of 0.01 mPa · s to 10000 Pa · s. The measurement of the viscosity can be performed using, for example, an E-type viscometer (Tokyo Kikazu: EMD type cone-plate type rotary type). The liquid or paste-like organic component is not particularly limited, but preferably has transdermal absorption-promoting effect. Examples of the liquid or paste organic component include glycols such as ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol and polypropylene glycol; glycerin; Oils such as olive oil, castor oil, squalane, and lanolin; Hydrocarbons such as liquid paraffin; Surfactants such as polyoxyethylene hydrogenated castor oil; Stearyl alcohol ethoxylate; Glycerin monoesters such as oleic acid monoglyceride, caprylic acid monoglyceride and lauric acid monoglyceride, glycerin triesters such as glycerin diesters and caprylic acid triglyceride, or mixtures thereof; Fatty acid alkyl esters such as ethyl laurate, isopropyl myristate, isotridecyl myristate, octyl palmitate, isopropyl palmitate, ethyl oleate, diisopropyl adipate and diethyl sebacate; Fatty acids such as oleic acid and caprylic acid; Long-chain alcohols such as 1-dodecanol, 1-tetradecanol, 1-hexadecanol, 2-hexyl-1-decanol, 2-octyl-1-dodecanol and 2-hexyl-1-tetradecanol; N-methylpyrrolidone; 1,3-butanediol, and the like. Fatty acid alkyl esters and long-chain alcohols are suitably used as organic components in the form of a liquid or paste because they greatly contribute to the promotion of absorption of nonsofrolol and the improvement of solubility of nonsofrolol to the pressure-sensitive adhesive layer. The liquid or paste-like organic components may be used singly or in combination of two or more.

Use of a fatty acid alkyl ester and a long-chain alcohol as a liquid or paste-like organic component in combination is preferable in that the permeability and solubility of nonsofrolol and further the skin adhesiveness of the pressure-sensitive adhesive layer are further improved. The weight ratio (c: d) of the fatty acid alkyl ester (c) to the long chain alcohol (d) is preferably from 1: 0.01 to 1: 2, more preferably from 1: 0.01 to 1: 1.5. When the blend weight ratio (d / c) of the long-chain alcohol (d) to the fatty acid alkyl ester (c) in the two kinds of organic components is 0.01 to 2, the solubility of nonsofrolol and the skin adhesiveness of the pressure- I see this.

When the pressure-sensitive adhesive layer contains a liquid or a paste-like organic component, the content of the organic component in the pressure-sensitive adhesive layer is preferably 5 to 70% by weight in order to prevent the organic component from being released from the pressure- More preferably from 10 to 65% by weight, and most preferably from 20 to 50% by weight.

Further, in the adhesive agent of the present invention, a suitable filler may be contained in the pressure-sensitive adhesive layer, if necessary, in view of improving the cohesive strength of the pressure-sensitive adhesive layer. Examples of such fillers include, but are not limited to, inorganic microfine particles such as silica, titanium oxide, zinc oxide, magnesium oxide, iron oxide, aluminum hydroxide, talc, kaolin, bentonite, barium sulfate, calcium carbonate and the like, lactose, carbon black, polyvinylpyrrolidone , Organic fine particles such as polyester, polyolefin, polyurethane, polyamide, cellulose, and acrylic resin, and furthermore, fibers such as polyester, polyolefin, polyurethane, polyamide, cellulose, acrylic resin and glass.

In addition, a cover tape or the like may be adhered to cover a part or the whole surface of the adhesive preparation of the present invention to reinforce skin adhesiveness and to complement the skin adhesion, if desired.

Further, physical crosslinking by irradiation with radiation such as ultraviolet irradiation or irradiation with an electron beam, an isocyanate compound such as trifunctional isocyanate, an organic peroxide, an organic metal salt, a metal alcoholate, a metal chelate compound, a polyfunctional compound Chemical crosslinking treatment using various crosslinking agents such as an external crosslinking agent or a polyfunctional internal crosslinking monomer such as diacrylate or dimethacrylate) may be performed.

