JPH11123235A - Novel sticking agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sticking agent and sticking formulation in which adhesive force is different between the surface and back of adhesive, in which one side has no adhesive force substantially, and in which a carrier is not necessarily required. SOLUTION: Sticking agent comprises an adhesive polymer (A) and an adhesive comprising parfluoroalkyl(meth)acrylate copolymer (B) comprising 25-85 wt.% pearfluoro(meth)acrylate and 10-75 wt.% at least one component of components included in the adhesive polymer (A) copolymerized with each other after blending at a rate of A:B=7:3-1:9.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a patch comprising a pressure-sensitive adhesive blended with perfluoroalkyl (meth) acrylate. More specifically, the present invention relates to a patch and a patch which do not necessarily require a support because the pressure-sensitive adhesive has different adhesive strengths on the front and back sides and has substantially no adhesive strength.

[0002]

2. Description of the Related Art In recent years, various transdermal patches have been developed for administering drugs into the living body through the skin surface. These transdermal patches comprise a pressure-sensitive adhesive layer and a support, and a non-woven fabric or a polymer film is used as the support. However, conventional percutaneous absorption patches using these supports have problems in that the patch is peeled off and skin irritation is likely to occur due to the ability to follow the expansion and contraction of the skin.

[0003] In order to improve these, a method using a flexible support is disclosed in Japanese Patent Application Laid-Open Nos. Hei 5-38931 and Hei 6-142178, but the elastic modulus of the polymer used for the support is disclosed. Is larger than the pressure-sensitive adhesive layer, so the problem of skin irritation has not been solved.

[0004] In addition, as an adhesive which does not require a support, an incompatible blend is formed by using an acrylic polymer and an acrylic polymer and an incompatible fluorine polymer, whereby a gradient structure is developed, and the adhesive is adhered on both sides of the adhesive. It is known that pressure sensitive adhesives with different properties can be obtained (Abstracts of the 35th Annual Meeting of the Adhesive Society of Japan, p5-8 (1997)).

[0005]

However, the formation of a gradient structure using the above incompatible polymer blend is greatly limited by the type of polymer used and the film forming conditions, and the formation of the gradient structure is not easy. There is.

Further, Japanese Patent Publication No. 60-56686 discloses a pressure-sensitive adhesive in which a perfluoroalkyl (meth) acrylate is blended, but does not show that the pressure-sensitive adhesive has different tackiness on the front and back sides. JP-B-60-56686 also discloses and suggests a pressure-sensitive adhesive obtained by blending the pressure-sensitive adhesive polymer (A) of the present invention with a perfluoroalkyl (meth) acrylate copolymer (B). Not.

[0007] That is, an object of the present invention is to provide a patch and a patch preparation comprising a novel pressure-sensitive adhesive having different pressure-sensitive adhesive forces on the front and back, and substantially no pressure on one of the front and back.

Another object of the present invention is to provide a patch and a patch preparation comprising a novel pressure-sensitive adhesive having different adhesive strengths on the front and back sides and substantially no adhesive strength on one side, and requiring no support. To provide.

It is a further object of the present invention to provide a novel patch and adhesive which can be easily obtained, having different adhesive strengths on the front and back sides of the pressure-sensitive adhesive and having substantially no adhesive strength on one of the front and back sides and requiring no support. It is to provide a formulation.

Further, an object of the present invention is to achieve a function with a smaller amount of fluorine compared to the prior art, and at the same time, have simple film forming conditions, and have excellent economical and industrial properties.
It is an object of the present invention to provide a novel patch and a patch preparation which have different adhesive strengths on the front and back sides of the pressure-sensitive adhesive and have substantially no adhesive strength on one side, and do not require a support.

The inventors of the present invention have conducted intensive studies to achieve such an object, and as a result, have found that a perfluoro (meth) acrylate obtained by copolymerizing an adhesive polymer and at least one component contained in the adhesive polymer. It has been found that the object of the present invention can be achieved by blending with a copolymer, and the present invention has been completed.

[0012]

That is, the present invention provides:
(1) The adhesive polymer (A), (2) 25% to 85% by weight of perfluoroalkyl (meth) acrylate, and 10% to 75% by weight of at least one of the components contained in the adhesive polymer (A). And a perfluoroalkyl (meth) acrylate copolymer (B) copolymerized with
It is intended to provide a patch comprising an adhesive blended at a ratio of A: B = 7: 3 to 1: 9, and a patch preparation comprising a drug in the adhesive.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The perfluoroalkyl (meth) acrylate copolymer (B) used in the present invention comprises:
25 weight% to 85 weight% of perfluoroalkyl (meth) acrylate, and 10 weight% of at least one component contained in the following adhesive polymer.
(t)% to 75% by weight (wt).

