HK1163249A - Patch and evaluation method of patch - Google Patents

Description

Adhesive patch and method for evaluating adhesive patch

The present application is a divisional application of an invention patent application having chinese application No. 200780043258.8 (the name of the original application is "patch and evaluation method of patch", and the date of application of the original application is 11/29/2007).

Technical Field

The present invention relates to an adhesive patch, and more particularly to an adhesive patch including an adhesive layer containing a styrene-isoprene-styrene block copolymer. In addition, the present invention relates to a method for evaluating the characteristics of the patch.

Background

Conventionally, a patch (e.g., a plaster) for application to the skin has been widely used. These patches are products for percutaneous absorption of drugs by being applied to the skin, and therefore adhesiveness (attachment property) of the patch to the skin is important.

Therefore, the skilled person has made various studies on the adhesiveness of the patch, and attempts have been made to use a styrene-isoprene-styrene block copolymer (hereinafter also referred to as SIS block copolymer) as an adhesive component in view of the fact that the patch can be produced by hot melting without using a solvent.

For example, the following patches have been disclosed: an adhesive patch containing indomethacin (indomethacin), an SIS block copolymer, liquid paraffin (liquid paraffin), and polyethylene glycol (see patent document 1), an adhesive patch containing an SIS block copolymer, crotamiton (crotamiton), and an anti-inflammatory analgesic (see patent document 2), or the like is provided in the adhesive layer.

According to these patches, since the SIS block copolymer is blended in the adhesive layer, the patch can be produced by hot melting without using a solvent, can be produced easily and at low cost, and can reduce the environmental load.

Patent document 1: japanese patent laid-open No. 2001-302502

Patent document 2: japanese patent laid-open No. Hei 4-321624

Disclosure of Invention

However, the conventional adhesive patches described above have the following problems.

First, since the self-adhesion of the adhesive patch (here, "self-adhesion" means the adhesive force, the sticking property, and the like between the surfaces of the adhesive agent layers of the adhesive patch, which does not include the concept of not adhering to an object other than the adhesive surface) is too strong, the adhesive surfaces easily adhere to each other and it is difficult to peel off the already-adhered surfaces when the release film is peeled off, the adhesive patch is attached to the skin, and the skin is attached again.

Second, the adhesive patch has too strong adhesion to the skin, and thus causes great pain to the user when it is peeled from the skin.

Accordingly, an object of the present invention is to provide an adhesive patch using an SIS block copolymer as an adhesive component, which can improve the usability and can reduce the irritation to the user.

The present inventors have found that when the tan δ at 32 ℃ determined by measuring the dynamic viscoelasticity of an adhesive is in a predetermined range, the usability of the adhesive can be improved and the irritation to the user can be reduced, and have completed the present invention. The present invention specifically provides the following.

(1) An adhesive patch comprising a flexible support and an adhesive layer laminated on the support, wherein the adhesive layer contains a styrene-isoprene-styrene block copolymer, and the tan delta value at 32 ℃ obtained by measuring dynamic viscoelasticity satisfies the following formula 1 at least at one point of frequencies of 0.04Hz to 0.25 Hz.

0.25x +0.05 ≤ y ≤ 0.25x +0.10

(wherein x is frequency (Hz) and y is tan. delta.)

(2) The adhesive patch according to (1), wherein the tan δ value at 32 ℃ obtained by measuring the dynamic viscoelasticity satisfies the above formula 1 at any point of the frequency of 0.04Hz to 0.25 Hz.

(3) An adhesive patch comprising a flexible support and an adhesive layer laminated on the support, wherein the adhesive layer contains a styrene-isoprene-styrene block copolymer, and the tan δ value at 32 ℃ obtained by measuring dynamic viscoelasticity satisfies the following numerical formula 2 at least one point of frequencies of 0.04Hz to 0.10 Hz.

0.25x +0.05 ≤ y ≤ 0.65x +0.09

(wherein x is frequency (Hz) and y is tan. delta.)

(4) The adhesive patch according to (3), wherein the tan δ value at 32 ℃ obtained by measuring the dynamic viscoelasticity satisfies the above numerical formula 2 at any point of the frequency of 0.04Hz to 0.10 Hz.

(5) The patch according to any one of (1) to (4), wherein the adhesive layer further contains a tackifier and a plasticizer.

(6) The patch according to (5), wherein the styrene-isoprene-styrene block copolymer is contained in an amount of 10 to 40 mass%, the tackifier is contained in an amount of 10 to 35 mass%, and the plasticizer is contained in an amount of 20 to 60 mass%, with respect to the entire adhesive agent layer.

