JP2018083791A - Medical adhesive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a medical adhesive film having a good feeling in use and also excellent chemical resistance.SOLUTION: A medical adhesive film has a base material composed of polyurethane, and an adhesive layer in contact with the base material and containing a drug component. When the base material is subjected to differential scanning calorimetry, the glass transition temperature width is 23°C or less, and the energy from glass metastasis is 0.5 mJ/°C mg or less. Preferably, when the base material is immersed in water, the dimensional change rate is 5% or less.SELECTED DRAWING: Figure 2

Description

The present invention relates to a medical adhesive film.

The medical adhesive film is used by being attached to the skin as, for example, a patch, a dressing tape, or the like. As a medical adhesive film, the structure by which a base material and an adhesive layer are laminated | stacked is mentioned, for example. Depending on the intended use of the medical adhesive film, the adhesive layer may contain a drug component (see, for example, Patent Document 1).

JP 2014-105325 A

In conventional medical pressure-sensitive adhesive films (particularly dressing tapes), polyurethane is sometimes used as a base material. Since the base material made of polyurethane has flexibility capable of following the movement of the skin and can be formed into a thin film, a medical pressure-sensitive adhesive film having an excellent usability can be realized.

However, when the base material is made of polyurethane and the pressure-sensitive adhesive layer contains a drug component, the drug component may move to the base material, and the base material may be deformed due to wrinkles or shrinkage. Therefore, there has been a demand for a medical pressure-sensitive adhesive film excellent in chemical resistance in which the migration of the drug component contained in the pressure-sensitive adhesive layer to the base material is suppressed.

On the other hand, there is a method in which a chemical transfer prevention layer is disposed by attaching a polyethylene terephthalate (PET) film excellent in chemical resistance to the surface of the base material on the pressure-sensitive adhesive layer side or depositing aluminum. Proposed. However, when such a drug migration prevention layer is provided on a medical pressure-sensitive adhesive film, the feeling of use decreases due to a decrease in flexibility (for example, a polyethylene terephthalate film is hard), or the productivity increases due to an increase in the number of processing steps. It sometimes dropped.

This invention is made | formed in view of the said present condition, and it aims at providing the medical adhesive film which was excellent also in chemical-resistance, while having the outstanding usability | use_condition.

The inventors of the present invention have made various studies focusing on using polyurethane as a base material of a medical adhesive film from the viewpoint of securing an excellent usability. When a differential scanning calorimetry is performed, the glass transition temperature range and the energy derived from the glass transition are in a predetermined range, and a medical base with excellent chemical resistance is used. The present invention was completed by finding that an adhesive film was realized.

The medical pressure-sensitive adhesive film of the present invention comprises a base material made of polyurethane, a pressure-sensitive adhesive layer in contact with the base material and containing a drug component, and when the differential scanning calorimetry of the base material is performed, The glass transition temperature width is 23 ° C. or less, and the energy derived from the glass transition is 0.5 mJ / ° C. · mg or less.

The dimensional change rate when the substrate is immersed in water is preferably 5% or less.

The 100% modulus of the substrate is preferably 0.1 to 15 MPa.

The elongation of the substrate is preferably 350% or more.

The thickness of the substrate is preferably 1 to 100 μm.

The medical adhesive film of the present invention is excellent in chemical resistance while having an excellent feeling of use.

It is sectional drawing which shows typically an example of the medical adhesive film of this invention. It is explanatory drawing of the determination method of the energy derived from the glass transition temperature width of a base material, and the glass transition of a base material. 6 is a DSC chart of the base material of the medical pressure-sensitive adhesive film of Example 3. 6 is a DSC chart of a base material of a medical adhesive film of Comparative Example 1. It is explanatory drawing of the evaluation method of the dimensional change rate of a base material. It is explanatory drawing of the measuring method of 100% modulus of a base material.

