JP2001163771A - Film for patch material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a film for a patch material that is flexible and stretchable, fits to affected parts and shows excellent tracebility when the affected parts are moved without strong oppression and causes no winding oppression. SOLUTION: The objective film is a polyolefin resin film and the initial stress on 10% elongation F(10) is represented by the following formula (1) and the ratio of the residual stress after 5 minutes f (10) to the initial stress F (10) is represented by the following formula (2): formula (1) 0.98 MPa (10 kgf/ cm2)<F(10)<4.9 MPa (50 kgf/cm2)... (1) formula (2) 0.7<f(10)/F(10)<1.0... (2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film for a patch, and more particularly, it is flexible and stretchable, does not strongly press the affected part, has no feeling of tightness in the wound, and has a feeling of fitting and moving the affected part. The present invention relates to a film for a patch material made of a polyolefin resin, which has excellent followability and is preferably used for a transdermal absorption preparation, a bandage, and the like.

[0002]

2. Description of the Related Art Conventionally, a large number of medical patches such as transdermal preparations and adhesive plasters containing a drug in an adhesive layer have been produced. Generally, an adhesive bandage is obtained by applying an adhesive on one surface of a soft film layer, pasting a gauze or the like thereon, laminating a release paper thereon, and then punching the laminate into a predetermined size. As the soft film used for the bandage, many soft polyvinyl chloride films have conventionally been used. Transdermal preparations are also formed by applying a drug-containing pressure-sensitive adhesive layer or a drug-containing drug layer and a pressure-sensitive adhesive layer to a support, and by applying the drug to the skin, mucous membranes, etc. The drug can be absorbed directly from the skin, mucous membranes, etc. to treat it.
It is used as a topical therapeutic agent such as a tape for skin diseases, an antipruritic patch, and a wound agent, and the use of a transdermal therapeutic system (TTS) is increasing as a systemic therapeutic agent such as a sickness medicine. are doing. Many soft vinyl chloride films have been used as such a support for a transdermal absorption preparation, similarly to the above-mentioned bandage.

However, since a soft polyvinyl chloride film contains a large amount of a plasticizer, the plasticizer transfers from the film to the pressure-sensitive adhesive layer, and the adhesive strength of the pressure-sensitive adhesive layer is reduced.
The adhesive strength between the film and the pressure-sensitive adhesive layer is reduced, and there are drawbacks such as the percutaneous absorption preparation and the adhesive bandage being peeled off, and the pressure-sensitive adhesive being transferred to the peripheral portion to be stained. As a material, the use of a flexible, stretchable film made of a polyolefin-based resin or the like is being studied, but a film having sufficient elasticity and stress relaxation at the time of sticking required for the film has not been obtained. However, there have been problems such as a strong feeling of tightness of the winding of the film, poor followability of the film to the skin at a bent portion such as an elbow, and peeling of the film.

[0004]

SUMMARY OF THE INVENTION The present invention relates to an adhesive material which is flexible and stretchable, fits on an affected part, does not strongly press, has no feeling of tightness, and has excellent followability when the affected part is moved. It is intended to provide a film for use.

[0005]

According to the present invention, there is provided a film made of a polyolefin resin, wherein an initial stress F (10) at 10% elongation is represented by the following formula (1),
The film for a patch is characterized in that the ratio of the residual stress f (10) after 5 minutes to (10) is represented by the following formula (2).

[0006]

## EQU3 ## 0.98 MPa (10 kgf / cm ² ) <F (10) <4.9 MPa (50 kgf / cm ² ) (1)

[0007]

0.7 <f (10) / F (10) <1.0 (2)

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The adhesive film of the present invention satisfies the above formulas (1) and (2). Initial stress F (10) at 10% elongation is 0.98 MPa (10 kgf / cm
² ) When the content is less than the above range, the film is too soft and easily wrinkles or the like are formed during processing such as application of an adhesive, which is not practical. Also 4.
When the pressure is 9 MPa (50 kgf / cm ² ) or more, the tight wound feeling is great when wound around hands or fingers, and the affected part is pressed.

The ratio of the residual stress f (10) after 5 minutes to the initial stress F (10) (f (10) / F (10))
If it is 0.7 or less, it will not fit the affected part when it is wrapped around the joint of the hand or finger and bends the finger to extend it again, and if it is 1.0 or more, the feeling of tightness is large, It is oppressed. Further, the tensile modulus of the film is 49-196.
When the pressure is MPa (500 to 2000 kgf / cm ² ), it is preferable because the flexibility of the film is sufficient, there is no feeling of tightness in winding, and there is no uncomfortable feeling when wound around a finger or the like.

