JP6045892B2 - Composite film for coating material used by coating an object subject to bending deformation - Google Patents

Description

  The present invention relates to a composite film for a covering material used by covering an object that undergoes bending deformation.

  Films for coating materials are used for the purpose of covering the surface of objects to be coated such as skin, human body, daily necessities and molded products so that the surface is not damaged, protected from contamination, or kept warm. It is done.

  An adhesive film laminated with a pressure-sensitive adhesive is used as such a purpose. (For example, see Patent Document 1)

  The object to which the film is applied may be subjected to bending deformation after the film is applied. The object is, for example, the surface of a joint such as a finger, the base of a book cover, the surface of a bag, the back of a folded wallet, or the surface of a metal plate to be pressed.

  When such an object is subjected to bending deformation after sticking, if the film does not follow the bending to be deformed, the film tends to peel at the time of deformation.

  In particular, the film is easy to peel off for a complicated surface deformation such as a surface of a joint portion such as a finger that causes many wrinkles on the surface by bending the finger. In addition, the conventional material has a characteristic that a corresponding stress is required for the deformation, the stress is less relaxed, and the stress is always applied when the deformation state is maintained. This means that when the deformation such as bending is restored, the material is restored as it is, but if the stress is continuously applied during the deformation, the adherend may be adversely affected. The greatest use is that when it is applied to the body, deformation always occurs, and if stress due to the deformation continues to be applied, there is a concern about damage to the skin, and a sense of incongruity and discomfort such as a feeling of tension will continue. The main objective of the present invention is to solve this type of problem.

  In addition, an acrylic resin film having a special composition can be considered as a material film suitable for such a purpose, but it has been difficult to realize. In addition, even an acrylic resin having a special composition has performance that cannot be achieved by an acrylic resin film alone, and a film combined with another material is required. However, the performance may deteriorate due to the combination with other materials, and in the present invention, the performance superior to that of the acrylic resin film alone is obtained, and the performance does not deteriorate due to the combination with other materials. It is a further focus of the present invention to obtain a composite film.

Japanese Patent Laid-Open No. 08-024288

  The present invention relates to a composite film for a coating material that is subject to bending deformation after coating and deforms following the bending, and the coating state is difficult to change, such as being difficult to peel off at the time of deformation, and the composite for coating material It aims at providing the adhesive tape using a film.

The gist of the present invention is that
A copolymer containing 0 to 20 mol% of a polymer unit comprising an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group and an alkyl methacrylate as main components and other polymerizable monomers or prepolymers copolymerizable therewith; ,
It is a film made of a mixed resin that is blended with polyurethane,
The copolymer has a 20% tensile load of 3 N / 25 mm or less,
An elastic modulus of 0.2 to 15 MPa,
Viscosity is 0.1-25 GPa · s,
The glass transition temperature is 15 ° C. or less,
Used by covering an object subject to bending deformation,
It is to be a composite film for a covering material.

In addition, the gist of the present invention is that
From a copolymer containing 0 to 20 mol% of a polymer unit comprising an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group and an alkyl methacrylate as main components and other polymerizable monomers or prepolymers copolymerizable therewith. And a membrane
It is a laminated film formed by laminating a film made of polyurethane,
The copolymer has a 20% tensile load of 3 N / 25 mm or less,
An elastic modulus of 0.2 to 15 MPa,
Viscosity is 0.1-25 GPa · s,
The glass transition temperature is 15 ° C. or less,
Used by covering an object subject to bending deformation,
It is to be a composite film for a covering material.

In addition, the gist of the present invention is that
The film made of polyurethane is a film for a covering material partially laminated so as to form a pattern on one side of the film made of the copolymer.

In addition, the gist of the present invention is that
From a copolymer containing 0 to 20 mol% of a polymer unit comprising an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group and an alkyl methacrylate as main components and other polymerizable monomers or prepolymers copolymerizable therewith. And a membrane
It is a composite film formed by combining fibers,
The copolymer has a 20% tensile load of 3 N / 25 mm or less,
An elastic modulus of 0.2 to 15 MPa,
Viscosity is 0.1-25 GPa · s,
The glass transition temperature is 15 ° C. or less,
Used by covering an object subject to bending deformation,
It is to be a composite film for a covering material.

In addition, the gist of the present invention is that
The present invention resides in the composite film for a covering material in which yarns made of elastic fibers are arranged in stripes or lattices in the surface direction and are buried or laminated in a film made of the copolymer.

In addition, the gist of the present invention is that
The cloth is a composite film for a covering material in which a cloth is embedded or laminated in a film made of the copolymer. .

In addition, the gist of the present invention is that
The cloth is a non-woven fabric, and the non-woven fabric is the composite film for a covering material composed of elastic fibers.

In addition, the gist of the present invention is that
Copolymer 100 containing, as main components, alkyl acrylate and alkyl methacrylate having 1 to 8 carbon atoms in the alkyl group, and 0 to 20 mol% of polymerized units composed of other polymerizable monomers or prepolymers copolymerizable therewith. It is a film made of a resin obtained by adding 0.2 to 5 parts by weight of silicone oil to parts by weight,
The copolymer has a 20% tensile load of 3 N / 25 mm or less,
An elastic modulus of 0.2 to 15 MPa,
Viscosity is 0.1-25 GPa · s,
The glass transition temperature is 15 ° C. or less,
Used by covering an object subject to bending deformation,
It is in the composite film for a covering material.

In addition, the gist of the present invention is that
The alkyl methacrylate is methyl methacrylate, the alkyl acrylate is ethyl acrylate, and the coating film composite film has a molar ratio of methyl methacrylate to ethyl acrylate of 40:90 to 40: 180. .

In addition, the gist of the present invention is that
In the composite film for a coating material, wherein the alkyl methacrylate is methyl methacrylate, the alkyl acrylate is butyl acrylate, and a molar ratio of methyl methacrylate to butyl acrylate is 1: 1.6 to 1: 2.5. There is to be.

In addition, the gist of the present invention is that
For the coating material, wherein the polymer unit includes a structural unit selected from alkyl acrylate having a hydroxyl group, alkyl acrylamide having a hydroxyl group, and acrylic acid, and the structural unit is contained in an amount of 1 to 10 mol% and crosslinked by a crosslinking agent. Being a composite film.

The cross-linking agent may be an isocyanate-based cross-linking agent.

The structural unit can be hydroxyethylacrylamide.

The structural unit may be hydroxyethyl acrylate.

The polymerized unit may include a silicone-based macromonomer.

The polymer unit may include a urethane prepolymer.

The polymer unit is composed mainly of methyl methacrylate and ethyl acrylate, the molar ratio of methyl methacrylate to ethyl acrylate is 40:90 to 40: 200, and can contain 1 to 10 mol% of hydroxyethyl acrylamide, isocyanate. It can consist of a copolymer crosslinked by a system crosslinking agent.

The polymerized unit may include 0.5 to 5% by weight of a silicone-based macromonomer based on the whole copolymer.

The polymerized unit may further contain methoxyethyl acrylate, and the molar ratio of the total molar amount of methyl methacrylate and ethyl acrylate to methoxyethyl acrylate may be 170: 15 to 140: 60.

Further, the gist of the present invention is that
The adhesive tape is formed by laminating an adhesive layer on the composite film for covering material.

Further, the gist of the present invention is that
It is a medical pressure-sensitive adhesive tape in which a paste is supported on the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape.

Further, the gist of the present invention is that
It is a medical tape in which a plaster is laminated on the composite film for covering material.

  According to the present invention, when an object to be coated is subjected to bending deformation after coating, the composite film for the coating material which is deformed following the bending and is difficult to be peeled at the time of the deformation, and the coating material for the coating material. An adhesive tape using the composite film is provided.

Sectional drawing which shows the state which laminated | stacked the layer of the adhesive on the composite film for coating | covering materials of this invention. Sectional drawing which shows the state which laminated | stacked the layer of the adhesive on the composite film for coating materials of this invention, and also laminated | stacked the release paper. Sectional drawing which shows the state which laminated | stacked the layer of the adhesive on the composite film for coating materials of this invention, and also stuck the paste. It is a cross-sectional schematic diagram which shows the state which affixed the adhesive film on skin, FIG. 4 (a) is the case of the conventional adhesive film, FIG.4 (b) is the case of the adhesive tape of this invention. The photograph which shows the state which stuck the adhesive film using the raw material film used for this invention, and a comparative product on the finger | toe. The schematic diagram which shows the state which affixed the composite film for coating | covering materials of this invention on the bending part of the cover of a book.

  The composite film for a coating material of the present invention is formed by combining a resin made of an acrylic copolymer and a functional material. In the present invention, “composite” means lamination or blending.

The composite film for a covering material of the present invention is used by covering an object. In the present specification, the term “coating” means covering and covering a predetermined part of an object, and covering means including pasting via an adhesive or the like.

  Examples of the functional material used in the present invention include urethane resin and silicone oil. These functional materials are combined by blending with an acrylic copolymer. When silicone oil is added, it is preferably crosslinked with an acrylic copolymer.

  Furthermore, a fiber is mentioned as a functional material combined with an acrylic copolymer used in the present invention. The fibers are compounded by blending with an acrylic copolymer as short fibers such as chopped fibers. Alternatively, the film is obtained by randomly or regularly arranging in a planar shape and combining with an acrylic copolymer. Furthermore, it is combined by being embedded in a resin film made of an acrylic copolymer or being laminated as a cloth such as a knitted fabric or a non-woven fabric.