The medical pressure-sensitive adhesive film of the present invention comprises a base material made of polyurethane, a pressure-sensitive adhesive layer in contact with the base material and containing a drug component, and when the differential scanning calorimetry of the base material is performed, The glass transition temperature width is 23 ° C. or less, and the energy derived from the glass transition is 0.5 mJ / ° C. · mg or less.

FIG. 1 is a cross-sectional view schematically showing an example of the medical pressure-sensitive adhesive film of the present invention. As shown in FIG. 1, the medical pressure-sensitive adhesive film 1 includes a base material 2 and a pressure-sensitive adhesive layer 3 in contact with the base material 2.

[Base material]
The substrate 2 is made of polyurethane. Polyurethane is obtained by curing a polyurethane composition with heat, moisture, light or the like.

Polyurethane is obtained by reacting a polyol component and a polyisocyanate component as shown in the following reaction formula, and has a structure shown in the following formula (A).

In said formula (A), R represents the site | part except the NCO group of the polyisocyanate component. R 'represents a site excluding the OH group of the polyol component. n represents a repeating unit.

Polyurethane has a flexibility that can follow the movement of the skin and can be formed into a thin film, so that it is excellent in usability. Polyurethanes stretch well when subjected to tensile stress due to their excellent flexibility and are very difficult to tear off.

(Polyol component)
It does not specifically limit as a polyol component, For example, polyether polyol, polycaprolactone polyol, polycarbonate polyol, polyester polyol etc. are mentioned. These may be used alone or in combination of two or more.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polypropylene triol, polypropylene tetraol, polytetramethylene glycol, polytetramethylene triol, polyalkylene glycols such as copolymers thereof, and side chains introduced into these. Examples thereof include derivatives, modified products, and mixtures thereof in which a branched structure is introduced.

Examples of the polycaprolactone polyol include polycaprotectone glycol, polycaprolactone triol, polycaprolactone tetraol, derivatives in which side chains are introduced or branched structures are introduced, modified products, and mixtures thereof. It is done.

Examples of the polycarbonate polyol include a reaction product of a dialkyl carbonate and a diol.

Examples of the dialkyl carbonate include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; diaryl carbonates such as diphenyl carbonate; and alkylene carbonates such as ethylene carbonate. These may be used alone or in combination of two or more.

Examples of the diol include 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and 2-methyl-1,8. -Octanediol, 1,9-nonanediol, 1,10-dodecanediol, 2-ethyl-1,6-hexanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5- Examples include pentanediol, neopentyl glycol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2′-bis (4-hydroxycyclohexyl) -propane, and the like. These may be used alone or in combination of two or more. The diol is preferably an alicyclic or alicyclic diol having 4 to 9 carbon atoms, such as 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl. -1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1, It is preferable to use only one type of 8-octanediol and 1,9-nonanediol or use two or more types in combination. Further, as the diol, a copolycarbonate diol composed of 1,6-hexanediol and 3-methyl-1,5-pentanediol, and a copolycarbonate composed of 1,6-hexanediol and 1,5-pentanediol Diols are also preferred.

As the polycarbonate polyol, for example, polycarbonate glycol, polycarbonate triol, polycarbonate tetraol, derivatives in which side chains are introduced or branched structures are introduced, modified products, and mixtures thereof can be used. .

Examples of the polyester polyol include those obtained by dehydration condensation of a dicarboxylic acid and a glycol component.

Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid; oxalic acid; malonic acid; succinic acid; glutaric acid; adipic acid; azelaic acid; It is done.

Examples of the glycol component include ethylene glycol, 1,4-butanediol, diethylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,5-pentanediol, 1,9-nonanediol, and triethylene. Aliphatic glycols such as glycol; Alicyclic glycols such as 1,4-cyclohexanedimethanol; Aromatic diols such as p-xylenediol; Polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. It is done.

(Polyisocyanate component)
The polyisocyanate component is not particularly limited, and examples thereof include tetramethylene diisocyanate, dodecamemethylene diisocyanate, 1,4-butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexa Diisocyanates such as methylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate; isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1, , 4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexa Alicyclic diisocyanates such as toluene; tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4 ′ -Aromatic diisocyanates such as dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate; dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α And araliphatic diisocyanates such as α-tetramethylxylylene diisocyanate. These may be used alone or in combination of two or more.

