JP4998356B2 - Medical release film - Google Patents

Description

  The present invention relates to a medical release film, and more particularly to a medical release film that protects a pressure-sensitive adhesive layer such as a patch by gas barrier properties, has a low transmittance of medicinal ingredients, and is excellent in release properties.

  Conventionally, patches have been used for the purpose of alleviating and suppressing inflammation and pain in the affected area. In order to supply a clinically effective amount of drug to the affected area, the patch is based on a knitted fabric made of microporous hollow fibers, etc., and has a drug layer containing a medicinal ingredient on one side, on which a medical release It is formed by laminating films. It is a kind of so-called transdermal absorbent, which is used by peeling off a medical release film and sticking an exposed drug layer on a trunk when in use. It is a drug that is frequently used in recent years because there is almost no difference in drug efficacy from that of orally administered drugs and there are few systemic side effects due to local action.

As a medical release film used for such a patch, an aluminum oxide layer impregnated with a barrier resin is provided on at least one surface of a polyester film, and a curable silicone resin layer is provided thereon. There is a medical release film (Patent Document 1). The medical release film described in Patent Document 1 uses a polyethylene terephthalate film having a high gas barrier property in order to extend the life of the medical release film, but the gas barrier property is not sufficient. In view of this point, an aluminum oxide layer is provided on one side of a polyester film by a reactive vapor deposition method, and this aluminum oxide layer is impregnated with a barrier resin to ensure gas barrier properties.
JP 2005-170865 A

  However, the medicinal layer of the medicated patch contains a medicinal component in an adhesive base sufficient to adhere to the affected area, and a medical release film is used to prevent contamination by the adhering component. It is laminated on the outermost layer. Therefore, the release film for medical use is expected to have excellent releasability from the drug layer in addition to maintaining the medicinal component, but the release film for medical use described in Patent Document 1 is not sufficient for release.

  Therefore, an object of the present invention is to provide a medical release film that is excellent in gas barrier properties, and particularly excellent in gas barrier properties even when embossing is performed.

As a result of examining the release film for medical use in detail, the present inventor supplied an organosilicon compound as a vapor deposition monomer by chemical vapor deposition and formed a vapor deposition film of carbon-containing silicon oxide on one surface of the base film. Provided, on the surface of the vapor-deposited film of carbon-containing silicon oxide, a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms; Represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), and at least one alkoxide represented by A laminated film containing a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer and further provided with a gas barrier coating film by a gas barrier composition obtained by polycondensation by a sol-gel method is a flexible and gas barrier. Excellent Therefore, it is possible to ensure excellent gas barrier properties even when embossing is performed, and because it has excellent adhesion to the curable silicone resin layer, by laminating the curable silicone resin layer, it has excellent release properties as well as gas barrier properties. As a result, the present invention was completed.

That is, the present invention is a medical release film comprising at least a gas barrier laminate film and a release layer, and the gas barrier laminate film supplies an organosilicon compound as a vapor deposition monomer by chemical vapor deposition. Then, a vapor-deposited film of carbon-containing silicon oxide is provided on one surface of the base film, and a general formula R ¹ _nM (OR ² ) _m (wherein R ¹ , R ² represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents an atom of M A gas barrier composition obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by formula (1)) and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. Depends on the thing It is a laminated film provided with a gas barrier coating film, and the release layer provides a medical release film which is a curable silicone resin layer.

According to the present invention, the preservability of the medicinal component of the drug layer of the patch can be improved due to the excellent gas barrier property.
The release film for medical use of the present invention can improve the mold release property and form various designs by embossing since the deterioration of the gas barrier property is suppressed even when embossing is performed.

The medical release film according to the present invention will be described in more detail below with reference to the drawings.
(1) Medical Release Film First, the medical release film according to the present invention is a medical release film comprising a gas barrier laminate film (20) and a release layer (30) as shown in FIG. In the gas barrier laminate film (20), a carbon-containing silicon oxide vapor deposition film (23) is provided on the base film (21), and the carbon-containing silicon oxide vapor deposition film (23) has the general formula R. ¹ _n M (OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.) and contains a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. And obtained by polycondensation by the sol-gel method. A laminated film in which a gas barrier coating film (25) by gas barrier composition. In addition, the medical release film of this invention is characterized by including a gas-barrier laminated film (20) and a release layer (30), and may further contain other layers.

(2) Gas barrier laminate film The gas barrier laminate film used in the present invention comprises a base film, a carbon-containing silicon oxide vapor deposition film, and a gas barrier coating film made of a gas barrier composition.