  As shown in FIG. 1, generally, the composite film 2 for a covering material can be used as an adhesive tape 6 in which an adhesive layer 4 is laminated.

  When the adhesive tape 6 is used as a medical adhesive tape such as a wound dressing, as shown in FIG. 2, the adhesive tape 6 is formed by laminating the release paper 8 on the surface of the adhesive layer 4, and the release paper 8 is peeled off during use. It is preferable to apply the adhesive tape 6 to the affected area.

  The composite film for a covering material of the present invention may be used as a medical pressure-sensitive adhesive tape in which a paste 10 is laminated on a part of the surface of the pressure-sensitive adhesive layer 4 as shown in FIG. Alternatively, as another aspect, the plaster body 10 may be embedded and disposed between the pressure-sensitive adhesive layer 4 and the material film 2. Furthermore, the aspect in which the fine particles of the paste are dispersed in the pressure-sensitive adhesive layer 4 may be used. Thus, the adhesive tape of the structure by which the paste was carry | supported by the adhesive layer is used suitably as a medical adhesive tape.

  Furthermore, the composite film for a coating material of the present invention can be coated on an article that undergoes bending deformation as a coating material or a patch, thereby protecting the surface of the article. Generally, when such an object to be coated is subjected to bending deformation after coating, if the film does not follow the bending to be deformed, the film tends to peel off at the time of deformation, but the material film is coated with this film. Even if the covering object is bent and deformed, the film follows the bending and deforms, so that the close contact state with the object can be maintained even during the deformation.

  Furthermore, functional components, such as a rust preventive agent, can be included in the composite film used for such a use. Or an adhesive can be laminated | stacked on a composite film, and these functional components can be included in the adhesive and it can be set as a sticking material. Thereby, it can use for the use which performs protection and surface treatment of the sticking target object surface. This film has a low elastic modulus, has a large elongation at a constant load, has a high stress relaxation property, and adheres well to the curved surface of the surface of the object to be applied.

  Such coverings include the base of the book cover, the surface of the bag, the back of a folded wallet, the metal plate to be pressed, the metal product to be rust-proof, and the surface. Examples include members and products to be protected, members and products to be surface-treated, and the like. In addition, it is suitable for protecting and covering surfaces that undergo complex bending deformation. Furthermore, the usage is not limited to flat surfaces, and even if affixed to places with irregularities such as the human body, the film can be deformed along the irregularities so that stress can be greatly reduced and adhered to the surface. The function of this film is utilized effectively. It can be used for applications such as a buffer material having a slight thickness change between two layers.

  Furthermore, the film for a patch of the present invention can be applied not only to a wound dressing but also to a finger without a sense of incongruity during water work, and can be used to prevent rough skin and redness.

  In addition, the surface of the joint on the front side of the finger is wrinkled when the finger is stretched, and is stretched when the finger is bent. When an adhesive tape is applied to a site where wrinkles increase or decrease as a result of bending and stretching, the conventional adhesive film 50 cannot follow the movement of the skin surface as shown in FIG. There is a tendency that a gap 52 is formed in the valley portion. There is a risk that water may enter the gap 52 or a germ may enter and propagate. On the other hand, the pressure-sensitive adhesive tape 6 of the present invention follows a curved surface, as shown in FIG. 4B, and does not generate a gap between the skin surface 56 and the pressure-sensitive adhesive tape 6 even when the skin surface 56 is wrinkled. Adhesion between the surface 56 of the skin 58 and the adhesive tape 6 is maintained, and water does not enter between the surface 56 of the skin 58 and the adhesive tape 6, so that there is almost no possibility that bacteria will enter and propagate.

  The composite film for a coating material according to the present invention includes an antibacterial component typified by a fragrance component, a hinokithiol that is a vaporizable antibacterial agent, and a component derived from wasabi on a resin composed of an acrylic copolymer that is one of its constituent elements. By adding other physiologically active ingredients and medicinal ingredients, it can also be used as a coating material that provides aroma, antibacterial effect, and other medicinal effects under the environment of coating and pasting. Alternatively, a patch having a paste can be prepared by including these physiologically active ingredients in the adhesive layer 4 described later. Such a pressure-sensitive adhesive layer having a function that has some effect on the living body, such as a wound protecting action, a wound healing action, an antibacterial action, and a pharmacological action by a drug, is called a plaster. Thereby, it can use for the use which exhibits the therapeutic effect, antibacterial, bactericidal effect, etc. which a medicine has with respect to a person to a sticking site or a patient. Since the composite film for a coating material according to the present invention has a low elastic modulus and high stress relaxation properties, it follows the unevenness and expansion and contraction of the skin surface, enters the wrinkles, and enlarges the contact area. Since it has a function of extracting permeation, it is suitable for these applications. That is, it can be suitably used as a medical pressure-sensitive adhesive tape by laminating a paste on the composite film for covering material of the present invention.

  First, the acrylic copolymer used in the present invention will be described.

The acrylic copolymer used in the present invention has a glass transition temperature of 15 ° C. or lower,
When formed into a film, the film
Tensile load at 20% tension is 3 N / 25 mm or less Elastic modulus is 0.2 to 15 MPa
Viscosity is 0.1-25GPa · s
It is.

  A film made of an acrylic copolymer used in the present invention (hereinafter referred to as a material film) has a 20% tensile load of 3 N / 25 mm or less, so that it is a target to be applied when it is applied to a target object such as human skin. Since it easily stretches and deforms following the elongation of the object, it is difficult to float or peel when the surface of the object to be applied is stretched and deformed. Moreover, when it sticks on a sticking target object, a load is not given and a sticking target object is not distorted. For example, when applied to human skin, the feeling of tension is small.

  Since the elastic modulus of the material film is 15 MPa or less, the material film can be attached without causing wrinkles following the curved surface when it is attached to the curved surface. Furthermore, when the elastic modulus is 0.2 MPa or more, although it is as thin as 10 to 60 μm, it has moderate elasticity and stiffness and is excellent in handleability. Films without firmness and stiffness are difficult to handle, and the positioning of the film becomes unstable during the product manufacturing process or during the operation of attaching, and it is easy to cause trouble that the films stick together during the operation.

  It is more preferable that the material film has an elastic modulus of 0.2 to 5 MPa in order to achieve both ease of handling and the ability to stick without causing wrinkles following a curved surface. It is most preferable to be 1 to 5 MPa in order to achieve both easy handling and the ability to follow the curved surface without causing wrinkles.

The elastic modulus is measured as follows.
Let the specimen creep. The measurement is performed at 35 ° C. in a nitrogen atmosphere. First, an initial load of 1 mN is applied for 10 minutes so as to keep the film temperature at equilibrium with the ambient temperature. Thereafter, the film is stretched at 100 mN / min until the load reaches 30 kPa, and then creeped in a state where the load is 30 kPa.
The sample length (distance between chucks) when an initial load of 1 mN is applied for 10 minutes is L0, and the sample length when the load reaches 30 kPa is L30.
E = W × L0 / (L30-L0)
Ask for. Here, W is 30 kPa.
In the present invention, the value E thus measured is defined as the elastic modulus.
In addition, the length of the sample after 7 minutes and 10 minutes after the load reaches 30 kPa is set to L7 and L10, respectively, and R = (L10−L7) / L7,
V = W × T / R
Ask for. Here, T is 180 sec. In the present invention, the value V thus measured is defined as viscosity.

  In addition, when the material film follows the curved surface, it is at least partially stretched. However, when the material film has a viscosity of 0.1 to 25 GPa · s, the material film is applied following the curved surface. Since the stretched state is relaxed in a short time, peeling is unlikely to occur. In other words, even if the surface of the object to be applied is elongated due to bending deformation of the object to be applied after the application, the stress due to the expansion of the adhesive material is reduced in a short time when the adhesive is expanded following the extension. Since it is alleviated, peeling does not occur easily. In particular, when affixed to the human skin, the feeling of depression associated with the movement of the human body is small. Further, by following the curved surface of the human body and its deformation by relaxation of the stretched state, the stuck state can be maintained without the attached tape lifting from the skin surface.

  A material film whose viscosity exceeds this range is large, and when the patch is stretched following the stretch even if the surface of the paste target is stretched due to bending deformation of the paste target, etc. Since the stretched state of the patch is not relaxed in a short time, peeling easily occurs. Moreover, when it is applied to the human skin, there is a feeling of being depressed as the human body moves. Moreover, it is easy to produce a peeling wrinkle following the curved surface of a human body or its deformation, and it is difficult to maintain the pasted state. The smaller the viscosity, the easier it is to stretch during the sticking operation, and the sticking operability tends to decrease. When the viscosity is less than 0.1 GPa · s, the pasting operability is poor due to excessive elongation during the pasting operation.

  It is more preferable that the material film has a viscosity of 1 to 10 GPa · s in order to achieve both the operability of adhesion and the difficulty of peeling when being applied following a curved surface. It is most preferable to be 1.8 to 10 GPa · s in order to achieve both the pasting operability and the difficulty of peeling when pasted following a curved surface.

Viscosity V is the formula V = W × T / (S × R)
It is a value represented by.
Here, a state in which a constant load W is applied to the strip-shaped sample (film) in the longitudinal direction is maintained, and the load time is T. The cross-sectional area of the sample to be used is S, and the rate of change of the sample length due to this load is R.

  In the present invention, the viscosity V is defined as described in paragraph [0056].