(7) The patch according to any one of (1) to (6), wherein the styrene-isoprene-styrene block copolymer has a mass ratio of styrene to isoprene (styrene/isoprene) of 20/80 to 25/75.

(8) A method for evaluating an adhesive patch, characterized in that the adhesive patch comprises a flexible support and an adhesive layer laminated on the support, and the adhesive patch is evaluated on the basis of a tan delta value, which is obtained by measuring the dynamic viscoelasticity of the adhesive layer and is at a temperature at which the adhesive patch is applied.

According to the present invention, since the tan δ value at 32 ℃ and at a frequency of 0.04Hz to 0.25Hz, which is obtained by measuring the dynamic viscoelasticity, is set to a predetermined range, the usability of the patch using the SIS block copolymer as an adhesive component can be improved and the irritation to the user can be reduced.

Further, according to the present invention, since the tan δ value at 32 ℃ and at a frequency of 0.04Hz to 0.10Hz, which is obtained by measuring the dynamic viscoelasticity, is set to a predetermined range, the usability of the patch using the SIS block copolymer as an adhesive component can be improved and the irritation to the user can be reduced.

Drawings

FIG. 1: is a graph showing the relationship between the frequency and tan δ of the patch of the example of the present invention.

FIG. 2: is a graph showing the relationship between the frequency and tan δ in a specific range of the patch of the example of the present invention.

FIG. 3: is a graph showing the average load required for the patch of the example of the present invention to peel off at the time of self-adhesion.

Detailed Description

An example of the embodiment of the present invention will be described below, but the present invention is not limited to the embodiment below.

The adhesive patch of the present invention comprises a flexible support and an adhesive layer laminated on the support. Here, the patch of the present invention is mainly used for application to the skin, and includes a plaster agent, a cataplasm (cataplasma), an adhesive plaster, a sheet agent, a wound dressing, a cosmetic dressing, etc., but does not include an industrial adhesive plaster.

< adhesive agent layer >

The adhesive layer constituting the patch contains an SIS block copolymer as an essential component, and preferably further contains a tackifier and a plasticizer. In the present specification, all components contained in the adhesive layer are referred to as an adhesive.

[ SIS Block copolymer ]

The SIS block copolymer is one of rubber adhesives, belongs to A-B-A type polymers, and is a styrene thermoplastic elastomer with the following molecular structure model: the end block A is polystyrene and the rubber mid block B is polyisoprene.

The SIS block copolymer used in the present invention is not particularly limited, and may be an SIS block copolymer having a solution viscosity (MPa.s [ cps ], 25 ℃) of about 100 to 3000, a mass ratio of styrene to isoprene may be 10/90 to 30/70, and a mass ratio of styrene to isoprene (styrene/isoprene) is 20/80 to 25/75. Thus, by using an SIS block copolymer having a large styrene mass ratio, the production of an adhesive can be facilitated.

Specifically, the following commercially available SIS-based resin can be used. Examples thereof include: an SIS-based resin having a styrene/rubber ratio (% by mass) of 15/85 and a solution viscosity (MPa.s [ cps ], 25 ℃) of 1,500 (trade name: Kraton D-1107); an SIS resin having a styrene/rubber ratio (% by mass) of 15/85 and a solution viscosity (MPa.s [ cps ], 25 ℃) of 900 (trade name: KratonD-1112); an SIS resin having a styrene/rubber ratio (% by mass) of 17/83 and a solution viscosity (MPa.s [ cps ], 25 ℃) of 500 (trade name: Kraton D-1117P); an SIS resin having a styrene/rubber ratio (% by mass) of 22/78 (trade name: Kraton D-KX 401); an SIS resin having a styrene/rubber ratio (% by mass) of 16/84 (trade name: Kraton D-KX 406); an SIS resin having a styrene/rubber ratio (% by mass) of 30/70 and a solution viscosity (MPa.s [ cps ], 25 ℃) of 300 (trade name: Kraton D-1125 x); an SIS-based resin (trade name: Kraton D-1320x) having a styrene/rubber ratio (% by mass) of 10/90 and a solution viscosity (MPa.s [ cps ], 25 ℃) of 2,500 (each manufactured by Kraton JSR Elastomers Co., Ltd.). The SIS block copolymer used in the present invention may contain one or two or more kinds of these SIS resins, and an SIS resin having a styrene/rubber ratio (% by mass) of 22/78 (trade name: KratonD-KX401) is preferable.

The content of the SIS block copolymer is not particularly limited, and is preferably 10 to 40 mass% with respect to the entire adhesive. When the content of the SIS block copolymer is too small, the aggregating power is insufficient; on the other hand, an excessively high content of the SIS block copolymer is not preferable because the skin-adherability is insufficient.