In the perfluoroalkyl (meth) acrylate copolymer (B), if the perfluoroalkyl (meth) acrylate is less than 25% by weight, it is not possible to substantially eliminate the adhesive strength of one of the front and back of the pressure-sensitive adhesive,
It is difficult to obtain adhesives having different adhesive strengths on the front and back.
On the other hand, the perfluoroalkyl (meth) acrylate
If the content is more than wt%, the solubility or compatibility of the perfluoroalkyl (meth) acrylate copolymer with the adhesive polymer dope becomes poor, and it becomes difficult to form a uniform adhesive, which is not preferable.

In the perfluoroalkyl (meth) acrylate copolymer (B) of the present invention, at least one of the components contained in the following tacky polymer (A) contains 1
It is important that the copolymer is copolymerized at a ratio of 0 wt% to 75 wt%. If the copolymerization ratio is less than 10% by weight, the compatibility between the perfluoroalkyl (meth) acrylate copolymer (B) and the adhesive polymer (A) becomes poor, and it becomes difficult to obtain adhesives having different adhesive strengths on the front and back. In addition, the cohesive force of the pressure-sensitive adhesive is reduced, and adhesive residue is likely to be generated, which is not preferable. On the other hand, if the copolymerization ratio exceeds 75% by weight, the difference in the adhesive strength between the front and back of the pressure-sensitive adhesive is less likely to appear.

The perfluoroalkyl (meth) acrylate used in the present invention is, for example, 2-perfluorooctylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate , 2-perfluorododecylethyl (meth) acrylate, perfluoroheptylmethyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate and the like.

Of these, the perfluoroalkyl (meth) acrylates of the present invention include those having 2 to 18 carbon atoms.
Perfluoroalkyl (meth) acrylate comprising an alkyl group of the above is preferred, and perfluoroalkyl (meth) acrylate comprising an alkyl group having 6 to 12 carbon atoms is particularly preferred.

Further, at least one of the components contained in the adhesive polymer (A) used in the perfluoroalkyl (meth) acrylate copolymer (B) of the present invention is, for example, (meth) acrylic acid, carbon number Examples thereof include 1-20 alkyl (meth) acrylates and vinyl acetate, and among these, acrylic acid, 2-ethylhexyl acrylate, and vinyl acetate can be particularly preferred.

Therefore, the perfluoroalkyl of the present invention
Perfluoro constituting (meth) acrylate copolymer
As a preferred combination of the (meth) acrylate and at least one component contained in the adhesive polymer (A), the former is a perfluoroalkyl (meth) acrylate comprising an alkyl group having 2 to 18 carbon atoms, and the latter is a Carbon number 1
To 20 (meth) acrylic acid alkyl esters, vinyl acetate, etc., in particular, the former is a perfluoroalkyl (meth) acrylate composed of an alkyl group having 6 to 12 carbon atoms, and the latter is 2-ethylhexyl acrylate. Particularly preferred combinations can be mentioned.

In this case, the mixing ratio of the perfluoro (meth) acrylate to at least one of the components contained in the adhesive polymer (A) is 25 to 85% by weight for the former and 10 to 75% by weight for the latter. Are preferred.

The adhesive polymer (A) used in the present invention can be basically used without any limitation as long as it has adhesiveness to the skin. Specific examples include a polyacrylate adhesive polymer, a polyvinyl acetate adhesive polymer, and a rubber adhesive polymer.

Preferred specific examples include, for example, a polyacrylate ester-based adhesive polymer and a polyvinyl acetate-based adhesive polymer, and one or more selected from such adhesive polymers. Things can be used.

The polyacrylate-based adhesive polymer is an alkyl (meth) acrylate mainly containing an alkyl (meth) acrylate having 1 to 20 carbon atoms and containing 10% by weight or less of acrylic acid. Ester copolymers are preferred. Among them, a copolymer containing 2-ethylhexyl acrylate as a main component is particularly preferable from the viewpoint of adhesive strength.

As the polyvinyl acetate-based adhesive polymer, a copolymer containing vinyl acetate as a main component and containing 10% by weight or less of acrylic acid is preferable from the viewpoint of adhesive strength and cohesive strength.

In the present invention, it is important that the adhesive polymer (A) and the perfluoroalkyl (meth) acrylate copolymer (B) are blended in a ratio of A: B = 7: 3 to 1: 9. . When the ratio of the adhesive polymer exceeds 70%, it is difficult to develop a difference in adhesive strength between the front and back of the adhesive layer, and it is difficult to obtain an adhesive having substantially no adhesive strength on one side. On the other hand, when the adhesive polymer is 10
%, It becomes impossible to obtain a sufficient adhesive force to the skin, which is not practical.