The thickness of the pressure-sensitive adhesive layer is preferably 10 to 300 占 퐉, more preferably 10 to 250 占 퐉, and most preferably 15 to 250 占 퐉. When the pressure-sensitive adhesive layer contains a liquid or a paste-like organic component, there is a possibility that the organic component or the like may come out from the perforated line formed on the peripheral edge of the adhesive agent before use or the release liner. However, when the content of the organic component in the liquid phase or the paste and the thickness of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive layer fall within the above-mentioned range, the organic component or the like is prevented from coming out from the perforated line formed in the peripheral portion of the adhesive agent before use or the release liner .

The support is not particularly limited, and a plastic film, a nonwoven fabric, paper, woven fabric, knitted fabric, metal foil or a laminate thereof can be used. Alternatively, the support may be subjected to metal vapor deposition.

The material of the plastic film is not particularly limited, and examples thereof include polyvinyl chloride; Copolymers of monomers such as ethylene, propylene, vinyl acetate, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylonitrile, styrene and vinylidene chloride and other monomers; Olefin polymers such as polyethylene, polypropylene and ethylene-vinyl acetate copolymer; Polyester polymers such as polyethylene terephthalate (PET) and polyether polyester; And polyether-based polymers such as polyether polyamide block copolymers.

The thickness of the support is, for example, 5 to 500 mu m, preferably 10 to 200 mu m.

The adhesive agent of the present invention may further include a release liner on the surface opposite to the support side of the pressure-sensitive adhesive layer (adhering surface to the skin). The release liner covers the pressure sensitive adhesive layer and is intended to protect the adhesive formulation until use.

The release liner is not particularly limited and includes, for example, a plastic film (for example, a polyester film such as a PET film, a polyimide film, a polypropylene film, a polyethylene film, a polycarbonate film and the like); A metal-deposited plastic film on which a metal is deposited on the plastic film; Paper such as paper (Japanese paper), paper (western paper), kraft paper, glasin paper, Fibrous materials such as nonwoven fabric and fabric; Metal foil. Further, laminated sheets of plastic film and paper, laminated sheets of plastic film and metal foil, and the like can also be used as the release liner.

A plastic film is preferable as a release liner, a polyester film is more preferable, and a PET film having a thickness suitable for use in a PET A film is more preferable. The thickness of the release liner is not particularly limited and is, for example, 10 to 200 占 퐉, preferably 25 to 150 占 퐉.

In the release liner, a perforated line may be formed to easily peel off from the pressure-sensitive adhesive layer, or a light-release layer to which a releasing treatment is applied may be formed on the side in contact with the pressure-sensitive adhesive layer.

The stress relaxation rate and shear stress in the present invention are calculated by the following measuring method. As shown in Fig. 2, two separate bakelite plates 21 (100 mm wide × 30 mm long) were fixed on the upper and lower chuck portions 31 of a tensile tester (EZ-S manufactured by SHIMADZU) And the distance between the bakelite plates 21 is adjusted to be 0.1 mm. The lengthwise direction of the adhesive preparation (test piece) cut into a width of 30 mm and a length of 12 mm was attached in parallel with a 2 kg roller so as to cover two bakelites, and then left for 2 minutes under an environment of 23 ° C. and a relative humidity of 65% . Thereafter, the stress was measured at a speed of 1 mm / minute in the direction of the front end of the pressure-sensitive adhesive layer from the starting point to a length of 0.5 mm (0.1 mm + 0.5 mm), and the stress was measured as the shear stress F1 Respectively. Then, the stress (F2) after holding the state at the time of deformation of 0.5 mm (0.1 mm + 0.5 mm) length from the starting point for 120 seconds was measured. The stress relaxation rate was calculated according to the following formula.