[ tackifier ]

The tackifier used in the present invention is not particularly limited, and for example, alicyclic saturated hydrocarbon resins (synthetic petroleum resins), rosin ester (rosin ester) derivatives, terpene resins, phenol resins, and the like are preferable.

The alicyclic saturated hydrocarbon resin is not particularly limited, and may be, for example, "Arkon P-100 (trade name)" (manufactured by Ishikawa chemical industries, Ltd.).

The rosin ester derivative is not particularly limited, and examples thereof include "Estergum H (trade name)" (manufactured by Mitsuwa chemical industries, Ltd.), "KE-311 (trade name)" (manufactured by Mitsuwa chemical industries, Ltd.), "KE-100 (trade name)" (manufactured by Mitsuwa chemical industries, Ltd.).

The terpene Resin is not particularly limited, and may be, for example, "YS Resin (trade name)" (manufactured by Yasuhara Chemical corporation).

The tackifier used in the present invention may contain one or two or more of these tackifiers, for example.

The content of the tackifier is not particularly limited, and is preferably 10 to 35 mass% with respect to the entire adhesive. When the content of the thickener is too small, the adhesive force is insufficient; on the other hand, if the content of the thickener is too large, the adhesive force is too strong, and the user is greatly affected when the thickener is peeled off from the skin.

[ plasticizer ]

The plasticizer used in the present invention is not particularly limited, and may be, for example: and higher alcohols such as liquid paraffin, hydrogenated oil, hydrogenated castor oil, and octyldodecanol, and fatty acid esters such as squalane, squalene, castor oil, liquid rubber (polybutene), and isopropyl myristate. The plasticizer used in the present invention may contain, for example, one or two or more of these plasticizers. Among these plasticizers, liquid paraffin, hydrogenated oil, and hydrogenated castor oil are preferable.

The content of the plasticizer is preferably 20 to 60 mass% with respect to the entire adhesive. If the content of the plasticizer is too small, the adhesive layer is excessively cured, thereby resulting in insufficient adhesive force. On the other hand, if the amount of the plasticizer to be blended is too large, the adhesive layer is excessively softened, and there arise problems such as excessive stickiness, great pain to the user when peeled from the skin, and adhesive residue. The content of the plasticizer is more preferably 25 to 50% by mass, and still more preferably 30 to 50% by mass.

[ optional Components ]

The adhesive agent layer constituting the patch may contain, in addition to the above components, optional components such as a medicinal component, an excipient, an antioxidant, a drug dissolving agent, a transdermal absorption enhancer, a perfume, and a coloring agent, as required. The arbitrary component may be one or two or more of these arbitrary components.

(pharmaceutical composition)

The pharmaceutical agent component may be, for example: examples of the skin-whitening agent include agents having a skin-whitening effect such as general anesthetics, hypnotics, analgesics, anti-inflammatory analgesics, steroid hormones, stimulants/conscious agents, psychotropics, local anesthetics, skeletal muscle relaxants, autonomic nerves, antiallergic agents, antihistamines, cardiotonics, arrhythmia agents, diuretics, hypotensives, vasoconstrictors, vasodilators, calcium antagonists, antibacterial/antibacterial agents, agents for parasitic skin diseases, skin softeners, antibiotics, antidotes, antitussives, antipruritics, hypnotics, psychostimulants, anti-ulcer agents, vitamins, and skin-beautifying ingredients.

Further, when the patch of the present invention is used as a patch of a topical action type, examples of the agent contained in the patch include: anti-inflammatory analgesics such as indomethacin, ketoprofen (ketoprofen), flurbiprofen (flurbiprofen), loxoprofen (loxoprofen), loxoprofen sodium (loxoprofen sodium), piroxicam (piroxicam), meloxicam (meloxicam), ketorolac (ketorolac), felbinac (felbinac), diclofenac (diclofenac), and diclofenac sodium. Among these agents, at least one agent selected from the group consisting of indomethacin, ketoprofen, felbinac, loxoprofen, diclofenac, and salts thereof is preferable. The content of the chemical is not particularly limited, and is usually about 0.1 to 20 mass% with respect to the entire adhesive.

(excipients)

The excipient is not particularly limited, and examples thereof include: silicon compounds such as anhydrous silicic acid, light anhydrous silicic acid, and hydrous silicic acid, cellulose derivatives such as ethyl cellulose, methyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose, water-soluble polymers such as polyvinyl alcohol, aluminum compounds such as dried aluminum hydroxide gel and hydrous aluminum silicate, kaolin, titanium oxide, and the like.