The patch of the present invention comprises the above adhesive polymer (A), 25% to 85% by weight of perfluoroalkyl (meth) acrylate, and the adhesive polymer (A).
10% by weight of at least one of the components contained in
A: B = 7: 3 to 1: 9 with a perfluoroalkyl (meth) acrylate copolymer (B) copolymerized with
, And then applying the adhesive solution onto a release film coated with silicone and drying, for example. The pressure-sensitive adhesive of the present invention thus obtained is
The pressure-sensitive adhesive has different pressure-sensitive adhesive forces on the front and back sides and has substantially no pressure-sensitive adhesive force on one side, and thus can be used as the patch of the present invention without providing a support.

If necessary, such a patch may be provided with another adhesive means, for example, a support or a protective layer for assisting the simplicity of handling. And / or a plurality of pressure-sensitive adhesive layers using another pressure-sensitive adhesive layer or the like.

The patch preparation of the present invention can be prepared by incorporating a drug into the adhesive of the present invention. The drug to be contained is not particularly limited, but specific examples include anti-inflammatory analgesics, steroids, antihypertensive diuretics, anesthetics, antihistamines, antitumor agents, antihypertensives, antidepressants, vitamins, and the like. . The content of the drug is set depending on the purpose of the treatment, and is usually 0.1 to 40 wt%, preferably 1 to 30 wt%.
t%. If the content is less than 0.1 wt%, transdermal absorption of the drug in an amount usually required for treatment may not be obtained. On the other hand, when the content exceeds 40% by weight, the adhesive strength of the patch decreases and the amount of the drug remaining in the patch after use increases, which is uneconomical. In addition, as a method for containing a drug, a drug solution is preliminarily mixed with a solution-type pressure-sensitive adhesive to form a drug-containing pressure-sensitive adhesive layer, or the drug is not contained by a method such as impregnation, transfer, spraying, or the like. Conventionally known methods can be employed depending on the physical properties of the drug to be contained, for example, by allowing the pressure-sensitive adhesive layer not sufficiently containing the drug to contain the drug in an amount sufficient for transdermal absorption.

[0029]

As described above, by blending an adhesive polymer and a perfluoro (meth) acrylate copolymer obtained by copolymerizing at least one of the components contained in the adhesive polymer, the adhesive strength between the front and back surfaces can be improved. However, a pressure-sensitive adhesive having substantially no adhesive force on one of the front and back sides can be easily obtained, and a patch and a patch preparation requiring no support can be obtained.

[0030]

EXAMPLES The present invention will be described below with reference to examples. In Examples, parts and% mean parts by weight and% by weight, respectively. In the examples, "adhesive strength" and "cohesive strength" were measured by the following methods. (1) Adhesive strength A sample cut to a width of 12 mm and a length of 50 mm was attached to a bakelite plate, and a roller having a load of 850 g was reciprocated once, and allowed to stand in a thermostat at 37 ° C. for 30 minutes.
0 mm / min. At a speed of 180 degrees, and the peeling force at that time was defined as the adhesive strength. (2) Cohesive force After measuring the adhesive force by the method of the above (1), it was visually determined whether or not the adhesive remained on the bakelite plate.

Example 1 Under a nitrogen gas atmosphere, azobisisobutyronitrile was used as a polymerization initiator in a solution of 40 g of 2-perfluorooctylethyl methacrylate, 45 g of 2-ethylhexyl acrylate, 15 g of acrylic acid, and 100 g of ethyl acetate. After adding 0.5 mol% of the total monomer, nitrogen gas was passed through the solution for 1 hour.
Polymerization was performed for a period of time to obtain a perfluoroalkyl methacrylate copolymer. Similarly, a polyacrylic acid alkyl ester copolymer comprising 90 parts of 2-ethylhexyl acrylate, 7 parts of methyl methacrylate, and 3 parts of acrylic acid was obtained. 40 g of perfluoroalkyl methacrylate copolymer, alkyl acrylate copolymer 60
g of an ethyl acetate solution was coated on a silicone-coated release film so that the thickness of the dried adhesive layer was 50 μm, and dried at 60 ° C. for 30 minutes to obtain an adhesive layer.
The obtained pressure-sensitive adhesive was cut into a width of 12 mm and a length of 50 mm to obtain a sample for measuring the adhesive strength. The surface side (air side) was affixed to a bakelite plate to measure the adhesive strength, but no measurement was possible due to lack of adhesive strength. The back side (release film side) was affixed to a bakelite plate, and the adhesive strength was measured. In other words, a pressure-sensitive adhesive having no support was obtained, since the adhesive force was different between the front and back surfaces of the pressure-sensitive adhesive. When applied to the skin, no discomfort was felt.