  Since the glass transition temperature is 15 ° C. or less, the material film has stable characteristics (elastic modulus, 20% tensile load and viscosity) when used in normal indoor work. In addition, when the object to be applied is a human body such as a finger, the material film expands and contracts following the deformation of the human body even if the human body of the part to which the material film is applied touches cold water. Peeling trouble is unlikely to occur.

  It is more preferable that the glass transition temperature is 10 ° C. or less in that a trouble of peeling during work in a state where the human body where the material film is attached is in contact with cold water hardly occurs.

  In the present invention, the glass transition temperature is the midpoint (intermediate point) where the sample is rapidly cooled to −50 ° C. and heated to 60 ° C. at 10 ° C./min, and the baseline of the differential heat-temperature chart changes stepwise. Point glass transition temperature).

When the material film is used by being attached to the skin, it is preferable that the moisture permeability is 900 g / (m ² · day) or more because there is little stuffiness. Moreover, when it affixes on the sticking target object which consists of a hygroscopic material, the degree which affects the moisture absorption / release property of a sticking target object is small.

The moisture permeability is more preferably 1000 g / (m ² · day) or more from the viewpoint of less feeling of stuffiness when affixed to the skin. 1190 g / (m ² · day) or more is most preferable in terms of less stuffiness when applied to the skin.

  As the material film, a film made of an acrylic copolymer is preferably used.

As the acrylic copolymer used for the material film, the main component of the random copolymer is an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group and an alkyl methacrylate, and other polymerizable properties copolymerizable with these. A copolymer containing 0 to 20 mol% of a polymerization unit composed of a monomer, oligomer or prepolymer is preferred.
The carbon number of the alkyl methacrylate is not particularly limited, but methyl methacrylate or ethyl methacrylate is preferable. The arrangement of the repeating units of the polymer may be a block.

  Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, etc. Among them, ethyl acrylate and butyl acrylate are preferable.

  Examples of the alkyl methacrylate include methyl methacrylate and ethyl methacrylate.

  When the acrylic copolymer is not crosslinked and the alkyl methacrylate in the acrylic copolymer is methyl methacrylate and the alkyl acrylate is ethyl acrylate, the molar ratio of methyl methacrylate to ethyl acrylate is 40:90 to 40: 180 is preferable for obtaining the above-described physical property values. If the ratio of methyl methacrylate is reduced outside this range, the elastic modulus of the raw material film is lowered, and the physical properties may not be obtained, resulting in poor handling. When the ratio of methyl methacrylate is increased outside this range, the glass transition temperature increases, resulting in a relatively hard and brittle film, which is optimal in terms of the feeling of use (discomfort) in the target application and the difficulty of lifting and peeling. I can't say that. Also, the water vapor transmission rate is lowered.

  When the alkyl methacrylate in the acrylic copolymer is methyl methacrylate and the alkyl acrylate is butyl acrylate, the molar ratio of methyl methacrylate to butyl acrylate is 1: 1.6 to 1: 2.5. It is preferable. If the ratio of the methyl methacrylate is reduced outside this range, the film will not be stiff and firm, and the handleability will deteriorate depending on how it is handled. If the ratio of methyl methacrylate is increased outside this range, the glass transition temperature increases, resulting in increased viscosity at room temperature, resulting in a relatively hard and brittle film, and a feeling of use (discomfort) in the target application, and difficulty in floating and peeling off. This is not optimal. Also, the water vapor transmission rate is lowered.

  Examples of other polymerizable monomers that can be copolymerized include polymerizable monomers having a partial structure such as alkoxyalkyl acrylate, urethane, and amide and an ethylenically unsaturated double bond, acrylonitrile, methacrylonitrile, styrene, vinyl acetate, Examples include vinyl chloride, vinylidene chloride, alkyl vinyl ether, and benzyl acrylate.

  When the alkyl methacrylate is methyl methacrylate, the alkyl acrylate is ethyl acrylate, and the other polymerizable monomer that can be copolymerized includes methoxyethyl acrylate, the total molar amount of methyl methacrylate and ethyl acrylate and methoxyethyl acrylate Is preferably 170: 15 to 140: 60 in order to obtain the above-mentioned physical property values. Such a copolymer is more preferably crosslinked to obtain the optimum physical property values.

  Furthermore, the other polymerizable monomer that can be copolymerized includes a macromonomer that is a high molecular weight monomer having a polymerizable functional group. Examples include silicone-based macromonomers such as polysiloxane macromonomers in which polymerizable groups are bonded to the siloxane main chain, and styrene-based macromonomers in which polymerizable groups are bonded to the styrene main chain. AA-6, AA-2, AS-6, AN-6S, AB-6, AK-5, AK-32 (all manufactured by Toagosei Co., Ltd.) and the like can be used.

  The slipperiness of the film is improved by copolymerizing the silicone-based macromonomer. The content of the silicone-based macromonomer is preferably 0.5 to 5% by weight with respect to the entire copolymer.

  Examples of copolymerizable oligomers include urethane acrylate oligomers.

  Still further, other polymerizable monomers that can be copolymerized include hydroxyalkyl acrylamide, hydroxyalkyl acrylate, and acrylic acid. When such a hydroxyl group-containing monomer is copolymerized, the firmness of the film is improved. Moreover, the strength and alcohol resistance of the film can be improved by reacting with a functional group such as a hydroxyl group to crosslink the copolymer. However, excessive crosslinking results in an increase in elastic modulus, a decrease in moisture permeability, and an increase in glass transition temperature. Two or more types of monomers having a hydroxyl group may be copolymerized in the copolymer.

  Examples of the crosslinking agent that performs such crosslinking include an isocyanate crosslinking agent, a melamine crosslinking agent, a urea resin crosslinking agent, a polybasic acid crosslinking agent, and an epoxy crosslinking agent. Among these, an isocyanate-based crosslinking agent is preferable for improving the stiffness, strength, and alcohol resistance while maintaining the viscosity and flexibility of the film.

  Examples of the isocyanate-based crosslinking agent include polyvalent isocyanate, and include hexamethylene diisocyanate, isophorone diisocyanate, and tolylene diisocyanate.

  In the case where the alkyl methacrylate in the acrylic copolymer is methyl methacrylate, the alkyl acrylate is ethyl acrylate, and the copolymer is crosslinked with the crosslinking agent as described above, the moles of methyl methacrylate and ethyl acrylate are A ratio of 40:90 to 40: 200 is preferable for obtaining the optimum physical property values. If the ratio of methyl methacrylate is reduced outside this range, the elastic modulus will be low, and handling will be poor unless care is taken. When the ratio of methyl methacrylate is increased outside this range, the glass transition temperature increases, resulting in a relatively hard and brittle film, which is optimal in terms of the feeling of use (discomfort) in the target application and the difficulty of lifting and peeling. I can't say that. Also, the water vapor transmission rate is lowered.

  The material film can be applied not only to a wound dressing but also to a finger without a sense of incongruity at the time of water work, and can be used to prevent rough skin and redness.

  As shown in FIG. 1, generally, the material film 2 can be used as an adhesive tape in which an adhesive layer 4 is laminated.

  In addition, the surface of the joint on the front side of the finger is wrinkled when the finger is stretched, and is stretched when the finger is bent. When the adhesive tape 6 is affixed to a site where wrinkles increase or decrease with such bending and stretching, the conventional adhesive film cannot follow the movement of the skin surface, and there is a tendency that a gap is formed in the valley portion of the wrinkles. . There is a risk of water intrusion into the gap or breeding with fungus. On the other hand, the adhesive tape 6 does not create a gap between the skin surface and the adhesive tape 6 even when the skin surface is wrinkled following the curved surface, and the adhesion between the skin surface and the adhesive tape 6 is maintained. The water does not enter between the surface of the skin and the adhesive tape 6, and there is almost no possibility of bacteria and the like to propagate.

The compatibility between the difficulty of occurrence of such floating and peeling and the pasting operability is brought about by the characteristics of the material film described above. That is,
Material film
Tensile load at 20% tension is 3 N / 25 mm or less Elastic modulus is 0.2 to 15 MPa
Viscosity is 0.1-25GPa · s
It is brought about by being.

  In order to achieve both the difficulty of occurrence of such floating and peeling and the pasting operability, it is more preferable that the viscosity of the material film is 1 to 10 GPa · s. Most preferably 1.8 to 10 GPa · s

  In this way, the material film is used as an adhesive film by laminating an adhesive layer, and even if it is applied to the skin part where wrinkles change by moving, no gap is formed between the skin surface and the adhesive film. In addition, it is possible to maintain a close contact state with the skin surface.

First, an experimental example regarding a material film, a comparative experimental example , and a reference experimental example will be described. Films obtained in the following experimental examples can be used as this material film.

Measurement;
Tensile test Tensile test is performed at a distance between chucks of 50 mm, tensile speed of 300 mm / min, sample size length 80 mm x width 20 mm x thickness 30 μm, elongation at break and strength, stress at a specific elongation (20% elongation) The stress at the point (20% modulus, etc.) was measured.

Moisture permeability was measured by a cup method according to JIS Z0208. Using calcium chloride as the hygroscopic agent and paraffin (melting point: 52-54 ° C.) commercially available as a reagent for the sealant, it was installed in a constant temperature and humidity chamber at a temperature of 40 ° C. and a humidity of 90% RH. The increasing weight of the entire cup was measured three times every 1.5 hours, and the moisture permeability was determined from the average value of the second and third measurements.