Stress relaxation ratio (%) = [1- (Stress F2 after holding for 120 seconds after deformation of 0.5 mm) / (Stress (F1) at deformation of 0.5 mm)] 100

The shear stress suitable for the present invention is 1.0 to 6.5 N / 30 mm wide, more preferably 1.0 to 4.0 N / 30 mm wide, particularly preferably 1.5 to 3.0 N / 30 mm wide. By setting the shear stress to 1.0 to 6.5 N / 30 mm in width, the pressure-sensitive adhesive layer is easily deformed easily, contributing to improvement of the soft feeling of the pressure-sensitive adhesive layer, suppressing the pulling feeling during adhesion, I will exert. Further, when the shear stress exceeds 6.5 N / 30 mm width, the pressure sensitive adhesive layer is hardly deformed, and satisfactory followability to the skin surface can not be obtained.

The stress relaxation rate suitable for the present invention is 20 to 90%, preferably 40 to 90%, particularly preferably 50 to 80%. By setting the stress relaxation rate to 20 to 90%, stress relaxation occurs quickly even when the pressure-sensitive adhesive layer is deformed, and this stress tends to be rapidly reduced. As a result, even when adhered to the skin surface, it acts to reduce the stress applied to the adhesive preparation against movement of the skin surface, so that the peripheral edge of the preparation is not curled while adhered and exhibits excellent skin adhesiveness. When the stress relaxation ratio exceeds 90%, the pressure-sensitive adhesive layer tends to become excessively soft, so that the pressure-sensitive adhesive tends to remain at the time of peeling.

The stress relaxation rate and the shearing stress may be varied depending on the kind of the pressure-sensitive adhesive contained as an essential component in the pressure-sensitive adhesive layer, the tackifier contained as required, the liquid or paste organic component, etc., Accordingly, the thickness of the pressure-sensitive adhesive layer can be set within the above range by increasing or decreasing. For example, when the first polyisobutylene (a) and the second polyisobutylene (b) having different viscosity average molecular weights are used as the rubber-based pressure-sensitive adhesive, the first polyisobutylene (a ) And the second polyisobutylene (b) is preferably 15 to 70% by weight, more preferably 30 to 65% by weight, and most preferably 50 to 65% by weight. The blend weight ratio (a: b) of the first polyisobutylene (a) and the second polyisobutylene (b) is preferably 1: 0.1 to 1: 3, more preferably 1: 0.5 to 1: 2, more preferably from 1: 0.65 to 1: 0.97, and most preferably from 1: 0.77 to 1: 0.97. The thickness of the pressure-sensitive adhesive layer is preferably 10 to 300 占 퐉, more preferably 10 to 250 占 퐉, and most preferably 15 to 250 占 퐉. As described above, when the first polyisobutylene (a) and the second polyisobutylene (b) are used as the rubber adhesive, the total amount of the components (a) and (b) in the pressure- And the combined weight ratio of the component (a) and the component (b) fall within the above-mentioned preferable range, the stress relaxation rate and the shearing stress can be set within the above-mentioned preferable range, and their numerical values can be increased or decreased.

<Examples>

EXAMPLES Next, the present invention will be described in detail by way of examples, but these examples are not intended to limit the present invention. The abbreviations used in Examples and the like are as follows.

BSP: Glass type non-soaprolol

PIB1: polyisobutylene, viscosity average molecular weight 4,000,000

PIB2: polyisobutylene, viscosity average molecular weight 400,000

PIB3: polyisobutylene, viscosity average molecular weight 55,000

SIS1: Styrene-isoprene-styrene block copolymer (styrene content: 25% by weight, diblock ratio: 17% by weight)

SIS2: styrene-isoprene-styrene block copolymer (styrene content: 25% by weight, diblock ratio: 42% by weight)

SIS3: styrene-isoprene-styrene block copolymer (styrene content: 22% by weight, diblock ratio: 15% by weight)

SIS4: styrene-isoprene-styrene block copolymer (styrene content: 14% by weight, diblock ratio: 26% by weight)

TF1: tackifier, alicyclic saturated hydrocarbon resin, softening point 100 캜

TF2: tackifier, alicyclic saturated hydrocarbon resin, softening point 140 캜

Liquid Para: Liquid Paraffin

IPM: isopropyl myristate

ODO: 2-octyl-1-dodecanol

(Examples 1 to 8 and Comparative Examples 1 to 8)