(antioxidant)

The antioxidant is not particularly limited, and examples thereof include: dibutylhydroxytoluene, ascorbic acid, tocopherol ester derivatives, butylhydroxyanisole, 2-mercaptobenzimidazole, and the like.

(drug dissolving agent-percutaneous absorption enhancer)

The drug-dissolving agent or transdermal absorption enhancer is not particularly limited, and there may be mentioned: polyethylene glycol (average molecular weight 200 to 30000), polyhydric alcohols such as glycerol, ethylene glycol and diethylene glycol, fatty acids such as oleic acid, isostearic acid and citric acid, fatty acid esters such as isopropyl myristate, isopropyl palmitate and diisopropyl adipate, fatty acid polyol esters such as caprylic monoglyceride, caprylic triglyceride and sorbitan fatty acid ester, terpenes such as menthol, menthol derivatives, peppermint oil and limonene, N-methyl-2-pyrrolidone, crotamiton and polyvinyl alcohol.

< support >

The support used in the present invention is not particularly limited, and a stretchable or non-stretchable woven fabric or nonwoven fabric such as polyethylene or polypropylene, a film such as polyethylene, polypropylene, an ethylene-vinyl acetate copolymer or polyvinyl chloride, or a foamable support such as urethane or polyurethane may be used. The support may be used alone or in a stack of two or more of these supports.

< liner >

The adhesive patch of the present invention includes a flexible support and an adhesive layer having an adhesive applied to one surface of the support, and generally, the adhesive patch includes a releasable liner laminated on the adhesive layer.

Examples of the release liner generally used in the present invention include: a film of polyethylene, polypropylene, an ethylene-vinyl acetate copolymer, polyvinyl chloride, or the like, a metallic film deposited with aluminum, or the like, or a liner having a surface subjected to a release treatment such as a siliconizing treatment. The "releasable liner" used in the present invention is preferably, for example, in terms of easy releasability: a liner having a linear or curved cut, a liner having a configuration in which 2 or more liners are partially overlapped, and a liner having a folded portion.

< production method >

(preparation of adhesive)

The adhesive of the patch of the present invention is produced by the following method: the raw material composition containing the SIS block copolymer is mixed and stirred under a shear load (stirring speed of 50 to 1500 rpm) by using a Henschel mixer (registered trademark) or the like from the time of melting to the time of becoming a molten state (room temperature to 250 ℃). By using the method, the adhesive having the physical parameters of the present invention can be manufactured.

The mixing and stirring are not particularly limited, and the raw material composition may be stirred from the start of melting until it is in a molten state. The temperature during mixing and stirring is preferably 50 ℃ or higher. Preferably, the stirring is performed simultaneously with the shear load, and the stirring speed in this case is preferably 50rpm or more, more preferably 100rpm or more.

Examples of the apparatus used for mixing and stirring include: a henschel mixer (registered trademark), a kneader, an open roll, a mixing roll, an internal mixer (internnalmixer), a Banbury mixer (Banbury mixer), a Plastomill mixer, a twin-screw mixer, an extrusion mixer, and the like. Among these apparatuses, a henschel mixer (registered trademark) is preferable in terms of ease of high-speed stirring.

(preparation of Patch (ointment preparation))

The adhesive layer applied to the support of the adhesive patch of the present invention preferably has a thickness of 90 to 250 μm. If the thickness of the adhesive agent layer is too large, the edge portion of the adhesive agent is easily scraped to clothes and the like during use and is easily peeled off, while if the thickness of the adhesive agent layer is too small, the adhesive agent loses its support property and a problem of erroneous sticking is easily caused.

The method for producing the adhesive patch of the present invention is not limited to the above-mentioned steps, and the temperature conditions, the stirring rotation speed, the stirring time, and the like may be adjusted in accordance with the production equipment, the production scale, and the like.

As described later, according to the manufacturing method, the following adhesive can be easily manufactured: the tan delta value at 32 ℃ obtained by measuring the dynamic viscoelasticity satisfies the following formula 1 at least at one point of frequencies of 0.04Hz to 0.25 Hz.

0.25x +0.05 ≤ y ≤ 0.25x +0.10

(wherein x is frequency (Hz) and y is tan. delta.)

< measurement of tan. delta. >

tan δ is a physical property value calculated from a loss modulus (G ″) and a storage modulus (dynamic shear modulus) (G') according to the following formula.

tanδ＝G″/G′

the tan δ can be measured, for example, using a Rheometric dynamic analyzer (Rheometric dynamic analyzer) as a measuring device in the following manner.