Elastic modulus, viscosity Co., Ltd. Rigaku Thermo plus EVO TMA / HUM-1 was attached to a film tensile test jig to an initial length of 10 mm, and the sample was creeped. The measurement was performed at 35 ° C. in a nitrogen atmosphere. The sample width was 5 mm and the thickness was 150 μm. First, an initial load of 1 mN was applied for 10 minutes so as to keep the film temperature at equilibrium with the ambient temperature. Thereafter, the film was stretched at 100 mN / min until the load reached 30 kPa, and then creeped in a state where the load was 30 kPa.
The sample length (distance between chucks) when an initial load of 1 mN is applied for 10 minutes is L0, and the sample length when the load reaches 30 kPa is L30.
E = W × L0 / (L30-L0)
The elastic modulus defined by Here, W is 30 kPa.
In addition, the length of the sample after 7 minutes and 10 minutes after the load reaches 30 kPa is set to L7 and L10, respectively, and R = (L10−L7) / L7,
V = W × T / R
The viscosity defined by is obtained. Here, T is 180 sec.

Glass transition temperature PerkinElmer DSC8500 was used, and the sample temperature was adjusted to 50 ° C., then rapidly cooled to −50 ° C. and increased to 60 ° C. at 10 ° C./min. The measurement was performed in a nitrogen atmosphere. The intermediate point (intermediate point glass transition temperature) where the baseline of the differential heat-temperature chart changes stepwise was defined as the glass transition temperature.

Evaluation alcohol resistance x: Deforms or dissolves so that the shape cannot be maintained when immersed in ethanol.
Δ: Shape and physical properties change due to swelling when immersed in ethanol, but withstands use.
○: When immersed in ethanol, the shape and physical properties hardly change, and the same use state as before immersion is obtained.

Preparation of sample film When polymerizing monomers in each of the following experimental examples, comparative experimental examples, and reference experimental examples, unless otherwise specified, an appropriate amount of azobisisobutyronitrile (AIBN) was used as a polymerization initiator, and a nitrogen atmosphere was used. Polymerization was carried out in solution.

Regarding crosslinking, aging (40 ° C., 72 hr) after film formation was performed on the samples crosslinked using a crosslinking agent in the following experimental examples and comparative experimental examples in order to terminate the crosslinking reaction.

Experimental example 1
Acetic acid to 120 g of a mixture of ethyl acrylate (EA) / methyl methacrylate (MMA) = 140/40 (mol / mol) and hydroxyethyl acrylamide (HEAA) in a molar ratio HEAA / (MMA + EA + HEAA) of 3 mol% with respect to the whole monomer 180 g of ethyl was added, 0.064 g of AIBN was added as a polymerization initiator, and polymerization was performed at 70 ° C. for 5 hours. The solution after polymerization was cast on release paper and dried to obtain a film having a thickness of 30 μm.

Experimental example 2
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 1 except that HEAA was replaced with hydroxyethyl acrylate (HEA) and the amount of AIBN added was 160 mg.

Experimental example 3
MMA / EA is mixed at a molar ratio of 40:99, and acrylic acid (AA) is added in an amount of 3.7 mol% (AA / (MMA + EA + AA)) to a total of 120 g, 180 g of ethyl acetate and 160 mg of AIBN are added to form a nitrogen atmosphere. The solution after polymerization was cast on release paper and dried to obtain a film having a thickness of 30 μm.

Experimental Example 4-0
MMA / EA in a molar ratio of 40:99 is added to a total of 120 g, 180 g of ethyl acetate as a solvent and 200 mg of AIBN as an initiator are mixed and copolymerized, and the solution after polymerization is cast on release paper and dried, and the thickness is 30 μm. A film was obtained.

Experimental example 4-1
MMA / EA was set to a molar ratio of 40:99, 3 mol% of HEAA was added at a molar ratio of HEAA / (MMA + EA + HEAA) to the whole monomer, a total of 480 g, 720 g of ethyl acetate as a solvent, and 800 mg of AIBN as an initiator were mixed. The solution after polymerization was cast on release paper and dried to obtain a film having a thickness of 30 μm.

Experimental example 4-2
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 4-1, except that HEAA was used in a molar ratio of 6 mol% with respect to the whole monomer, the amount of the whole monomer was 120 g, ethyl acetate was 180 g, and AIBN was 200 mg.

Experimental Example 4-3
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 4-2, except that HEAA was used in a molar ratio of 10 mol% with respect to the whole monomer.

In Experimental Examples 3 and 4, ethyl acetate was used as a solvent and AIBN was used as a polymerization initiator. The concentration of the acrylic monomer at the start of the reaction was about 40% by weight.

Experimental Example 5-0
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 4-1, except that the total amount of monomers was 150 g, the solvent was 150 g of DMF instead of ethyl acetate, AIBN 125 mg, and the reaction temperature and time were 70 ° C. and 5 hours.

Experimental Example 5-1
To the solution of the copolymer obtained in Experimental Example 5-0, 1% by weight of a tolylene diisocyanate curing agent (manufactured by Nippon Polyurethane Industry: Coronate L-55) (TDI) is added to the solution. After the solution was cast on release paper, it was subjected to a crosslinking reaction simultaneously with heat drying at 100 ° C. for 3 minutes to obtain a film having a thickness of 30 μm.

Experimental Example 5-2
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 5-1, except that the amount of TDI was changed to 2% by weight.

Experimental Example 6-1
150 g of MMA / EA molar ratio of 40:99 and 150 g of toluene as solvent are mixed, 80 mg of AIBN is added as an initiator, copolymerized at 70 ° C. for 5 hours, and the polymerized solution is cast on release paper Thereafter, the film was dried to obtain a film having a thickness of 30 μm.

Experimental Example 6-2
MMA / EA was mixed at a molar ratio of 40:99, and an acrylic macromonomer having a styrene chain (Toagosei: AS-6) was added at a weight ratio (AS-6 / (MMA + EA + AS-6)) to the entire monomer. % Was copolymerized. Toluene was used as the solvent and AIBN was used as the initiator. The solution after polymerization was cast on release paper and dried to obtain a film having a thickness of 30 μm.

Experimental Example 6-3
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 6-2 except that 3% by weight of AS-6 was added to the whole monomer.

Experimental Example 7-1
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 6-1 except that acrylic macromonomer having an acrylonitrile-styrene copolymer chain (Toagosei: AN-6S) was used instead of AS-6.

Experimental Example 7-2
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 7-1 except that the amount of AN-6S added was changed to 3% by weight.

Experimental Example 8
MMA / EA was mixed at a molar ratio of 40: 120, and 3 mol% of HEAA was added at a molar ratio of HEAA / (MMA + EA + HEAA) to the whole monomer for copolymerization, and the polymerized solution was cast on release paper and dried. A film having a thickness of 30 μm was obtained.

Experimental Example 9
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 1 except that the HEAA ratio was 1 mol%.

Experimental Example 10
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 1 except that the HEAA ratio was changed to 5 mol%.

Experimental Example 11
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 1, except that the HEAA ratio was 10 mol%.

Experimental Example 12
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 3 except that the AA ratio was 3 mol%.

Experimental Example 13
MMA / EA is mixed at a molar ratio of 40: 140, and 3 mol% of AA is added at a molar ratio of AA / (MMA + EA + AA) to the whole monomer for copolymerization, and the solution after polymerization is cast on release paper and dried. A film having a thickness of 30 μm was obtained.

Experimental Example 14
MMA / EA was mixed at a molar ratio of 40:99, copolymerized by adding 3 mol% of HEA at a molar ratio of HEA / (MMA + EA + HEA) to the whole monomer, and the solution after polymerization was cast on release paper and dried. A film having a thickness of 30 μm was obtained.

Experimental Example 15
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 2 except that the HEA ratio was changed to 5 mol%.

Experimental Example 16
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 2, except that the HEA ratio was 10 mol%.

Experimental Example 17
MMA / butyl acrylate (BA) is added in a molar ratio of 2: 3, and HEAA / (MMA + BA + HEAA) is 3 mol%. HEAA is added to 120 g, and ethyl acetate 180 g of solvent and AIBN 160 mg of initiator are added to react. The solution after polymerization was cast on release paper and dried to obtain a film having a thickness of 30 μm.

Comparative Experiment Example 1
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 17 except that the molar ratio of MMA / butyl acrylate (BA) was 1: 2.

Comparative Experiment Example 2
A film having a thickness of 30 μm was obtained in the same manner as Comparative Experimental Example 1 except that the molar ratio of MMA / BA was 1: 1.

Reference Experiment Example 1
MMA / octyl acrylate (OA) was mixed at a molar ratio of 6: 4, and 3 mol% of HEAA was added at a molar ratio of HEAA / (MMA + OA + HEAA) to the total monomer to make 120 g, 180 g of ethyl acetate as a solvent, 160 mg of AIBN as an initiator The solution after polymerization was cast on a release paper and then dried to obtain a film having a thickness of 30 μm.

Comparative Experiment Example 3
Ethyl methacrylate (EMA) / EA was mixed at a molar ratio of 9: 5, and 3.1 mol% of HEAA was added and copolymerized at a molar ratio of HEAA / (EMA + EA + HEAA) to the whole monomer, and the solution after polymerization was peeled off. After casting on paper, it was dried to obtain a film having a thickness of 30 μm.

Comparative Experiment Example 4
A film having a thickness of 30 μm was obtained in the same manner as Comparative Example 3 except that the molar ratio of EMA / EA was 1: 1 and HEAA was 3 mol%.