(Plasticizer)
The polyurethane composition may further contain a plasticizer. According to the plasticizer, since the hardness of the polyurethane is lowered, the flexibility of the substrate 2 can be increased.

The plasticizer is not particularly limited, and examples thereof include phthalic acid esters (phthalic plasticizers) such as diundecyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, and dibutyl phthalate; 1,2-cyclohexanedicarboxylic acid Diisononyl ester; adipic acid ester; trimellitic acid ester; maleic acid ester; benzoic acid ester; poly-α-olefin and the like. These may be used alone or in combination of two or more.

(catalyst)
The polyurethane composition may further contain a catalyst. The catalyst is not particularly limited as long as it is a catalyst used in the urethanization reaction. For example, organotin compounds such as di-n-butyltin dilaurate, dimethyltin dilaurate, dibutyltin oxide, and octane tin; An organic zirconium compound; a carboxylic acid tin salt; a carboxylic acid bismuth salt; and an amine-based catalyst such as triethylenediamine.

If necessary, the polyurethane composition may be, for example, a lubricant, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a colorant, a modifier, a flame retardant, an antistatic agent, an antifogging agent, and a filler. Various additives such as an agent, a diluent, and an antifungal agent may be added.

When the differential scanning calorimetry (DSC) of the substrate 2 is performed, the glass transition temperature width is 23 ° C. or less, and the energy derived from the glass transition is 0.5 mJ / ° C./mg or less. is there. The glass transition temperature reflects the motion of the soft segment of the polyurethane. Therefore, the state where the glass transition temperature width is small and the energy derived from the glass transition is small corresponds to a state where the soft segment of the polyurethane is homogeneous and the energy required for the glass transition is small. Such a state is seen when the polyurethane soft segment is hardly constrained by the hard segment, in other words, the polyurethane soft segment and the hard segment are phase-separated. If the glass transition temperature width is 23 ° C. or less and the energy derived from the glass transition is 0.5 mJ / ° C. or less, the polyurethane soft segment and the hard segment are highly phase-separated. It is considered that the crystal domain due to the aggregation of the hard segments formed acts as a barrier for preventing the migration of the drug component contained in the pressure-sensitive adhesive layer 3 to the base material 2. Therefore, excellent chemical resistance can be realized without arranging a drug migration prevention layer between the base material 2 and the pressure-sensitive adhesive layer 3. The glass transition temperature width is preferably 20 ° C. or less, and more preferably 18 ° C. or less. The energy derived from the glass transition is preferably 0.45 mJ / ° C. · mg or less.

The glass transition temperature width and the energy derived from the glass transition are determined by the following method with respect to the substrate 2. FIG. 2 is an explanatory diagram of a glass transition temperature width of a base material and a method for determining energy derived from the glass transition of the base material.

The glass transition temperature range is calculated by the following formula (1).
“Glass transition temperature range (unit: ° C.)” = “Glass transition end temperature (unit: ° C.)” − “Glass transition start temperature (unit: ° C.)” (1)
The glass transition start temperature and the glass transition end temperature are determined in a DSC chart obtained by differential scanning calorimetry. First, as shown in FIG. 2, in the DSC chart, the straight line L ₁ which extended the baseline on the low temperature side to the high temperature side, the inflection point P _{0 (glass} transition point: In FIG. 2, the convex curve upward A tangent line L ₀ at a point that changes to a downwardly convex curve is drawn, and the temperature T ₁ (unit: ° C.) corresponding to the intersection point P _{1 of} both lines is defined as “glass transition start temperature”. Next, as shown in FIG. 2, in the DSC chart, a straight line L _{2 obtained} by extending the base line on the high temperature side to the low temperature side and a tangent line L ₀ at the inflection point P ₀ are drawn, and the intersection point P _{2 of} both lines is drawn. A temperature T ₂ (unit: ° C.) corresponding to is defined as “glass transition end temperature”. Then, the “glass transition temperature width” is calculated as T ₂ −T ₁ (unit: ° C.). If glass transition occurs at the time of temperature rise, the baseline shifts downward (on the negative side of the vertical axis) in the DSC chart.