A viscous composition toluene solution of the pressure-sensitive adhesive composition was prepared in accordance with the compounding ratios shown in Table 1 and the obtained solution was coated on a polyethylene terephthalate (PET) liner (thickness 75 탆) And dried in a hot-air circulating drier at 100 DEG C for 5 minutes to form a pressure-sensitive adhesive layer. This pressure-sensitive adhesive layer was bonded to the nonwoven fabric side of a laminated film of a PET film having a thickness of 2 탆 and a PET nonwoven fabric having a weight of 12 g / m ² to obtain a sheet-like adhesive preparation. Table 2 shows the results of the measurement of the stress relaxation rate and shear stress of the obtained adhesive preparation by the above-mentioned method. The blending ratios of the respective components shown in Table 1 are the ratios (% by weight) to the whole of the pressure-sensitive adhesive composition.

(1) Adhesion

The adhesive strengths of the adhesive preparations obtained in Examples 1 to 8 and Comparative Examples 1 to 8 were measured by the following methods. The surface of the stainless steel plate (SUS304 steel sheet specified in JIS G4305) was uniformly polished with 360 times of water-resistant abrasive paper, followed by washing with a cloth soaked with ethyl acetate. The non-soaprolol-containing adhesive preparation was cut to prepare a test piece having a width of 24 mm and a length of 50 mm. The adhesion side of the test piece from which the liner was peeled was bonded to the polished and cleaned surface of the stainless steel plate using a rubber roller having a mass of 2 kg (rubber roller passing speed 300 mm / min, number of times of passing twice). The stainless steel plate to which the test piece was bonded was allowed to stand for 30 minutes under an atmosphere of 23 ± 2 ° C. and 65 ± 10% RH. One end of the test piece was peeled from the stainless steel plate by about 5 mm, folded at an angle of 180, and an auxiliary paper (width 30 mm) was attached. One end of the auxiliary paper was sandwiched between the upper claws using a tensile tester and the stainless steel plate was sandwiched between the claws at the bottom and 180 ° at a speed of 300 mm / min under an atmosphere of 23 ± 2 ° C. and 65 ± 10% And the adhesive strength was measured. The results are shown in Table 3.

(2) Adhesiveness

From the adhesive force, adhesion was judged by the following criteria.

If the adhesive force is 0.1 N / 24 mm or less, the adhesive force is weak and there is a possibility of peeling at the time of attachment.

When the adhesive strength was more than 0.1 N / 24 mm width and less than 2.0 N / 24 mm width, it was judged that the adhesive property was good (O) because there was no fear of skin irritation upon peeling with proper adhesive force.

When the adhesive strength was not less than 2.0 N / 24 mm width and less than 3.0 N / 24 mm width, it was judged that the adhesive property was excellent (⊚) because of excellent skin adhesiveness and no skin irritation upon peeling.

When the adhesive strength was not less than 3.0 N / 24 mm width and less than 3.9 N / 24 mm width, skin irritation upon peeling may occur.

When the adhesive strength was 3.9 N / 24 mm or more, the adhesive strength was strong and skin irritation occurred at the time of peeling.

The results are shown in Table 3.

(3) Elasticity of the pressure-sensitive adhesive layer

From the stress relaxation rate, the stretchability of the pressure-sensitive adhesive layer was determined according to the following criteria.

If the stress relaxation rate is less than 20%, it is judged that stretchability is not possible (X) because the followability to the skin surface is not sufficient and there is a fear of pulling or peeling off at the time of sticking.

When the stress relaxation rate was 20% or more and 90% or less, it was judged that the stretchability was good (O) because it had proper followability and did not cause uncomfortable feeling at the time of attachment or curling of peripheral edges.

If the stress relaxation rate is more than 90%, the pressure-sensitive adhesive layer becomes excessively soft and there is a possibility that adhesive residue may be formed at the time of peeling.

The results are shown in Table 3.