Experimental Example 18
A film having a thickness of 30 μm was obtained in the same manner as in Comparative Experimental Example 5 except that the molar ratio of EMA / EA was 1: 2.

Experimental Example 19
A film having a thickness of 30 μm was obtained in the same manner as in Comparative Experimental Example 5 except that the molar ratio of EMA / EA was 1: 3.

Experimental Example 20
MMA / EA / MEA (methoxyethyl acrylate) was mixed at a molar ratio of 40: 120: 20, and 3 mol% of HEAA was added at a molar ratio of HEAA / (MMA + EA + MEA + HEAA) to the total monomer to give 120 g, and then 180 g of ethyl acetate was added. The solvent of AIBN and 160 mg of initiator were added for copolymerization, and the polymerized solution was cast on a release paper and dried to obtain a film having a thickness of 30 μm.

Experimental Example 21
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 20, except that the molar ratio of MMA / EA / MEA was 40: 100: 40.

Experimental Example 22
MMA / EA = 40/140 (molar ratio), HEAA was added so that HEAA / (HEAA + MMA + EA) would be 3 mol%, and 1 wt% of AK-32 (methacrylic acid having a polydimethylsiloxane structure) was added to this mixture. System macromonomer: manufactured by Toagosei Co., Ltd.) was added, 120 g of a mixed solution of HEAA + MMA + EA + AK-32 was taken, 180 g of toluene and 160 mg of AIBN were added, and copolymerization was performed in a nitrogen atmosphere. The solution after polymerization was cast on release paper and dried to obtain a film having a thickness of 30 μm.

Experimental Example 23
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 22 except that AK-5 was added to the mixture instead of AK-32. The solid content of AK-5 was 40 wt%, and the solid content of AK-5 was added so as to be 1 wt% with respect to the mixture.

Comparative Experiment Example 5
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 6-2 except that the added amount of AS-6 was 10% by weight and 80 mg of AIBN was used.

Experimental Example 24
MMA / EA was mixed at a molar ratio of 40: 140, 3 mol% of hydroxyethyl methacrylate (HEMA) was added and copolymerized at a molar ratio of HEMA / (MMA + EA + HEMA) with respect to the whole monomer, and the polymerized solution was released onto a release paper. And then dried to obtain a film having a thickness of 30 μm.

Experimental Example 25
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 6-2 except that the molar ratio of MMA / EA was 40: 140.

Experimental Example 26
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 25 except that the addition amount of AS-6 was 3% by weight.

Experimental Example 27
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 25 except that the addition amount of AS-6 was changed to 5% by weight.

Experimental Example 28
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 25 except that the addition ratio of AS-6 was changed to 10% by weight.

Experimental Example 29
To the copolymer solution obtained by the copolymerization in Experimental Example 1, 5.2 parts by weight of a curing agent TDI is added to 100 parts by weight of the solution, and the solution is cast on release paper and heated at 100 ° C. for 3 minutes. A film having a thickness of 30 μm was obtained by carrying out a crosslinking reaction simultaneously with drying.

Experimental Example 30
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 29 except that the ratio of the curing agent to be added was 1.9 parts by weight with respect to 100 parts by weight of the copolymer solution.

Experimental Example 31
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 29 except that the ratio of the curing agent to be added was 0.94 parts by weight with respect to 100 parts by weight of the copolymer solution.

Experimental Example 32
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 29 except that the ratio of the curing agent added was 0.47 parts by weight with respect to 100 parts by weight of the copolymer solution.

Experimental Example 33
1.9 parts by weight of TDI is added to 100 parts by weight of the solution obtained in Example 13 after polymerization, the solution is cast on a release paper, and then crosslinked at the same time with heat drying at 100 ° C. for 3 minutes. Reaction was performed to obtain a film having a thickness of 30 μm.

Experimental Example 34
To the solution after polymerization obtained in Experimental Example 2, 1.9 parts by weight of TDI is added to 100 parts by weight of the solution. After the solution is cast on a release paper, the crosslinking reaction is simultaneously performed by drying at 100 ° C. for 3 minutes. And a film having a thickness of 30 μm was obtained.

Experimental Example 35
To the solution after polymerization obtained in Experimental Example 1, 1.2 parts by weight of a hexamethylene diisocyanate curing agent (manufactured by Nippon Polyurethane Industry: Coronate HX) (HDI) with respect to 100 parts by weight of the solution, After the solution was cast on release paper, it was subjected to a crosslinking reaction simultaneously with heat drying at 100 ° C. for 3 minutes to obtain a film having a thickness of 30 μm.

Experimental Example 36
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 35 except that the ratio of the curing agent to be added was 0.59 parts by weight with respect to 100 parts by weight of the solution.

Experimental Example 37
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 35 except that the ratio of the curing agent to be added was 0.30 part by weight with respect to 100 parts by weight of the solution.

Experimental Example 38
A film having a thickness of 30 μm was obtained in the same manner as in Experimental Example 35 except that the ratio of the curing agent to be added was 0.15 parts by weight with respect to 100 parts by weight of the solution.
Sample film characteristics

Experimental Example 39
To the solution after polymerization obtained in Experimental Example 15, 3.2 parts by weight of TDI is added to 100 parts by weight of the solution, and the solution is cast on a release paper, followed by heat drying at 100 ° C. for 3 minutes and a crosslinking reaction. And a film having a thickness of 30 μm was obtained.

Experimental Example 40
To the solution after polymerization obtained in Experimental Example 16, 6.3 parts by weight of TDI is added to 100 parts by weight of the solution, and the solution is cast on a release paper, followed by heat drying at 100 ° C. for 3 minutes and a crosslinking reaction. And a film having a thickness of 30 μm was obtained.

Experimental Example 41
To the solution after polymerization obtained in Experimental Example 20, 1.9 parts by weight of TDI is added to 100 parts by weight of the solution, and the solution is cast on a release paper, followed by heat drying at 100 ° C. for 3 minutes and a crosslinking reaction. And a film having a thickness of 30 μm was obtained.

Experimental Example 42
1.9 parts by weight of TDI with respect to 100 parts by weight of the solution obtained in Experimental Example 21 was added, and the solution was casted on a release paper, followed by heat drying at 100 ° C. for 3 minutes and a crosslinking reaction. And a film having a thickness of 30 μm was obtained.

Experimental Example 43
1.9 parts by weight of TDI is added to 100 parts by weight of the solution obtained by polymerization in Experimental Example 22, and the solution is cast on a release paper, followed by heat drying at 100 ° C. for 3 minutes and a crosslinking reaction. And a film having a thickness of 30 μm was obtained.

Experimental Example 44
To the solution after polymerization obtained in Experimental Example 23, 1.9 parts by weight of TDI is added with respect to 100 parts by weight of the solution, the solution is cast on a release paper, and then heated and dried at 100 ° C. for 3 minutes simultaneously with the crosslinking reaction. And a film having a thickness of 30 μm was obtained.

Comparative Experiment Example 6
A urethane film (MF30BE-TB) (thickness 30 μm) manufactured by Nisshinbo Chemical Co., Ltd. was used.

Comparative Experiment Example 7
A polyurethane film (thickness 10 μm) was prepared using a urethane resin (Chrisbon ASPU-112) manufactured by DIC.

Comparative Experimental Example 8
A vinyl chloride film (thickness 60 μm) was prepared.

Characteristics and test results

a. The film obtained in Pasting Test Experimental Example 1, Comparative Experimental Example 6 , Comparative Experimental Example 7 and Comparative Experimental Example 8 was cut into a strip shape having a width of 20 mm and a length of 40 mm, and an acrylic adhesive layer (thickness 30 μm) on one side. Were laminated to obtain an adhesive tape. A monitor test was conducted in which this adhesive tape was wrapped around the first joint of the index finger and pasted. The results are shown in Table 1.

  The state of sticking is shown in FIG.

Also, ease of pasting (easy to paste), feeling of use (uncomfortable feeling), difficulty in lifting and peeling (difficult to lift when finger is bent and difficult to peel), ease of peeling, feeling of stuffiness About 10 monitors scored according to the following criteria.
Table 2 shows the average value of 1 point: bad, 3 points: satisfaction, 5 points: very good score.

  Looking at the feeling of use (no discomfort), Experimental Example 1 is superior to the Comparative Experimental Example, and excluding the difficulty of peeling, it has excellent characteristics with a score of 4.2. However, since it is easy to stretch, the evaluation score is low in terms of ease of peeling.

  Table 3 shows the characteristics of each film.

b. Changes in physical properties due to addition of HEAA Table 4 shows the characteristics when HEAA, which is an acrylic monomer having a hydroxyl group, is copolymerized with MMA and EA. The molar ratio of MMA / EA was 40:99. Addition of HEAA increases the glass transition temperature, viscosity, and elastic modulus.

c. Changes in physical properties due to crosslinking Table 5 shows changes in physical properties when a copolymer obtained by copolymerizing HEAA, which is an acrylic monomer having a hydroxyl group, with MMA and EA is crosslinked with a crosslinking agent. TDI was used as a crosslinking agent. Alcohol resistance is improved by crosslinking.

d. Table 6 shows the characteristics of an acrylic copolymer containing a macromonomer as a structural unit. The molar ratio of MMA / EA was 40:99. Alcohol resistance is improved by introducing an acrylic macromonomer having a styrene chain.

Table 7 shows characteristic values for each of the experimental examples other than the above, the comparative experimental examples , and the reference experimental examples .