The energy (unit: mJ / ° C · mg) derived from the glass transition was converted to the energy (unit: mJ / ° C) required to change the unit temperature (1 ° C) during the glass transition per unit weight (1 mg). Means things. Specifically, as shown in FIG. 2, energy (unit: mW / min) per unit time (1 minute) indicated by a DDSC chart (a state obtained by differentiating the DSC chart) obtained by differential scanning calorimetry, The energy derived from the glass transition is calculated by converting to the energy (unit: mJ / ° C.) required for changing the unit temperature (1 ° C.) and converting the energy per unit weight (1 mg). The energy derived from the glass transition is calculated using, for example, the analysis program “EXSTAR” attached to the differential scanning calorimeter “DSC6200” manufactured by Hitachi High-Tech Science Co., Ltd. with respect to the DSC chart obtained by differential scanning calorimetry. The

Specifically, the differential scanning calorimetry of the substrate 2 is performed by measuring a test piece (weight: about 10 mg) at −130 ° C. to 250 ° C. at a temperature rising rate of 20 ° C./min in a nitrogen atmosphere (flow rate: 30 ml / min). The temperature is raised to

The dimensional change rate when the substrate 2 is immersed in water (hereinafter also simply referred to as dimensional change rate) is preferably 5% or less. When the dimensional change rate of the base material 2 exceeds 5%, the water resistance of the base material 2 is excessively lowered, and there is a concern that the feeling of use is lowered. The dimensional change rate of the substrate 2 is more preferably 2.5% or less.

Specifically, the dimensional change rate of the substrate 2 is calculated as follows. First, with respect to a 50 mm square test piece, a 30 mm length cut is made in one direction leaving a 10 mm margin from both ends. Then, the cut test piece is immersed in water for 1 week in an environment of a temperature of 23 ± 5 ° C. Then, after removing a test piece from water and wiping off moisture, the cut length (cut length after being immersed in water) is measured, and the dimensional change rate of the base material 2 is calculated by the following formula (2). .
“Dimensional change rate of base material 2 (unit:%)” = 100−100 × “cut length after being immersed in water (unit: mm)” / 30 (unit: mm) (2)
When “the rate of dimensional change of the substrate 2”> 0, it means that the test piece (substrate 2) contracts when immersed in water. On the other hand, when “the rate of dimensional change of the substrate 2” <0, it means that the test piece (substrate 2) expands when immersed in water. The dimensional change rate of the base material 2 may be in at least one direction (particularly, the width direction of the base material 2: for example, corresponding to the short direction of the base material 2 during calendar molding). Here, “the dimensional change rate of the substrate 2 is X% or less” means that the absolute value of the calculated value by the above formula (2) is X% or less.

The 100% modulus of the substrate 2 is preferably 0.1 to 15 MPa. When the 100% modulus of the base material 2 is less than 0.1 MPa, the stiffness of the base material 2 becomes too weak, and there is a concern that the feeling of use is lowered. When the 100% modulus of the substrate 2 exceeds 15 MPa, the stiffness of the substrate 2 becomes too strong, and there is a concern that the feeling of use is lowered. A more preferable lower limit value of the 100% modulus of the substrate 2 is 0.5 MPa, and a more preferable upper limit value is 10 MPa.

The elongation of the substrate 2 is preferably 350% or more. When the elongation of the base material 2 is less than 350%, there is a concern that it is difficult to follow the movement of the skin when the medical adhesive film 1 is attached to a movable part such as a joint part. The elongation of the substrate 2 is more preferably 500% or more. Although the upper limit of the elongation of the base material 2 is not particularly limited, it may be 2000%.