Example 2 A pressure-sensitive adhesive layer was obtained in the same manner as in Example 1 except that an ethyl acetate solution containing 60 g of the perfluoroalkyl methacrylate copolymer and 40 g of the alkyl acrylate copolymer was used. Was.
The pressure-sensitive adhesive strength on the front side of the obtained pressure-sensitive adhesive was so small that it could not be measured, the pressure-sensitive adhesive strength on the back side was 51 g, and the cohesive strength was also good. In other words, a pressure-sensitive adhesive having no support was obtained, since the adhesive force was different between the front and back surfaces of the pressure-sensitive adhesive. When applied to the skin, no discomfort was felt.

Example 3 39.2 g of the perfluoroalkyl methacrylate copolymer used in Example 1
58.8 g of a polyacrylic acid alkyl ester copolymer,
An adhesive layer was obtained in the same manner except that an ethyl acetate solution containing 2 g of ketoprofen was used as a drug. The pressure-sensitive adhesive strength on the front side of the obtained pressure-sensitive adhesive was so small that it could not be measured, the pressure-sensitive adhesive strength on the back side was 101 g, and the cohesive strength was also good. In other words, a pressure-sensitive adhesive having no support was obtained, since the adhesive force was different between the front and back surfaces of the pressure-sensitive adhesive. When applied to the skin, no discomfort was felt.

Comparative Example 1 An adhesive layer was obtained in the same manner as in Example 1, except that an ethyl acetate solution containing 10 g of the perfluoroalkyl methacrylate copolymer and 90 g of the alkyl acrylate copolymer was used. Was.
The obtained pressure-sensitive adhesive was cut into a width of 12 mm and a length of 50 mm to obtain a sample for measuring the adhesive strength. The surface side (air side) is attached to a bakelite plate, the release film is peeled off, and a 3.5 μm PET
When the film was stuck and the adhesive strength was measured, it was 258 g / 12
mm. In addition, the obtained pressure-sensitive adhesive was 12 mm wide and 5 mm long.
After a PET film was affixed to the surface of the sample obtained by cutting to 0 mm, the back surface (release film side) was affixed to a bakelite plate and the adhesive strength was measured to be 218 g / 12 mm. That is, no pressure-sensitive adhesive having different pressure-sensitive adhesive forces on the front and back sides and substantially no adhesion on one side was obtained.

Comparative Example 2 20 g of a homopolymer of 2-perfluorooctylethyl methacrylate and Example 1
An attempt was made to prepare an ethyl acetate solution containing 80 g of the above-mentioned polyacrylic acid alkyl ester copolymer, but the homopolymer of 2-perfluorooctylethyl methacrylate was not dissolved, and an adhesive could not be obtained.

Comparative Example 3 40 g of the perfluoroalkyl methacrylate copolymer used in Example 1, 50 parts of styrene-isoprene-styrene block polymer, 30 parts of rosin ester KE-311 (Arakawa Chemical Industries), and liquid paraffin 20 Rubber-based adhesive polymer 60
An adhesive layer was obtained in the same manner except that a chloroform / ethyl acetate (7/3) mixed solution containing g was used. The obtained pressure-sensitive adhesive was cut into a width of 12 mm and a length of 50 mm to obtain a sample for measuring the adhesive strength. Paste the front side (air side) on a bakelite plate,
The release film was peeled off, a 3.5 μm PET film was applied, and the adhesive strength was measured. The adhesive strength was 77 g / 12 mm, and the cohesive strength was low and adhesive residue was observed. Further, after the obtained pressure-sensitive adhesive was cut into a sample obtained by cutting the obtained pressure-sensitive adhesive into a width of 12 mm and a length of 50 mm, a PET film was stuck to the surface, and the back side (release film side) was stuck to a bakelite plate to measure the adhesion. 188g
/ 12 mm, the cohesive strength was low, and adhesive residue was observed. That is, although the adhesive strength differs between the front and back of the adhesive, a practical adhesive having low cohesive strength could not be obtained.

Claims (5)

[Claims] 1. An adhesive polymer (A) and (2)
Perfluoroalkyl (meth) acrylate copolymer obtained by copolymerizing 25% to 85% by weight of perfluoro (meth) acrylate and 10% to 75% by weight of at least one component contained in the adhesive polymer (A) (B) and A:
A patch comprising an adhesive blended in a ratio of B = 7: 3 to 1: 9. 2. The pressure-sensitive adhesive polymer (A) has 1 to 1 carbon atoms.
The patch according to claim 1, which is an acrylic polymer mainly composed of an alkyl (meth) acrylate 20 or a vinyl acetate polymer mainly composed of vinyl acetate. 3. The adhesive patch according to claim 1, wherein the adhesive has substantially no adhesive strength on one side and an adhesive strength on the other side of 40 g or more and 500 g or less. 4. The patch according to any one of claims 1 to 3, which does not have a support and consists essentially of the pressure-sensitive adhesive. 5. The patch preparation according to claim 1, wherein the adhesive contains a drug.