For each of the experimental examples in Tables 4 to 7, the comparative experimental example , and the reference experimental example , the film was cut into a strip shape having a width of 20 mm and a length of 40 mm, and an acrylic pressure-sensitive adhesive layer (thickness 30 μm) was laminated on one side. I got a tape. A monitor test was conducted in which this adhesive tape was wrapped around the first joint of the index finger and pasted. Tables 8 and 9 show the characteristics obtained in the monitor test (consultation of 10 persons). In addition, the comprehensive evaluation determination is a comprehensive evaluation of the individual evaluation items (excluding alcohol resistance) in Tables 8 and 9.

From Table 8, it is also shown in the experimental examples other than experimental example 1 that the items such as the feeling of use, the difficulty of peeling, the suffocating property, and the ease of sticking described above have good evaluation points. Moreover, although the peelability was inferior in Experimental Example 1, in other Experimental Examples, it was shown that this point was also modified by adding cross-linking or increasing the viscosity.
In Table 8,
◎◎ ... Excellent ◎ ... Excellent ○ ... Can be used well.
△ ・ ・ ・ No complaints in use × ・ ・ ・ Bad

Experimental Example 42
As shown in FIG. 6, an adhesive layer (not shown) was provided on one side of the material film 21 obtained in Experimental Example 1 and attached to the bent portion 24 at the base of the cover 22 of the book 20. By sticking, the surface of the bent portion 24 was protected, and it was difficult to be scratched. Further, the film 21 was not peeled off by bending of the bending portion 24 when the book was opened.

  As described above, the composite film for a covering material according to the present invention is formed by combining a resin made of the above acrylic copolymer such as an acrylic copolymer obtained in an experimental example and a functional material.

  The composite film for a coating material according to the present invention is a material film, “When the object to be coated is subjected to bending deformation after coating, the coating state is difficult to change, such as deformation following the bending and being difficult to peel off at the time of deformation”. While maintaining the performance, the composite material has added superior properties to the properties of the functional material. In addition, when an adhesive layer is provided on one side of a material film and affixed to an object, it maintains the performance that the object floats even if it is subjected to bending deformation and does not easily peel off. Excellent characteristics are added to the characteristics of the material.

  The composite film for a coating material of the present invention can be obtained by molding a blend resin obtained by blending a urethane resin as a functional material with the acrylic copolymer described above into a film. By composite, this composite film for coating materials has the performance that "when the object to be coated is subjected to bending deformation after coating, the coating state is difficult to change, such as deformation following the bending and difficult to peel off during this deformation" And the 20% tensile stress (20% modulus) increases, but the maximum tensile stress increases significantly while keeping it low in an acceptable range. Thus, when an adhesive layer is provided on one side of the composite film and affixed to an object, the operability is improved at the time of affixing / peeling operation, particularly peeling. That is, if the maximum tensile force of the composite film is not designed to be larger than the adhesive force between the pressure-sensitive adhesive and the adherend, it is easy to design the tape so that the tape does not break during peeling.

  By adding silicone oil as a functional material to the above-mentioned acrylic copolymer and then crosslinking and forming into a film, a composite film for a coating material according to another aspect of the present invention can be obtained. This composite film for a covering material maintains the performance that “when an object to be coated is subjected to bending deformation after coating, it deforms following the bending, and the covering state is difficult to change, such as being difficult to peel off at the time of deformation”. In addition, the coefficient of friction decreases due to the combination.

  By laminating a urethane film as a functional material on a film made of the aforementioned acrylic copolymer, a composite film for a coating material according to another embodiment of the present invention is obtained. This composite film for a covering material maintains the performance that “when an object to be coated is subjected to bending deformation after coating, it deforms following the bending, and the covering state is difficult to change, such as being difficult to peel off at the time of deformation”. In addition, the composite increases the 20% tensile stress (20% modulus), but greatly increases the maximum tensile stress while keeping it at a low level within an allowable range. Thus, when an adhesive layer is provided on one side of the composite film and affixed to an object, the operability is improved at the time of affixing / peeling operation, particularly peeling.

  A composite film for a coating material according to another aspect of the present invention is obtained by combining a cloth as a functional material with the above-mentioned acrylic copolymer. Examples of the composite mode include a two-layer stack, a sandwich stack, and a state in which a cloth is embedded in an acrylic copolymer film (film). This composite film for coating materials almost maintains the performance of "when the object to be coated is subjected to bending deformation after coating, it deforms following the bending, and the coating state is difficult to change, such as being difficult to peel off during this deformation". In addition, due to the composite, the stress at 20% tension (20% modulus) increases, but it can be kept at a low level within an allowable range. Also, the maximum tensile stress is greatly increased. Thus, when an adhesive layer is provided on one side of the composite film and affixed to an object, the operability is improved at the time of affixing / peeling operation, particularly peeling.

  Preferred fabrics include stretch nonwoven fabrics such as nonwoven fabrics made of elastic fibers, nonwoven fabrics formed by hydroentanglement, and stretch knitted fabrics. It is not limited to these. Moreover, the composite film suitably used for waterproof and moisture-permeable clothing can be obtained by laminating on clothing fabric.

  Moreover, the composite film for coating | covering material of the other aspect of this invention is obtained by shape | molding in a film, after adding a short fiber to the acrylic copolymer which consists of the above-mentioned acrylic copolymer as a functional material. This composite film for coating materials almost maintains the performance of "when the object to be coated is subjected to bending deformation after coating, it deforms following the bending, and the coating state is difficult to change, such as being difficult to peel off during this deformation". At the same time, the 20% tensile stress (20% modulus) increases, but the maximum tensile stress greatly increases while keeping it low in an allowable range. Thus, when an adhesive layer is provided on one side of the composite film and affixed to an object, the operability is improved at the time of affixing / peeling operation, particularly peeling. Depending on the orientation of the short fibers, the longitudinal and transverse tensile stresses can be changed.

  Furthermore, the composite film for a coating material according to still another aspect of the present invention can be obtained by arranging fibers as a functional material randomly or regularly in a plane and combining with an acrylic copolymer to form a film. can get. Examples of the composite mode include a two-layer laminate, a sandwich laminate, and a state where fibers arranged in a planar shape are embedded in an acrylic copolymer film (film).

  The fibers to be combined may be short fibers. Long fibers or yarns may be used. In the case of short fibers, for example, after blending with an acrylic copolymer, the composite film for a coating material of the present invention is obtained by forming into a film. In the case of long fibers or yarns, for example, the composite film for a coating material of the present invention is obtained by arranging in a striped pattern or a lattice pattern and combining with an acrylic copolymer to form a film. This composite film for coating materials almost maintains the performance of "when the object to be coated is subjected to bending deformation after coating, it deforms following the bending, and the coating state is difficult to change, such as being difficult to peel off during this deformation". At the same time, the 20% tensile stress (20% modulus) increases, but the maximum tensile stress greatly increases while keeping it low in an allowable range.

  If the composite fiber is an elastic fiber, or if the composite yarn contains an elastic fiber and has stretch properties, "If the object to be coated undergoes bending deformation after coating, it will follow the bending. The performance of “the coating state is difficult to change, such as being difficult to peel off at the time of deformation” is preferable. The elastic fiber is a fiber having rubber-like elasticity. Specifically, polyurethane-based elastic fibers, polyester-based elastic fibers, polyether-ester-based elastic fibers, polystyrene-based elastic fibers, or polytrimethylene terephthalate conjugate fibers typified by a bimetallic structure of multiple components, polytrimethylene terephthalate And a conjugate fiber of polyethylene terephthalate and the like. Among these, polyurethane elastic fibers are particularly preferable. Polyester fibers, polyamide fibers, polypropylene fibers, etc. constituting the false twisted yarn are also examples of elastic fibers. Usually, elastic fibers have a recoverability of 50% or more when stretched 50%.

  The composite film for a coating material of the present invention is often used by laminating an adhesive, but the adhesive is not particularly limited, and any material can be used. For this purpose, an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive (including those made of synthetic rubber) and the like can be used. Furthermore, a gel-like adhesive containing water or oil can also be used. The acrylic pressure-sensitive adhesive is copolymerized based on acrylic acid alkyl ester and acrylic acid having a polar group, acrylic acid ester having a hydroxyl group, or acrylamide, and a copolymer with a comonomer can be used if necessary. The thickness of the pressure-sensitive adhesive is in the range of 5 to 100 μm. However, since the composite film for a coating material of the present invention is very flexible, the thickness of the pressure-sensitive adhesive is 10 to 30 μm and suitable characteristics are often obtained.

Tensile test A sample of 80 mm × 20 mm was subjected to a tensile test at room temperature (23 ° C.) at 300 mm / min with a distance between chucks of 50 mm.

Dynamic friction coefficient measurement
Measurement was performed according to the JISK7312 dynamic friction coefficient measurement method. However, the size of the metal sled was 20 mm wide × 25 mm long, the weight of the sled was 25 g, and the flat plate on which the sled moves was 21 mm wide and about 100 mm long.
The film sample was stuck so that there was no wrinkle on both the flat plate on which the sled moves and the bottom surface of the metal sled, and the moving speed of the sled was changed to 100 mm / min to measure the dynamic friction coefficient between the films.

It measured by the method similar to the water vapor transmission rate of a water vapor transmission material film.

Comparative Reference Example 1 (H-0)
The film obtained in Experimental Example 1 was used as the film of Comparative Reference Example 1.