Specifically, the 100% modulus and elongation of the base material 2 are the conditions of a temperature of 23 ± 2 ° C., a distance between marked lines of 50 mm, a distance between chucks of 100 mm, and a tensile speed of 300 mm / min with respect to a 19 mm wide test piece. Measured in The 100% modulus and elongation of the base material 2 may be in at least one direction (particularly, the width direction of the base material 2: for example, corresponding to the short direction of the base material 2 during calendar molding).

The thickness of the base material 2 is preferably 1 to 100 μm. When the thickness of the base material 2 is less than 1 μm, the strength and stiffness of the base material 2 may be reduced. When the thickness of the base material 2 exceeds 100 micrometers, there exists a possibility that the softness | flexibility of the medical adhesive film 1 may fall and a usability | use_condition may fall. A more preferable lower limit value of the thickness of the substrate 2 is 5 μm, and a more preferable upper limit value is 70 μm.

[Adhesive layer]
The pressure-sensitive adhesive layer 3 contains a drug component. The drug component is not particularly limited, and examples thereof include ketoprofen, indomethacin, glycol salicylate, felbinac, diphenhydramine and the like.

Examples of the material of the pressure-sensitive adhesive layer 3 include acrylic pressure-sensitive adhesives and rubber-based pressure-sensitive adhesives. Each pressure-sensitive adhesive may be a solvent type or an emulsion type, but is preferably a hot melt type.

A hot-melt type pressure-sensitive adhesive is a pressure-sensitive adhesive that has adhesiveness in a solid state at room temperature and can be applied to an adherend by heating and melting. Moreover, since the hot-melt adhesive is a solventless type, the solvent does not remain in the medical adhesive film 1, there is no concern about adverse effects such as irritation to the skin, and the environmental load is small. Furthermore, when forming the pressure-sensitive adhesive layer 3 using a hot-melt pressure-sensitive adhesive, since a drying step (drying device) for volatilizing the solvent is unnecessary, its productivity (production rate) can be increased, It is also possible to reduce the size of production equipment.

The hot-melt pressure-sensitive adhesive preferably contains an acrylic polymer as a base polymer, and has a softening point of 100 to 140 ° C. and a melt viscosity of 8000 to 40,000 m · Pa · s / 160 ° C. Examples of the acrylic polymer used as the base polymer include 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. And (co) polymers having a monomer component.

The hot-melt pressure-sensitive adhesive preferably contains a synthetic rubber as a base polymer, has a softening point of 80 to 130 ° C. and a melt viscosity of 1000 to 20000 m · Pa · s / 160 ° C. Examples of the synthetic rubber to be a base polymer include a styrene-isoprene-styrene copolymer (SIS), a styrene-butadiene-styrene copolymer (SBS), and a SEPS rubber obtained by hydrogenating a styrene-isoprene-styrene copolymer. Is mentioned.

In the medical pressure-sensitive adhesive film 1, the base material 2 and the pressure-sensitive adhesive layer 3 are in contact with each other. Therefore, a drug migration prevention layer (for example, a polyethylene terephthalate film) is disposed between the base material 2 and the pressure-sensitive adhesive layer 3. Absent. That is, according to the medical pressure-sensitive adhesive film 1, excellent chemical resistance can be realized without arranging a drug migration preventing layer between the base material 2 and the pressure-sensitive adhesive layer 3.

The medical adhesive film 1 may further have a separator on the surface of the adhesive layer 3 opposite to the base 2. A conventionally well-known thing can be used as a separator, For example, a release film, a release paper, etc. are mentioned. Examples of the release film include those obtained by subjecting a resin film such as polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, and polypropylene to easy release treatment. Examples of the release paper include those obtained by subjecting paper such as high-quality paper and glassine paper to easy release treatment. The easy release treatment is performed by applying, for example, a silicone release agent, an alkyd release agent, a fluorine release agent, or the like to the surface of at least the pressure-sensitive adhesive layer 3 side of the separator (release film, release paper, etc.). be able to. In addition, what is necessary is just to peel a separator when sticking the medical adhesive film 1 on skin.