In the present invention, the terms "stress" and "tensile elastic modulus" mean "tensile stress" and "tensile elastic modulus" specified in JIS K7127, respectively. Examples of the polyolefin-based resin used for the adhesive film of the present invention include polyethylene-based resins, polypropylene-based resins, and mixtures thereof. Examples of the polyethylene resin include a homopolymer of ethylene and / or a copolymer of ethylene and another monomer copolymerizable therewith (low-density polyethylene (LDP)).
E), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), polyethylene (metallocene-based polyethylene) obtained by polymerization using a metallocene-based catalyst, ethylene-propylene copolymer rubber, ethylene-
Propylene non-conjugated diene rubber, ethylene-butadiene copolymer rubber, etc.), or a mixture (polymer blend) of the homopolymer and / or copolymer with another polymer. Examples of the polymer that can be mixed with the homopolymer and / or the copolymer to give a polymer blend include, for example, isoprene rubber, butadiene rubber,
Diene rubbers such as butyl rubber, propylene-butadiene rubber, acrylonitrile-butadiene rubber, acrylonitrile-isoprene rubber, and styrene-based thermoplastics such as styrene-butadiene copolymer rubber, styrene-butadiene block copolymer and styrene-isoprene copolymer rubber Elastomers. Among them, styrene-butadiene-based thermoplastic elastomers such as styrene-butadiene copolymer rubber and styrene-butadiene block copolymer are preferable. The styrene-based thermoplastic elastomer is preferably hydrogenated. The amount of the polymer to be mixed is preferably 5 to 80% by weight, particularly preferably 20 to 60% by weight.

Examples of the polypropylene resin include a homopolymer and / or copolymer of propylene, and a mixture (polymer blend) of the homopolymer and / or copolymer with another polymer. Examples of the copolymer include a random copolymer or a block copolymer of propylene and ethylene or another α-olefin, or a propylene graft copolymer having a polyolefin copolymer as a trunk polymer. . Among them, a random copolymer is preferred because the transparency and flexibility of the film are improved. Α- copolymerizable with propylene
As the olefin, those having 4 to 12 carbon atoms are preferable. For example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-
Examples thereof include pentene and 1-decene, and one or a mixture of two or more thereof is used. The mixing ratio of the α-olefin is preferably 1 to 10% by weight, particularly preferably 2 to 6% by weight based on propylene.

Examples of the polyolefin copolymer for the backbone polymer of the propylene graft copolymer include ethylene-propylene rubber, ethylene-butene rubber, and ethylene-propylene-diene rubber. Examples of the polymer which can be mixed with a propylene homopolymer and / or copolymer to give a polymer blend include the same polymers as those mixed with the polyethylene resin described above. Among them, styrene-butadiene-based thermoplastic elastomers such as styrene-butadiene copolymer rubber and styrene-butadiene block copolymer are preferable. The styrene-based thermoplastic elastomer is preferably hydrogenated. The amount of the polymer to be mixed is preferably 5 to 80% by weight, particularly preferably 20 to 60% by weight.

The film of the present invention may be a single layer or a multilayer. Furthermore, in each layer of the film of the present invention, if necessary, other synthetic resins and antioxidants, light stabilizers, UV inhibitors,
Lubricants, fillers such as talc, calcium carbonate, mica, and titanium oxide, flame retardants, antistatic agents, coloring agents, and the like can be added. Further, irregularities may be formed on at least one surface of the film. The shape of the unevenness may be any of a satin shape, a stripe shape, a lattice shape, a polka dot shape, and the like. The unevenness is preferably formed such that the surface roughness (10-point average roughness (Rz) specified in JIS B 0601) of the film is 1 to 20 μm. When Rz is less than 1 μm, the effect of forming the irregularities is small, and when Rz is more than 20 μm, there is a feeling of roughness, and the film is easily cut due to a notch effect. By providing the film with irregularities, the apparent thickness is increased with respect to the actual thickness of the film, and the feel of the film can be made more flexible.

The film may be produced by a known extruder or multi-layer co-extrusion machine. In order to make the film uneven, embossing is performed in-line using an embossing roll or the like stamped with embossing during film formation. Alternatively, the film that has been cooled may be heated and softened so that the film can be deformed under pressure, and then pressed on the surface provided with the uneven pattern to transfer the uneven pattern off-line.