First, an adhesive is scraped off from an adhesive patch, and 50 to 75mg of the adhesive is held in a cylindrical holder in the device. Then, at 32 ℃, the stress when the strain was applied by increasing the frequency from 0.01Hz to 80Hz at a common ratio of 1.259Hz was measured, and the loss modulus (G ″) and the storage modulus (dynamic shear modulus) (G') were calculated based on the measured values to obtain the tan δ value.

The adhesive constituting the adhesive patch of the present invention satisfies the following formula 1 at least one point of frequencies of 0.04Hz to 0.25Hz, and the tan δ value at 32 ℃ obtained by measuring the dynamic viscoelasticity.

0.25x +0.05 ≤ y ≤ 0.25x +0.10

(wherein x is frequency (Hz) and y is tan. delta.)

The tan δ value at 32 ℃ obtained by measuring the dynamic viscoelasticity preferably satisfies the formula 1 at any point of the frequency of 0.04Hz to 0.25Hz, from the viewpoint that the usability can be further improved and the irritation to the user can be further reduced. The "arbitrary point at a frequency of 0.04Hz to 0.25 Hz" means all the measurement points at a frequency of 0.04Hz to 0.25Hz, and the number of all the measurement points is not particularly limited.

The adhesive constituting the adhesive patch of the present invention satisfies the following formula 2 at least at one point of frequencies of 0.04Hz to 0.10Hz, and the tan δ value at 32 ℃ obtained by measuring the dynamic viscoelasticity.

0.25x +0.05 ≤ y ≤ 0.65x +0.09

(wherein x is frequency (Hz) and y is tan. delta.)

The adhesive constituting the adhesive patch of the present invention satisfies the following expression 3 or 4, more preferably expression 5, at least one point of the frequency of 0.04Hz to 0.10Hz, more preferably the tan δ value at 32 ℃ obtained by measuring the dynamic viscoelasticity.

0.25x +0.05 ≤ y ≤ 0.25x +0.10

Y is not less than 0.35x +0.04 and not more than 0.65x +0.09

0.35x +0.04 ≤ y ≤ 0.25x +0.10

(wherein x is frequency (Hz) and y is tan. delta.)

The tan δ value at 32 ℃ obtained by measuring the dynamic viscoelasticity preferably satisfies any one of the numerical expressions 2 to 5 at any point of the frequency 0.04Hz to 0.10Hz, from the viewpoint that the usability can be further improved and the irritation to the user can be further reduced. The "arbitrary point of frequency 0.04Hz to 0.10 Hz" means all the measurement points of frequency 0.04Hz to 0.10Hz, and the number of all the measurement points is not particularly limited.

From another viewpoint, the adhesive has a tan δ value at 32 ℃ and a frequency of 0.10Hz of 0.065 to 0.165, preferably 0.075 to 0.155, and more preferably 0.079 to 0.154, which is obtained by measuring dynamic viscoelasticity.

From another viewpoint, the adhesive has a tan δ value at 32 ℃ and a frequency of 0.05Hz, which is obtained by measuring dynamic viscoelasticity, of 0.053 to 0.150, preferably 0.0625 to 0.143, and more preferably 0.0625 to 0.113.

32 ℃ is the average temperature of the human epidermis to which the patch is normally applied. Therefore, it is presumed that the tan δ value at 32 ℃ obtained by measuring the dynamic viscoelasticity reflects the characteristics of the patch at the time of use. Therefore, when the temperature of the application target of the adhesive patch changes, the adhesive patch can be evaluated based on the tan δ value at that temperature obtained by measuring the dynamic viscoelasticity of the adhesive layer. As described above, the "temperature of the patch to be applied" can be appropriately set according to the use of the patch and the like.

The adhesive constituting the adhesive patch of the present invention preferably has a glass transition temperature (Tg) of-45 ℃ to-35 ℃, more preferably-43 ℃ to-35 ℃.

Examples

The present invention will be specifically illustrated below by way of examples, but the present invention is not limited to these examples.

< example 1>

In a Henschel mixer (registered trademark, manufactured by Mitsui mine Co., Ltd.), 22.5g of dibutylhydroxytoluene as an antioxidant and 2250g of "Ester gum H (trade name)" as a thickener heated in advance were added to 4162.5g of liquid paraffin (Moresco White P-350P; manufactured by Sonmura oil research institute Co., Ltd.) as a plasticizer, and the mixture was mixed at a rotation speed of 200rpm and a temperature of 100 ℃.

To the mixture was added 2250g of an SIS block copolymer (D-KX401 CS; manufactured by Kraton JSR Elastomers Co., Ltd.) in which the mass ratio of styrene to isoprene (styrene/isoprene) was 22/78, and the mixture was melted by shearing at a rotation speed of 900rpm and a temperature of 100 ℃ and heating to 190 ℃.