The medical adhesive film 1 may further have a protective layer on the surface of the substrate 2 opposite to the adhesive layer 3. A conventionally well-known thing can be used as a protective layer, For example, the resin layer which consists of polycarbonate-type resin, polypropylene-type resin, etc. is mentioned.

Although it does not specifically limit as a manufacturing method of the medical adhesive film 1, For example, the following method is mentioned.

First, a polyurethane composition is prepared. The polyurethane composition can be prepared by melt-kneading a predetermined amount of each component using, for example, a continuous kneader, a Banbury mixer, a kneader, an extruder or the like.

Next, the prepared polyurethane composition is coated on the surface of a separately prepared support using a comma coater or the like and then dried. And if a support body is peeled, the base material 2 will be obtained. Moreover, you may produce the base material 2 by performing calendar molding, extrusion molding, injection molding, etc. with respect to the prepared polyurethane composition, for example. Especially, it is preferable that preparation of the base material 2 is performed by calendar molding. According to the calendar molding, the thickness of the substrate 2 can be made uniform regardless of the composition of the polyurethane composition. Furthermore, since the calendar molding is suitable for processing into various sizes, it can easily cope with the production of small lots. Examples of the calendar format used for calendar molding include an inverted L shape, a Z shape, an upright two shape, an L shape, and an inclined three shape. The roll temperature at the time of calendering may be appropriately selected according to the composition of the polyurethane composition, but is preferably 140 to 190 ° C, more preferably 160 to 180 ° C.

Next, the pressure-sensitive adhesive layer 3 is formed on one surface of the substrate 2. As a result, the medical adhesive film 1 is completed. As a method for forming the pressure-sensitive adhesive layer 3, a conventionally known method can be used. For example, the pressure-sensitive adhesive may be directly coated on one surface of the substrate 2, or a support prepared separately. After coating once on the surface, the support may be pressed against the base material 2 from the pressure-sensitive adhesive side to transfer the pressure-sensitive adhesive onto one surface of the base material 2. If a separator is used as the support, the separator can be disposed simultaneously with the formation of the pressure-sensitive adhesive layer.

EXAMPLES Hereinafter, although an Example is hung up and demonstrated in more detail about this invention, this invention is not limited only to these Examples.

In Examples and Comparative Examples, materials used for producing medical adhesive films and their abbreviations are as follows.

(Base material: Polyurethane composition)
A1: “Nipporan (registered trademark) 5138” manufactured by Tosoh Corporation
A2: “Nipporan 5111” manufactured by Tosoh Corporation
A3: “Nipporan 5199” manufactured by Tosoh Corporation
A4: “Crisbon (registered trademark) NYT-18” manufactured by DIC
A5: “Crisbon NY-373” manufactured by DIC
A6: “UST-135” manufactured by DIC
A7: “Haimuren (registered trademark) Y-210B” manufactured by Dainichi Seika Kogyo

(Adhesive layer material: Adhesive)
B1: “Morse Tape (registered trademark)” manufactured by Hisamitsu Pharmaceutical Co., Ltd. (drug component: ketoprofen)
B2: "Acnipipp" manufactured by Teika Pharmaceutical Co., Ltd. (drug component: indomethacin)

Example 1
First, the polyurethane composition A1 was coated on the surface of a separately prepared polyethylene terephthalate film (support) using a comma coater and then dried. And the base material was produced by peeling a polyethylene terephthalate film. When measured using a dial gauge (diameter of measuring element: 5 mm), the thickness of the base material was 15 μm.

Next, the pressure-sensitive adhesive was directly applied (attached) on one surface of the base material to form a pressure-sensitive adhesive layer. As a result, a medical adhesive film was completed. The application of the pressure-sensitive adhesive was performed in two specifications: when the pressure-sensitive adhesive B1 was used (hereinafter also referred to as specification 1) and when the pressure-sensitive adhesive B2 was used (hereinafter also referred to as specification 2).