The embossing method is not particularly limited. For example, the embossing method may be performed between a metal roll having a fine uneven pattern on its surface and a silicone rubber roll having elasticity and good release properties. A method of transferring the fine uneven pattern provided on the metal roll surface to the film surface by nipping while being heated to a temperature suitable for each compounding composition, and the like.

The thickness of the film of the present invention is not particularly limited, but is preferably 40 to 120 μm. 40
If it is less than μm, the strength at the time of use tends to be insufficient, and if it exceeds 120 μm, it is too hard for a film for a patch, and the texture may be impaired. The film may be colorless or colored, transparent or opaque. As a preferred embodiment of the film of the present invention, a film made of a polyolefin resin is one having the following (1) to (3) and having specific physical properties represented by the above formulas (1) and (2). No. These films have a good balance of various properties such as flexibility, stretchability, followability, and tightness of the film, and are suitable as films for adhesive materials. (1) A polyolefin-based resin film was polymerized using a metallocene-based catalyst, and (a) the density was 0.87.
0.92 g / cm ³ , (b) melt flow rate is 0.5
And (c) the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.5 to 5
A polypropylene-based resin is contained on at least one surface of a base material layer containing a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, preferably 70 to 100% by weight, preferably 70 to 100% by weight. A surface layer containing 100 to 100% by weight is laminated, and the layer thickness ratio of the substrate layer and the surface layer (however, if there are surface layers on both sides of the substrate layer, the total thickness of both surface layers is determined as the surface Layer thickness.
The same applies to (2) and (3). ) Wherein the base material layer / surface layer = 1/1 to 20/1, preferably 4/1 to 10/1. (2) The film made of polyolefin resin is ethylene-
Containing propylene copolymer rubber, preferably 70 to 1
A surface layer containing low-density polyethylene and / or linear low-density polyethylene, preferably containing 70 to 100% by weight, is laminated on at least one surface of the substrate layer containing 00% by weight. The layer thickness ratio of the surface layer is as follows: substrate layer / surface layer = 1/1 to 20/1, preferably 4/1 to 10
/ 1 film. (3) The film made of polyolefin resin is ethylene-
Containing propylene copolymer rubber, preferably 70 to 1
A surface layer containing a polypropylene-based resin, preferably 70 to 100% by weight, is laminated on at least one surface of a substrate layer containing 00% by weight. Film wherein layer / surface layer = 1/1 to 20/1, preferably 4/1 to 10/1.

If the ratio of the thickness of each layer is less than 1/1, the rigidity of the film may be increased tactilely and the flexibility may be deteriorated.
If it exceeds 20/1, the stickiness of the surface may be increased. Incidentally, the metallocene-based catalyst (also referred to as a single-site catalyst or a Kaminski catalyst) is described in JP-A-3-16308.
8, JP-A-7-118431, JP-A-7-118431
A catalyst comprising a metallocene-based transition metal complex and an organoaluminum compound as shown in 148895 and the like, and may be used by being supported by an inorganic substance.

The metallocene transition metal complex includes, for example, a transition metal (titanium, zirconium, hafnium) selected from the group IVB, a cyclopentadienyl group, a substituted cyclopentadienyl group, a dicyclopentadienyl group, A cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group coordinated with one or two ligands, or Are covalently crosslinked two groups of which have a ligand such as a hydrogen atom, oxygen atom, halogen atom, alkyl group, alkoxy group, aryl group, acetylacetonate group, etc. Is mentioned. Also,
Examples of the organoaluminum compound include alkylaluminum and a chain or cyclic aluminoxane. Examples of the alkylaluminum include triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, and dimethylaluminum fluoride. Ride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like can be exemplified.The chain or cyclic aluminoxane can be produced by contacting the above-mentioned alkylaluminum with water. Add aluminum, add water later, or add water of crystallization of complex or organic Ku can be obtained by reacting the adsorbed water of an inorganic compound and an alkyl aluminum.