(4) presence or absence of transcription

In the above item (1), the surface of the stainless steel plate after the measurement of the adhesive force was visually observed, and the presence or absence of the transferred substance on the surface of the stainless steel plate was evaluated according to the following criteria. The results are shown in Table 3.

○: Transpositions do not exist

△: Some transit exists

X: Transmission is present on the entire surface of the attachment point

As apparent from Table 3, Examples 1 to 8, in which the shear stress and the stress relaxation rate are shown in Table 2 as being within a preferable range, show good adhesion and stretchability, and also exhibit excellent transferability to the adherend after peeling And exhibited good releasability. In addition, Examples 1 to 4 and 7 exhibited a sufficiently high stress relaxation rate, so that the effect of reducing the stress applied to the adhesive preparation against the movement of the skin surface when adhered to the skin surface was excellent, It is presumed that it is possible to prevent the curling of the hair.

On the other hand, in Comparative Examples 1 to 3 in which the shear stresses in Table 2 were found to be less than the lower limit of the acceptable range, the adhesive strength was remarkably low and the adhesiveness was poor. Further, since the pressure-sensitive adhesive layer component was not retained in the pressure-sensitive adhesive layer and blurring was observed on the surface, a transferred article was present on the adherend after peeling.

In Comparative Examples 4 to 8, in which the preparation was peeled off from the adherend during the stress relaxation test, it was estimated that the stress relaxation rate was 10% or less. The skin surface on which the adhered surface was stretched or contracted did not show sufficient follow- It was presumed to abandon it.

From the above, by making the stress relaxation rate 20 to 90% and the shear stress 1.0 to 6.5 N / 30 mm wide, it is possible to alleviate and disperse the stress when adhering to and peeling off the skin surface, As a result, it has become possible to reduce the irritation at the time of peeling.

Although the present invention has been described in detail with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

The present application is based on Japanese patent application (Japanese Patent Application No. 2013-185601) filed on September 6, 2013 and Japanese Patent Application (Japanese Patent Application No. 2014-177675 filed on September 2, 2014) , And is entirely cited by reference.

1: Support
2: Pressure-sensitive adhesive layer
3: peeling liner
10: Adhesive preparation (test piece)
21: bakelite plate
31:

Claims (8)

A pressure-sensitive adhesive sheet comprising a support, and a pressure-sensitive adhesive layer containing a glass-like non-soeprolol and a pressure-sensitive adhesive laminated on one side of the support,
The pressure-sensitive adhesive layer has a stress relaxation rate of 20 to 90%
Wherein the pressure-sensitive adhesive layer has a shear stress of 1.0 to 6.5 N / 30 mm in width. The pressure-sensitive adhesive sheet according to claim 1, wherein the pressure-sensitive adhesive layer has a stress relaxation rate of 40 to 90%
Wherein the pressure-sensitive adhesive layer has a shear stress of 1.0 to 4.0 N / 30 mm in width. 3. The adhesive preparation according to claim 1 or 2, wherein the pressure-sensitive adhesive comprises a rubber-based pressure-sensitive adhesive. The adhesion agent according to claim 3, wherein the rubber adhesive is polyisobutylene and / or styrene-isoprene-styrene block copolymer. 5. The adhesive formulation according to claim 4, wherein the polyisobutylene is polyisobutylene having a viscosity average molecular weight of 40,000 to 5,500,000. 5. The polyisobutylene according to claim 4, wherein the polyisobutylene comprises a first polyisobutylene (a) having a viscosity average molecular weight of 1,800,000 to 5,500,000 and a second polyisobutylene (b) having a viscosity average molecular weight of 40,000 to 85,000 , And the mixing ratio (a: b) of the first polyisobutylene (a) and the second polyisobutylene (b) in the weight ratio of 1: 0.1 to 1: 3. 5. The adhesive preparation according to claim 4, wherein the styrene-isoprene-styrene block copolymer has a styrene content of less than 30% by weight. The adhesive preparation according to claim 4 or 7, wherein the content of the styrene-isoprene-styrene block copolymer in the pressure-sensitive adhesive layer is 5 to 50% by weight.

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