The melt was then sheared at a rotational speed of 900rpm and stirred for 20 minutes. 135g of 1-menthol and 180g of N-methyl-2-pyrrolidone as a drug-dissolving agent and a transdermal absorption enhancer were added to the stirred mixture, and the mixture was mixed and stirred to prepare an adhesive.

Then spreading the prepared adhesiveThe weight per unit area is 100g/m²The knitted fabric (polyester) of (1) was laminated with a siliconized backing (PET) on the adhesive so that the thickness thereof was 150 μm, to prepare a patch (plaster).

< example 2>

An adhesive was prepared and a patch (plaster) was prepared in the same manner as in example 1 except that the amount of liquid paraffin added was 3870g, the amount of 1-menthol added was 270g, the amount of dibutylhydroxytoluene added was 90g, and diclofenac sodium was added 90 g.

< example 3>

An adhesive agent and a patch (plaster) were prepared in the same manner as in example 2 except that ketoprofen was added in place of diclofenac sodium and "KE-100 (trade name)" was added in place of "Ester gum H (trade name)".

< example 4>

An adhesive was prepared by the same procedure as in example 3 except that 3847.5g of liquid paraffin and 112.5g of dibutylhydroxytoluene were added and "Ester gum H (trade name)" was used instead of "KE-100 (trade name)", thereby preparing an adhesive patch (plaster).

< example 5>

An adhesive agent and an adhesive patch (plaster) were prepared in the same manner as in example 1 except that 3856.5g of liquid paraffin and 360g of N-methyl-2-pyrrolidone were added and "KE-100 (trade name)" was used instead of "Ester gum H (trade name)", and 90g of indomethacin and 36g of citric acid were further added.

< example 6>

An adhesive agent and a patch (plaster) were prepared in the same manner as in example 5, except that 3654g of liquid paraffin, 45g of dibutylhydroxytoluene, 180g of hydrogenated oil, and diclofenac sodium instead of indomethacin were added.

< example 7>

An adhesive agent was prepared by the same procedure as in example 1 except that the amount of addition of "D-KX 401CS (trade name)" was 3150g, the amount of addition of "Ester gum H (trade name)" was 2700g, the amount of addition of liquid paraffin was 3150g, and N-methyl-2-pyrrolidone, 1-menthol, and dibutylhydroxytoluene were not added, to thereby prepare a patch (plaster).

< example 8>

An adhesive agent was prepared by the same procedure as in example 1 except that the amount of addition of "D-KX 401CS (trade name)" was 1800g, the amount of addition of liquid paraffin was 3510g, the amount of addition of 1-menthol was 90g, 180g of hydrogenated oil and 90g of felbinac were further added, but dibutylhydroxytoluene was not added, and 3510g of "KE-100 (trade name)" was added instead of "Ester gum H (trade name)", to thereby prepare an adhesive patch (plaster).

< example 9>

An adhesive agent was prepared by the same procedure as in example 1 except that 1350g of "D-KX 401CS (trade name)" was added, 2700g of "Ester gum H (trade name)" was added, 3960g of liquid paraffin was added, and 900g of an SIS block copolymer (D-1107; manufactured by Kraton JSR Elastomers Co., Ltd.) in which the mass ratio of styrene to isoprene (styrene/isoprene) was 15/85 and N-methyl-2-pyrrolidone, 1-menthol and dibutylhydroxytoluene were not added, and 90g of ketoprofen were added, thereby preparing an adhesive patch (plaster).

< example 10>

An adhesive agent and a patch (plaster) were prepared in the same manner as in example 6 except that the amount of "D-KX 401CS (trade name)" was 2700g, 3127.5g, 450g, 22.5g, and 45g, respectively, of liquid paraffin, N-methyl-2-pyrrolidone, dibutylhydroxytoluene, and citric acid, respectively.

Comparative example 1

An adhesive and a patch (plaster) were prepared in the same manner as in example 3, except that the amount of N-methyl-2-pyrrolidone added was 270g, and "D-1107 (trade name)" was added instead of "D-KX 401CS (trade name)" and ketoprofen was not added.

Comparative example 2

An adhesive was prepared and an adhesive patch (plaster) was prepared in the same manner as in example 2 except that 3780g of liquid paraffin was added, 270g of N-methyl-2-pyrrolidone was added, and "D-1107 (trade name)" was added instead of "D-KX 401CS (trade name)".

The compositions of examples 1 to 10 and comparative examples 1 to 2 are summarized in Table 1.