(Examples 2-6 and Comparative Example 1)
Except having changed the base material (polyurethane composition) as shown in Table 1 and Table 2, it carried out similarly to Example 1, and manufactured the medical adhesive film of each case.

(Evaluation)
The following evaluation was performed about the medical adhesive film of each case. The results are shown in Tables 1 and 2.

(1) Differential scanning calorimetry (DSC)
Differential scanning calorimetry was performed on a medical adhesive film substrate using a differential scanning calorimeter “DSC6200” manufactured by Hitachi High-Tech Science. Differential scanning calorimetry was performed by heating a test piece (weight: about 10 mg) from −130 ° C. to 250 ° C. at a temperature rising rate of 20 ° C./min in a nitrogen atmosphere (flow rate: 30 ml / min). The results of differential scanning calorimetry are illustrated below.

The results of differential scanning calorimetry on the base material of the medical adhesive film of Example 3 will be described below with reference to FIG. FIG. 3 is a DSC chart of the base material of the medical pressure-sensitive adhesive film of Example 3.

(Glass transition temperature range)
First, as shown in FIG. 3, in the DSC chart, a straight line L _{1 obtained} by extending the low-temperature side base line to the high-temperature side and a tangent line L ₀ at the inflection point P ₀ are drawn, and an intersection P ₁ between the two lines is drawn. The corresponding temperature T ₁ (unit: ° C.) was defined as “glass transition start temperature”. Next, as shown in FIG. 3, in the DSC chart, a straight line L _{2 obtained} by extending the base line on the high temperature side to the low temperature side and a tangent line L ₀ at the inflection point P ₀ are drawn, and the intersection P _{2 of} both lines is drawn. The temperature T ₂ (unit: ° C.) corresponding to is defined as “glass transition end temperature”. The “glass transition temperature width” was calculated as T ₂ −T ₁ = 15.4 (unit: ° C.).

(Energy derived from glass transition)
For the DSC chart, the energy derived from the glass transition was calculated as 0.29 mJ / ° C./mg using the analysis program “EXSTAR” attached to the differential scanning calorimeter “DSC6200” manufactured by Hitachi High-Tech Science.

Similarly, for each of the other examples, the glass transition temperature range and the energy derived from the glass transition were calculated. For example, FIG. 4 is a DSC chart of the base material of the medical adhesive film of Comparative Example 1.

(2) Each of the medical adhesive films produced in chemical resistance specifications 1 and 2 was placed in an aluminum bag and allowed to stand in an environment at a temperature of 60 ° C. for 3 weeks (accelerated test was performed). . Then, the surface state of the base material of the medical adhesive film was visually observed. Judgment criteria were as follows.
5: No change in surface condition and very good (no occurrence of wrinkles, discoloration, etc.).
4: There was almost no change in the surface state, and it was good (there was little occurrence of wrinkles, discoloration, etc.).
3: There was a slight change in the surface condition (slight wrinkles, discoloration, etc. occurred).
2: There was a change in the surface state (wrinkles, discoloration, etc. occurred).
1: There was a remarkable change in the surface state (wrinkles, discoloration, etc. occurred remarkably).

(3) The surface of the base material of the textured medical pressure-sensitive adhesive film (the surface opposite to the pressure-sensitive adhesive layer) was touched by hand, and the tactile sensation was evaluated. Judgment criteria were as follows.
(Double-circle): There was no feeling of tension and the surface was very smooth.
○: There was no feeling of tension and the surface was smooth.
(Triangle | delta): There was a feeling of tension and the surface was not a little smooth.
X: There was a very tight feeling and the surface was not smooth.