Example 1 (H-1)
15 g of the polymer solution obtained in Experimental Example 1 (with a solid content of 50% by weight), 6.7 g of urethane solution (DIC: ASPU-112), and 6.7 g of isopropanol were uniformly mixed with a homogenizer. After stirring until it was (about 1.5 minutes), 40 μl of urethane catalyst was added and stirred for about 50 seconds. The obtained resin solution was cast on a release film with a baker type applicator and then heated at 100 ° C. for 1 hour to obtain a composite film having a thickness of about 30 μm.

Example 2 (H-2)
After stirring 10 g of a polymer solution similar to that used in Example 1, 13.3 g of a urethane solution (DIC: ASPU-112), and 6.7 g of isopropanol until homogenized with a homogenizer (about 1.5 minutes) Then, 80 μl of urethane catalyst was added and stirred for about 50 seconds. The obtained resin solution was cast on a release film with a baker type applicator and then heated at 100 ° C. for 1 hour to obtain a composite film having a thickness of about 30 μm.

  Table 10 shows the physical property values of the obtained film.

  The composite films obtained in Examples 1 and 2 are the same as the film obtained in Experimental Example 1 “When the object to be coated is subjected to bending deformation after coating, it deforms following the bending, and peels off at this deformation. While the performance of “the coating state is difficult to change such as difficult” is almost maintained, the force at 20% tension is increased compared to the film obtained in Experimental Example 1, but the maximum tensile force is maintained while maintaining a low value. Mechanical properties have been greatly improved.

Example 3 (H-3)
Polyethylene short fibers (Mitsui Chemicals Co., Ltd .: Chemibest FDSS-5) were added to the same polymer solution as used in Experimental Example 20, and diluted with ethyl acetate. The content of the short fibers is 3% by weight with respect to the solid content of the polymer, and the concentration of the polymer after dilution (polymer + short fibers) is 30% by weight. The diluted solution was cast on a release film with a baker type applicator and then heated at 100 ° C. for 1 hour to obtain a composite film having a thickness of about 30 μm.

Example 4 (H-4)
A composite film was obtained in the same manner as in Example 3 except that the short fiber content was 5% by weight based on the solid content of the polymer.

Example 5 (H-5)
A composite film was obtained in the same manner as in Example 3 except that polyethylene short fibers (Mitsui Chemical Co., Ltd .: Chemibest FD380) were used as the short fibers.

Example 6 (H-6)
A composite film was obtained in the same manner as in Example 5 except that polyethylene short fibers (Mitsui Chemical Co., Ltd .: Chemibest FD380) were used as the short fibers.

Example 7 (H-7)
Ube Nitto Kasei chopped fiber was added as a short fiber to the same polymer solution obtained in Experimental Example 1, and diluted with ethyl acetate. The content of the short fibers is 3% by weight with respect to the solid content of the polymer, and the concentration of the polymer after dilution (polymer + short fibers) is 30% by weight. The diluted solution was cast on a release film with a baker type applicator and then heated at 100 ° C. for 1 hour to obtain a composite film having a thickness of about 30 μm.

Example 8 (H-8)
Nylon short fibers (fiber length: 1.5 mm, fineness: 1.1 dtex) are used as the short fibers, and the polymer obtained in Experimental Example 1 is used as the polymer, and the short fiber content is determined with respect to the solid content of the polymer. A composite film was obtained in the same manner as in Example 3 except that the amount was 1% by weight.

Example 9 (H-9)
Nylon short fibers (fiber length: 1.5 mm, fineness: 1.1 dtex) are used as the short fibers, and the polymer obtained in Experimental Example 1 is used as the polymer, and the short fiber content is determined with respect to the solid content of the polymer. A composite film was obtained in the same manner as in Example 3 except that the amount was 2% by weight.

Example 10 (H-10)
A composite film was obtained in the same manner as in Example 9 except that the short fiber content was 3% by weight based on the solid content of the polymer.

Example 11 (H-11)
A composite film was obtained in the same manner as in Example 9 except that polyester short fibers (fiber length: 6 mm, fineness: 1.5 dtex) were used as the short fibers.

  The composite films obtained in Example 3 to Example 11 were deformed following the bending when the object to be coated was subjected to bending deformation after coating. While the performance of “the coating state is difficult to change, such as sometimes difficult to peel off” is almost maintained, the 20% tensile stress (20% modulus) increases compared to the film obtained in Experimental Example 1, but is low within an acceptable range. While keeping it in place, the maximum tensile stress increases significantly. This improves the operability at the time of sticking / peeling operation, particularly at the time of peeling.

  Table 11 shows physical property values of the composite films obtained in Example 7, Example 9, Example 10 and Example 11 (20% tensile force, maximum tensile force (N) (average value in length and width)). Shown in

Example 12 (H-12)
A urethane resin solution (manufactured by Seiko Kasei Co., Ltd .: Rack Skin U-390) was cast on release paper and dried to form a thin film having a thickness of 1 μm. On the other hand, the polymer solution (solid content 40% by weight) obtained in Experimental Example 1 was cast on release paper and dried to form a film having a thickness of 30 μm. Immediately after drying, it was bonded to a thin film to obtain a composite film.

Example 13 (H-13)
A composite film was obtained in the same manner as in Example 12 except that the thickness of the thin film was 5 μm.

Example 14 (H-14)
A composite film was obtained in the same manner as in Example 12 except that the thickness of the thin film was 10 μm.

  Table 12 shows the physical properties of the composite films obtained in Examples 12 to 14 (20% tensile force (longitudinal and lateral average values)).

Example 15 (H-15)
The polymer solution (solid content 40% by weight) obtained in Experimental Example 1 was cast on release paper and dried to prepare a film having a thickness of 20 μm. A urethane non-woven fabric (weight per unit: 20 g / m ² ; manufactured by KB Selen: T90-20) was thermally laminated on this film to obtain a composite film.

Example 16 (H-16)
The polymer solution (solid content 40% by weight) obtained in Experimental Example 1 was cast on release paper so that the thickness after drying was 20 μm, and before the drying was completed, a urethane nonwoven fabric (weight per unit: 20 g) / M ² ; made by KB Seiren: T90-20), dried and then heat laminated to obtain a composite film. What was manufactured in this example was a composite film in which an elastic nonwoven fabric was mostly integrated in a polymer thin film.

  The composite films obtained in Example 12 to Example 16 were deformed following the bending when the object to be coated was subjected to bending deformation after coating. While the performance of “the coating state is difficult to change sometimes, such as being difficult to peel off” is almost maintained, the force at 20% tension is kept at a low value (1 N or less) compared to the film obtained in Experimental Example 1, and the maximum The mechanical property of tensile force was greatly improved, and the elongation at the time of maximum tension was almost the same level as the film obtained in Experimental Example 1. The composite films obtained according to these examples have improved operability, particularly operability during peeling. Moreover, it had excellent moisture permeability.

  Table 12 shows the physical property values of the composite films obtained in Examples 12 to 16.

Comparative Reference Example 2 (H-02)
An acrylic pressure-sensitive adhesive was laminated on the film obtained in Experimental Example 1 so as to form a layer having a thickness of 30 μm. This acrylic pressure-sensitive adhesive is a copolymer of 93 parts by weight of 2-ethylhexyl acrylate and 7 parts by weight of acrylic acid.

Example 17 (H-17)
A composite film is obtained by thermally laminating a long film of urethane (Toray Operontex Co., Ltd .: Lycra T-127C) arranged in parallel at 1 mm intervals on the same film as obtained in Experimental Example 1. Obtained. An acrylic pressure-sensitive adhesive was laminated on this composite film so as to form a layer having a thickness of 30 μm. This acrylic pressure-sensitive adhesive is a copolymer of 93 parts by weight of 2-ethylhexyl acrylate and 7 parts by weight of acrylic acid.

Example 18 (H-18)
In the same film as obtained in Experimental Example 1, urethane long fibers (Toray Operontex Co., Ltd .: Lycra T-127C) were arranged in parallel at intervals of 1 mm vertically and at intervals of 5 mm vertically (laterally). The composite film was obtained by heat laminating. An acrylic pressure-sensitive adhesive was laminated on this composite film so as to form a layer having a thickness of 30 μm. This acrylic pressure-sensitive adhesive is a copolymer of 93 parts by weight of 2-ethylhexyl acrylate and 7 parts by weight of acrylic acid.

  The composite films obtained in Example 17 and Example 18 were deformed following the bending when the coating target of the film obtained in Experimental Example 1 was subjected to bending deformation after coating. The performance of the coating state is difficult to change, such as being difficult to peel off at times, and the mechanical properties of 20% tensile force and maximum tensile force are significantly higher than the film obtained in Experimental Example 1. Improved. Further, in the transverse direction, the maximum tensile stress greatly increases in the longitudinal direction while keeping the 20% tensile stress (20% modulus) low in the allowable range. This improves the operability at the time of sticking / peeling operation, particularly at the time of peeling.

Table 13 shows the physical property values of the composite films obtained in Example 17 and Example 18.

Example 19 (H-19)
A urethane solution (DIC: ASPU112) was coated on a release substrate by a bar coater No. 34 (Yasuda Seiki Seisakusho), and the polymer solution obtained in Experimental Example 1 was then obtained by a Baker type applicator. The diluted product (solid content 30% by weight) was continuously cast on a release substrate and then dried at 100 ° C. for 30 minutes to obtain a laminated film. The gap of the Baker type applicator was 100 μm.