TABLE 1

SIS: SIS block copolymers

EGH: ester gum H (rosin Ester derivative)

KE: KE-100 (rosin ester derivative)

BHT: dibutylhydroxytoluene

And (3) LP: liquid paraffin

NMP: n-methyl-2-pyrrolidone

L-MEN: 1-menthol

KP: ketoprofen

DFNa: diclofenac sodium

ID: indometacin

FB: biphenylacetic acid

The adhesive physical property values (tan δ) of the adhesive were measured for examples 1 to 10, comparative examples 1 to 2, and commercially available adhesive patches a to g containing SIS adhesive, and the self-adhesiveness (use property), skin irritation, skin adhesiveness, and skin adhesiveness in the presence of moisture (water resistance) were evaluated. The commercially available products are a "MOHRUS TAPE" (manufactured by JIUKI YAKUBAN Co., Ltd.), b "YAKUBAN" (manufactured by TOKURON Co., Ltd.), c "FLEX" (manufactured by JIUKI YAKUKAN Co., Ltd.), d "FALKEN" (manufactured by YOUDE KAYAKULIS CO., Ltd.), e "RHEILA TAPE" (manufactured by Imperial KAIKI KAIKAY Co., Ltd.), f "Voltaren TAPE" (manufactured by Nowa KAIKAIKAY Co., Ltd.), and g "KETOTAX" (manufactured by Toukai KAIKAIYX Co., Ltd.).

[ test example 1] measurement of tan. delta

The storage modulus (G') of the adhesive and the like were measured using a Rheometric Dynamic Analyzer "Dynamic Analyzer RDA III (trade name)" (manufactured by Rheometric Scientific Co., Ltd.).

Specifically, first, the adhesive was scraped off from the adhesive layer of each patch, and about 65mg of the adhesive was held in a cylindrical jig. For this adhesive, the frequency was increased from 0.01Hz to 80Hz at a rate of 1.259Hz at 32 ℃ with 1% strain applied, and the stress at this time was measured every 12 seconds and made into a graph. The plate (plate) used was a parallel plate 25mm in diameter, the Gap (Gap) was set to 1.2mm, and G' were calculated using computer software (Orchetrator Ver.6.5.6; manufactured by Rheometric Scientific Co., Ltd.). Tan δ (═ G "/G') was also calculated using computer software (orchelator ver.6.5.6; manufactured by Rheometric Scientific).

< measurement conditions >

Frequency: 0.01 to 80Hz (1.259 Hz plus in common ratio)

Temperature: 32 deg.C

Measurement mapping: the measurements were plotted every 12 seconds.

Plate: parallel plates, diameter 25mm

Gap (Gap): 1.2mm

The amount of strain: 1 percent of

The adhesives obtained in examples 1 to 10 and comparative examples 1 to 2 and the adhesives possessed by the commercially available products a to g were used for the measurement. Their tan delta at 32 ℃ are shown in Table 2. Further, the relationship between the frequency and tan δ shown graphically is shown in fig. 1 and 2. Fig. 1 is a graph showing a relationship between the frequency and tan δ in the entire range of 0.01 to 80Hz in logarithmic scale, and fig. 2 is a graph obtained by partially enlarging a portion having a frequency of 0 to 0.30 Hz.

TABLE 2

[ test example 2] evaluation of usability

After the backing of the adhesive patch was peeled off, the adhesive agent layer surfaces of the commercially available products a to g and the adhesive patches (10 cm. times.7 cm) of examples 1 to 10 and comparative examples 1 to 2 were folded in half and adhered to each other. The ease of peeling when the adhesive layer was pulled back to the original state separately was evaluated organoleptically according to the following criteria.

"evaluation Standard"

Very good: can be peeled off without resistance.

O: can be peeled off but with a slight resistance.

And (delta): it is somewhat difficult to peel.

X: the adhesive layer is difficult to peel and is pulled back to the original state, and a part of the adhesive layer peels off.

Test example 3 evaluation of skin irritation (pain feeling upon exfoliation)

The adhesive patches (10 cm. times.7 cm) of the commercially available products a to g and examples 1 to 10 and comparative examples 1 to 2 were applied to the upper right arm of 5 persons who were the test commentators. The pain sensation felt when each patch was peeled from the right upper arm was evaluated according to the following criteria.

"evaluation Standard"

Very good: no pain was felt at all.

O: a little pain is felt.

And (delta): the feeling of pain was felt.

X: strong pain was felt.