(4) As water resistance, the dimensional change rate of the substrate was evaluated. FIG. 5 is an explanatory diagram of a method for evaluating the dimensional change rate of the substrate. As shown in FIG. 5, with respect to the 50 mm square test piece 10a cut out from the base material 2 of the medical pressure-sensitive adhesive film, one direction (the width direction of the base material 2: the base material is left with 10 mm margins from both ends). (Corresponding to the width direction of 2), a 30 mm long cut was made. And the test piece 10a which put the cut | notch was immersed in water for 1 week in the environment of temperature 23 +/- 5 degreeC. Then, after taking out the test piece 10a from water and wiping moisture, the cut length (cut length after being immersed in water) is measured with a caliper, and the dimensional change rate of the base material 2 by the following formula (2) Was calculated.
“Dimensional change rate of base material 2 (unit:%)” = 100−100 × “cut length after being immersed in water (unit: mm)” / 30 (unit: mm) (2)

(5) Tensile properties As tensile properties, 100% modulus of the substrate and elongation of the substrate were evaluated.

(100% modulus)
The load when the base material of the medical adhesive film was stretched 100% in the width direction using an automatic recording type tensile tester was defined as “100% modulus” (unit: MPa). FIG. 6 is an explanatory diagram of a method for measuring 100% modulus of a substrate. First, as shown in FIG. 6, the test piece 10 b (length: 180 mm, width: 19 mm) cut out from the base material 2 of the medical adhesive film was sandwiched by the chuck 11 from both sides. The distance between the marked lines was 50 mm, and the distance between the chucks was 100 mm. And the test piece 10b was extended to the longitudinal direction (equivalent to the width direction of the base material 2) on the conditions of the temperature of 23 +/- 2 degreeC and the tension speed of 300 mm / min. Here, when the 100% modulus was 0.1 to 15 MPa, it was judged that the medical adhesive film had flexibility suitable for medical use.

(Elongation)
The base material of the medical pressure-sensitive adhesive film was stretched in the width direction under the same method and conditions as when measuring the 100% modulus, and the elongation percentage of the test piece when it was broken was defined as “elongation” (unit:%). . Here, when the elongation was 350% or more, it was determined that the medical adhesive film had flexibility suitable for medical use.

As shown in Table 1 and Table 2, Examples 1-6 were excellent in chemical resistance. In addition, Examples 4 and 5 were particularly superior in texture to Examples 1 to 3 and 6. In Examples 1 to 6, the dimensional change rate of the base material was 5% or less, and the water resistance was excellent. Furthermore, Examples 1-6 were excellent also in the tensile physical property (100% modulus and elongation), and had the high softness | flexibility which can track a skin movement.

On the other hand, as shown in Table 2, in Comparative Example 1, the glass transition temperature width exceeds 23 ° C., and the energy derived from the glass transition exceeds 0.5 mJ / ° C./mg. It was inferior to 1-6.

1: Medical adhesive film 2: Substrate 3: Adhesive layer 10a, 10b: Test piece 11: Chuck T ₁ : Glass transition start temperature T ₂ : Glass transition end temperature L ₀ : Tangent line (inflection point P in DSC chart) Tangent at ₀ )
L ₁ , L ₂ : Straight line obtained by extending the base line in the DSC chart P ₀ : Inflection point (glass transition point) in the DSC chart
P ₁ : intersection point between tangent line L ₀ and straight line L ₁ P ₂ : intersection point between tangent line L ₀ and straight line L ₂

Claims (5)

A substrate made of polyurethane;
A pressure-sensitive adhesive layer in contact with the base material and containing a drug component;
When the differential scanning calorimetry of the substrate is performed, the glass transition temperature width is 23 ° C. or less, and the energy derived from the glass transition is 0.5 mJ / ° C. · mg or less. Adhesive film. The medical adhesive film according to claim 1, wherein a dimensional change rate when the base material is immersed in water is 5% or less. The adhesive film for medical use according to claim 1 or 2, wherein the substrate has a 100% modulus of 0.1 to 15 MPa. The medical adhesive film according to claim 1, wherein the base material has an elongation of 350% or more. The thickness of the said base material is 1-100 micrometers, The medical adhesive film in any one of Claims 1-4 characterized by the above-mentioned.

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