Example 20 (H-20)
A urethane solution (DIC: ASPU112) was applied onto a release substrate by Bar Coater No. 22 (Yasuda Seiki Seisakusho), and the polymer solution obtained in Experimental Example 1 was then obtained using a Baker type applicator. The diluted product (solid content 30% by weight) was continuously cast on a release substrate and then dried at 100 ° C. for 30 minutes to obtain a laminated film. The gap of the Baker type applicator was 100 μm.

Example 21 (H-21)
A urethane solution (DIC: ASPU112) was applied onto a release substrate by a bar coater No. 12 (Yasuda Seiki Seisakusho), and then a polymer solution obtained in Experimental Example 1 with a Baker type applicator ( (Solid content 30% by weight) was continuously cast on a release substrate and then dried at 100 ° C. for 30 minutes to obtain a laminated film. The gap of the Baker type applicator was 100 μm.

Table 14 shows the physical property values of the composite films obtained in Examples 19 to 21.

Example 22 (H-22)
2.8 parts by weight of the curing agent TDI (manufactured by Nippon Polyurethane Industry: Coronate L-55) with respect to 100 parts by weight of the polymer solution used in Example 16, and 0.5 with respect to 100 parts by weight of the solution solid content. Part by weight of silicone oil (manufactured by Momentive: TSF433) was added, cast on release paper, heated at 100 ° C. for 3 minutes, and dried and crosslinked to obtain a composite film having a thickness of 30 μm.

Example 23 (H-23)
A composite film was obtained in the same manner as in Example 23 except that the amount of the silicone oil was 1 part by weight with respect to 100 parts by weight of the solution solid content.

Example 24 (H-24)
A composite film was obtained in the same manner as in Example 23 except that the amount of the silicone oil was 2 parts by weight with respect to 100 parts by weight of the solid content of the solution.

Example 25 (H-25)
A composite film was obtained in the same manner as in Example 23 except that the amount of the silicone oil was 5 parts by weight with respect to 100 parts by weight of the solid content of the solution.

  The composite films obtained in Example 22 to Example 25 were deformed following the bending when the object to be coated was subjected to bending deformation after coating. While the performance of “the coating state is hardly changed, such as sometimes difficult to peel off” was almost maintained, the dynamic friction coefficient was reduced to about ½ to 1/10 compared with the film obtained in Experimental Example 1.

  Table 15 shows the dynamic friction coefficients of the composite films obtained in Examples 22 to 25.

Adhesion test The film obtained in Experimental Example 1, Example 1, Example 2, and the composite film obtained in Examples 9 to 20 were cut into strips having a width of 20 mm and a length of 40 mm, and acrylic on one side. A pressure-sensitive adhesive tape (thickness 30 μm) was laminated to obtain a pressure-sensitive adhesive tape. A monitor test was conducted in which this adhesive tape was wrapped around the first joint of the index finger and pasted. Ten monitors scored according to the following criteria for ease of peeling and difficulty of lifting and peeling (hardness of lifting when fingers were bent and difficulty of peeling).
Table 16 shows the average points of 1 point: bad, 3 points: satisfied, 5 points: very good for all monitors.

  The composite films obtained in Example 1, Example 2, and Examples 9 to 20 are difficult to peel (hard to be lifted when fingers are bent and difficult to peel) in Experimental Example 1. It was inferior to the film obtained. On the other hand, the operability has been greatly improved, and there has been no sharpness at the time of peeling.

  The composite film for a covering material of the present invention can be suitably used not only for medical applications but also for protecting the surface of an article by applying or covering the article subjected to bending deformation in daily necessities and industrial materials. It can also be applied to moisture-proof and water-permeable clothing.

2: Composite film for coating material 4: Adhesive layer 6: Adhesive tape 8: Release paper 10: Plaster

Claims (22)

Alkyl acrylate carbon atoms in the alkyl group 1 to 8, and the alkyl methacrylate as a main component, a copolymer comprising polymerized units consisting copolymerizable with these other polymerizable monomer or prepolymer 0-20 mole% When,
It is a film made of a mixed resin that is blended with polyurethane,
When the film made of the copolymer is molded, the film made of the copolymer has a 20% tensile load of 3 N / 25 mm or less, an elastic modulus of 0.2 to 15 MPa, and a viscosity of 0.1 to 25 GPa · s, the glass transition temperature is 15 ° C. or less , and the moisture permeability is 900 g / (m ² · day) or more .
A composite film for a covering material made of the mixed resin , which is used by covering an object subject to bending deformation. Alkyl acrylate carbon atoms in the alkyl group 1 to 8, and the alkyl methacrylate as a main component, a copolymer comprising polymerized units consisting copolymerizable with these other polymerizable monomer or prepolymer 0-20 mole% A membrane consisting of
It is a laminated film formed by laminating a film made of polyurethane,
When the film made of the copolymer is molded, the film made of the copolymer has a 20% tensile load of 3 N / 25 mm or less, an elastic modulus of 0.2 to 15 MPa, and a viscosity of 0.1 to 25 GPa · s, the glass transition temperature is 15 ° C. or less , and the moisture permeability is 900 g / (m ² · day) or more .
A composite film for a covering material comprising the laminated film , which is used by covering an object to be bent and deformed.   The coating film according to claim 2, wherein the film made of polyurethane is partially laminated so as to form a pattern on one side of the film made of the copolymer. Alkyl acrylate carbon atoms in the alkyl group 1 to 8, and the alkyl methacrylate as a main component, a copolymer comprising polymerized units consisting copolymerizable with these other polymerizable monomer or prepolymer 0-20 mole% A membrane consisting of
It is a composite film formed by combining fibers,
When the film made of the copolymer is molded, the film made of the copolymer has a 20% tensile load of 3 N / 25 mm or less, an elastic modulus of 0.2 to 15 MPa, and a viscosity of 0.1 to 25 GPa · s, the glass transition temperature is 15 ° C. or less , and the moisture permeability is 900 g / (m ² · day) or more .
A composite film for a covering material comprising the composite film , which is used by covering an object to be bent and deformed.   The composite film for a covering material according to claim 4, wherein yarns made of elastic fibers are arranged in a striped pattern or a lattice shape in a plane direction and embedded or laminated in a film made of the copolymer.   The composite film for a coating material according to claim 4, wherein a cloth is embedded or laminated in a film made of the copolymer.   The composite film for a covering material according to claim 6, wherein the cloth is a nonwoven fabric, and the nonwoven fabric is composed of elastic fibers. Alkyl acrylate carbon atoms in the alkyl group 1 to 8, and the alkyl methacrylate as a main component, a copolymer comprising polymerized units consisting copolymerizable with these other polymerizable monomer or prepolymer 0-20 mole% It is a film made of a resin obtained by adding 0.2 to 5 parts by weight of silicone oil to 100 parts by weight,
When the film made of the copolymer is molded, the film made of the copolymer has a 20% tensile load of 3 N / 25 mm or less, an elastic modulus of 0.2 to 15 MPa, and a viscosity of 0.1 to 25 GPa · s, the glass transition temperature is 15 ° C. or less , and the moisture permeability is 900 g / (m ² · day) or more .
A composite film for a covering material made of the added resin , which is used by covering an object to be bent and deformed. The alkyl methacrylate is methyl methacrylate;
The alkyl acrylate is ethyl acrylate;
The composite film for a covering material according to any one of claims 1 to 8, wherein a molar ratio of methyl methacrylate to ethyl acrylate is 40:90 to 40: 180. The alkyl methacrylate is methyl methacrylate;
The alkyl acrylate is butyl acrylate,
The composite film for a coating material according to claim 9, wherein the molar ratio of methyl methacrylate to butyl acrylate is 1: 1.6 to 1: 2.5. The polymer unit includes a structural unit selected from alkyl acrylate having a hydroxyl group, alkyl acrylamide having a hydroxyl group, and acrylic acid, wherein the structural unit is contained in an amount of 1 to 10 mol% and crosslinked by a crosslinking agent. The composite film for a coating material according to claim 10.   The composite film for a coating material according to claim 11, wherein the crosslinking agent is an isocyanate-based crosslinking agent. The composite film for a coating material according to claim 11 or 12, wherein the structural unit is hydroxyethylacrylamide. The composite film for a coating material according to claim 11 or 12, wherein the structural unit is hydroxyethyl acrylate. The composite film for a coating material according to any one of claims 1 to 14, wherein the polymerization unit includes a silicone-based macromonomer. The composite film for a covering material according to any one of claims 1 to 15, wherein the polymerization unit includes a urethane prepolymer. The copolymer is mainly composed of methyl methacrylate and ethyl acrylate, the molar ratio of methyl methacrylate to ethyl acrylate is 40:90 to 40: 200, 1 to 10 mol% of hydroxyethyl acrylamide is contained, and isocyanate The composite film for a coating material according to any one of claims 1 to 8, comprising a copolymer crosslinked with a system crosslinking agent.   The composite film for a coating material according to claim 17, wherein the polymerized unit contains 0.5 to 5% by weight of a silicone-based macromonomer based on the entire copolymer.   The coating material according to claim 18, wherein the copolymer further contains methoxyethyl acrylate, and a molar ratio of a total molar amount of methyl methacrylate and ethyl acrylate to methoxyethyl acrylate is 170: 15 to 140: 60. Composite film. An adhesive tape in which an adhesive layer is laminated on the composite film for a covering material according to any one of claims 1 to 19.   The medical adhesive tape by which the paste was carry | supported by the said adhesive layer of the adhesive tape of Claim 20. A medical tape in which a paste is laminated on the composite film for a covering material according to any one of claims 1 to 19.

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