Test example 4 evaluation of skin adhesiveness

The adhesive patches (10 cm. times.7 cm) of the commercially available products a to g and examples 1 to 10 and comparative examples 1 to 2 were applied to the upper right arm of 5 persons who were the test commentators. After 8 hours had elapsed, the skin adhesion state (peeling state) of each patch was visually observed. The patch to be applied to the skin over the entire surface was referred to as "no peeling", and evaluated according to the following criteria.

"evaluation Standard"

Very good: no peeling.

O: there was an extremely slight peeling.

And (delta): slightly larger peels were observed at the four corners and the like.

X: there is a large shift in the peeled or stuck portion over a wide range.

[ test example 5] evaluation of skin-adherability (Water resistance) in the presence of moisture

After spraying purified water on the upper right arm of 5 test panelists, the commercially available products a to g and the adhesive patches (10 cm. times.7 cm) of examples 1 to 10 and comparative examples 1 to 2 were evaluated in the same manner as in test example 4, and the skin adhesiveness of each adhesive patch was evaluated.

The evaluation results of test examples 2 to 5 are shown in Table 3.

TABLE 3

As shown in Table 2 and FIGS. 1 to 2, the adhesives produced in examples 1 to 9 satisfied the formula 1 at any point of the frequency of 0.04Hz to 0.25Hz, as tan. delta. values at 32 ℃ obtained by measuring dynamic viscoelasticity. On the other hand, in the commercially available products a to g and comparative examples 1 to 2, the tan δ value at 32 ℃ obtained by measuring the dynamic viscoelasticity does not satisfy the formula 1 at any frequency of 0.04Hz to 0.25 Hz.

Further, the adhesives produced in examples 1 to 10 satisfied the numerical expression 2 at any point of frequencies of 0.04Hz to 0.10Hz in the tan delta value at 32 ℃ obtained by measuring the dynamic viscoelasticity. On the other hand, in the commercially available products a to g and comparative examples 1 to 2, the tan δ value at 32 ℃ obtained by measuring the dynamic viscoelasticity does not satisfy the formula 2 at any frequency of 0.04Hz to 0.10 Hz.

On the other hand, as shown in table 3, it is understood that the patch preparations prepared in examples 1 to 10 all have improved usability, skin adhesiveness and water resistance and reduced irritation to the skin. On the other hand, the patches prepared in the commercially available products a to g and comparative examples 1 to 2 were not improved in usability, skin adhesiveness and water resistance, and were not reduced in irritation to the skin.

[ example 6] evaluation of usability

After reinforcing each adhesive patch by sticking an adhesive tape to the support side of example 6 and commercially available products a and f, it was cut into 2.5cm wide, thereby obtaining a plurality of pieces. Subsequently, after the release liner was peeled off from each test piece, the adhesive layer surfaces were bonded to each other, and a 2kg roller was pressed onto the adhesive layer surfaces by one reciprocating. Subsequently, a grip portion was formed with an adhesive tape, thereby producing a test piece. The test piece was held between upper and lower grips of a tensile tester, and the test piece was peeled at a speed of 300 mm/min, and the load until the test piece was completely peeled was measured. The measurement was performed 3 times, and the average value of the measured load was calculated. The results are shown in FIG. 3.

As shown in FIG. 3, the adhesive patch prepared in example 6 was peeled off with a very small load as compared with commercially available products a and f. That is, the adhesive patch prepared in example 6 was easily peeled off when it was self-adhered, and the usability was improved.

As is apparent from the above, by satisfying the formula 1 at a tan δ value at 32 ℃ of 0.04Hz to 0.25Hz, which is obtained by measuring dynamic viscoelasticity of an adhesive containing an SIS block copolymer, excellent skin-attaching properties, improved usability and water resistance, and reduced irritation to a user can be achieved.

Further, it is also known that by making the tan δ value at 32 ℃ of an adhesive containing an SIS block copolymer satisfy the mathematical formula 2 at 0.04Hz to 0.10Hz, which is obtained by measuring the dynamic viscoelasticity, it is possible to have excellent skin adherability, improve the usability and water resistance, and reduce the irritation to the user.

The above results, if evaluated from another point of view, show: the skin adhesiveness, the usability, and the water resistance of the patch at the time of use, and the irritation to the user can be evaluated with certainty based on the tan δ value at 32 ℃, which is an average temperature of human epidermis as a representative application object of the patch, obtained by measuring dynamic viscoelasticity.

Claims (1)

1. A method for evaluating an adhesive patch, characterized in that the adhesive patch comprises a flexible support and an adhesive layer laminated on the support, and the adhesive patch is evaluated on the basis of a tan delta value, which is obtained by measuring the dynamic viscoelasticity of the adhesive layer and is at a temperature at which the adhesive patch is applied.