Examples of the carrier for supporting the metallocene catalyst include silica gel, zeolite, and diatomaceous earth. The film of the present invention can be suitably used for applications such as transdermal absorption preparations, adhesive bandages, adhesive plasters, wound guard films, and protect films. Adhesive bandage using the film of the present invention, after applying a corona discharge treatment or an anchor coat on the film surface as necessary, providing an adhesive layer, laminating gauze or the like thereon, and further releasing paper from above And the like are laminated and then punched out to a predetermined size. The type of the pressure-sensitive adhesive is not particularly limited. For example, various pressure-sensitive adhesives such as natural rubber, synthetic rubber, acrylic, urethane, vinyl ether, and silicone are preferably used. May be any of a solution type, an emulsion type, a hot melt type and the like. Further, various types of printing may be performed on any one surface of the film depending on the purpose.

A transdermal absorption preparation using the film of the present invention has a drug adhered to one side of the film. The percutaneous absorption preparation comprises a layer containing a drug and a pressure-sensitive adhesive layer laminated. Or by applying a drug-containing pressure-sensitive adhesive or by laminating a laminate comprising a drug-containing pressure-sensitive adhesive layer or a drug-containing layer and a pressure-sensitive adhesive layer provided in advance on release paper or the like. Obtained by pasting together.

The above-mentioned drug is not particularly limited as long as it is absorbed percutaneously into the body and exerts a pharmacological effect.
Examples thereof include anti-inflammatory agents, analgesics, local stimulants, antihistamines, local anesthetics, blood circulation enhancers, hypnotics and sedatives, tranquilizers, anti-blood pressure agents, antibacterial agents and the like. Note that an additional layer may be provided between the film of the present invention and the pressure-sensitive adhesive layer, if necessary.

[0022]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention. Evaluation method (Tensile modulus) The tensile modulus of the film was measured according to JIS K7127.

(Initial / residual stress) JIS K 6732
A film having the same shape and dimensions as the tensile elongation test piece described was used as a test piece, stretched 10% at a test speed of 300 mm / min, held, and its initial stress F (10) and residual stress after 5 minutes f (10) was measured. (Tightening feeling) A film having a width of 19 mm and a length of 75 mm was wrapped around the second joint of the forefinger, pressed down, and the presence or absence of tightness (tightening) when the finger was bent and stretched was evaluated.

(Slack when strain is released) Width 19 mm, length 7
A 5 mm film was wrapped around the second joint of the index finger and held down, and the film was evaluated for slackness after bending and stretching the finger. Examples 1 to 7 and Comparative Examples 1 and 2 <Preparation of Adhesive Film> Using the compositions shown in Table 1, T-die film forming equipment (65 m, manufactured by Toshiba Machine Co., Ltd.)
Each film (Examples 1 and 2, Comparative Examples 1 and 2 was a single layer, and Examples 3 to 7 were 3
A layer (surface layer / substrate layer / surface layer)) was prepared. The obtained film was evaluated, and the results are shown in Table 1.

[0025]

[Table 1]

[0026]

Industrial Applicability The film of the present invention is flexible and stretchable, fits on an affected part, does not strongly press, has no feeling of tightness, and has excellent followability when the affected part is moved. It is suitably used as a film.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) B32B 27/32 B32B 27/32 103 103 A61L 15/06

Claims (5)

[Claims] 1. A film made of a polyolefin resin, wherein an initial stress F (10) at 10% elongation is represented by the following formula (1), and a residual stress after 5 minutes with respect to the initial stress F (10): A film for a patch, wherein the ratio of f (10) is represented by the following formula (2). 0.98 MPa (10 kgf / cm ² ) <F (10) <4.9 MPa (50 kgf / cm ² ) (1) 0.7 <f (10) / F ( 10) <1.0 ... (2) 2. Tensile modulus of elasticity of 49-196 MPa (50
Patch film according to 0~2000kgf / cm ²⁾ according to claim 1 is. 3. A polyolefin resin film obtained by polymerization using a metallocene catalyst has a density (a) of 0.87 to 0.92 g / cm ³ and a melt flow rate (b) of 0.5. ５０50 g / 10 min, and (c) weight average molecular weight (M
w) and ethylene having a ratio (Mw / Mn) of 1.5 to 5 to a number average molecular weight (Mn) and α- having 3 to 12 carbon atoms.
A film in which a surface layer containing a polypropylene-based resin is laminated on at least one surface of a substrate layer containing a copolymer with an olefin, and a layer thickness ratio between the substrate layer and the surface layer is / Surface layer = 1/1 to 20/1.
Or the film for a patch according to 2. 4. A percutaneous absorption preparation comprising the film according to claim 1 and a drug adhered to one surface of the film. 5. A bandage film comprising the film according to any one of claims 1 to 3 provided with an adhesive layer on one surface.