(I) Base film The base film that can be used in the present invention is excellent in chemical or physical strength, withstands the conditions for forming a carbon-containing silicon oxide film, and the carbon-containing silicon oxide film. It is possible to use a resin film that can be satisfactorily maintained without impairing film properties such as the above. Specifically, for example, polyolefin resin such as polyethylene resin or polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile ruptage-styrene copolymer ( ABS resins), poly (meth) acrylic resins, polycarbonate resins, polyvinyl alcohol resins, saponified ethylene-vinyl ester copolymers, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, various nylons, etc. Various resin films such as polyamide resin, polyurethane resin, acetal resin, cellulose resin, and the like can be used. In the present invention, among the above resin films, it is particularly preferable to use a polyester resin, polyolefin resin, or polyamide resin film. As the base film, any of an unstretched film of the above resin and a film stretched in a uniaxial direction or a biaxial direction can be used.

  In the present invention, as the above-mentioned various resin films, for example, one or more of the above-mentioned various resins are used, and an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, etc. The above-mentioned film forming method is used to form a film of each of the above-mentioned various resins alone, or to form a multilayer co-extrusion film using two or more kinds of resins, Using the above resins, various resin films are manufactured by a method of forming a film by mixing before forming a film, and if necessary, for example, a tenter method or a tubular method, etc. Various resin films that are stretched in a uniaxial or biaxial direction using the above can be used.

In the present invention, the film thickness of various resin films is preferably about 6 to 2000 μm, more preferably about 9 to 100 μm.
It should be noted that one or more of the above-mentioned various resins are used, and in forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness Various plastic compounding agents and additives can be added for the purpose of improving and modifying mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. Can be optionally added from a very small amount to several tens of percent depending on the purpose.

  In the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. Furthermore, a modifying resin or the like can also be used.

(Ii) Surface treatment In this invention, although the vapor deposition film | membrane of carbon containing silicon oxide is formed in one surface of said base film, you may surface-treat a base film previously. As a result, the adhesion to the vapor-deposited film of carbon-containing silicon oxide and the gas barrier coating film can be improved.

  Such surface treatments include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc., and other pretreatments, etc. is there.

  In addition, a primer coating agent, an undercoat agent, an anchor coating agent, a vapor deposition anchor coating agent, or the like can be arbitrarily applied in advance to the surface of various films used in the present invention for surface treatment. Examples of the coating agent include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyolefins such as polyethylene or polypropylene. A resin composition containing a resin or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle can be used.

  Among such surface treatments, it is particularly preferable to perform corona treatment or plasma treatment. For example, as plasma processing, there is plasma processing in which surface modification is performed using a plasma gas generated by ionizing a gas by arc discharge. In addition to the above, an inorganic gas such as oxygen gas, nitrogen gas, argon gas, helium gas can be used as the plasma gas. For example, immediately before forming a vapor-deposited film of carbon-containing silicon oxide by chemical vapor deposition described later, in-line plasma treatment removes moisture, dust, etc. on the surface of the substrate film and smoothes the surface. Surface treatment such as activation, activation, etc. can be made possible. In addition, plasma treatment can be performed after vapor deposition to improve adhesion. In the present invention, as the plasma treatment, it is preferable to perform the plasma discharge treatment in consideration of the plasma output, the type of plasma gas, the supply amount of the plasma gas, the treatment time, and other conditions. Moreover, as a method for generating plasma, DC glow discharge, high frequency discharge, microwave discharge, and other devices can be used. In addition, plasma treatment can be performed by an atmospheric pressure plasma treatment method.

(Iii) Vapor-deposited film of carbon-containing silicon oxide A vapor-deposited film of carbon-containing silicon oxide is formed by chemical vapor deposition using an organosilicon compound as a vapor deposition monomer. As the chemical vapor deposition method, for example, a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, a photochemical vapor deposition method, or the like can be used. Among these, it is particularly desirable to produce a film by using a low temperature plasma chemical vapor deposition method.

  In the present invention, specifically, on one surface of the substrate film, a film-forming monomer gas composed of one or more organic silicon compounds is used as a raw material, and an inert gas such as argon gas or helium gas is used as a carrier gas. Of carbon-containing silicon oxide made of silicon oxide or the like using a low temperature plasma chemical vapor deposition method using oxygen gas or the like as an oxygen supply gas and using a low temperature plasma generator or the like. It can be manufactured by forming a single layer film consisting of one layer of a vapor deposition film, a multilayer film consisting of two or more layers, or a composite film.

  In the above, as a low-temperature plasma generator, for example, a generator such as high-frequency plasma, pulse wave plasma, microwave plasma can be used, and in the present invention, in order to obtain a highly active stable plasma, It is desirable to use a high frequency plasma generator.

An example of a method for forming a deposited film of carbon-containing silicon oxide by the low temperature plasma chemical vapor deposition method will be described with reference to FIG. 2 which is a schematic configuration diagram of a low temperature plasma chemical vapor deposition apparatus.
The plasma chemical vapor deposition apparatus (100) of FIG. 2 forms a carbon-containing silicon oxide layer on a base film supply chamber (110), a first film formation chamber (120) including a vacuum chamber, and the base film. It is comprised from the winding chamber (150) which winds up the converted film. The base film (101) is unwound from an unwinding roll (111) disposed in the base film supply chamber (110), and the base film (101) is assisted in the first film forming chamber (120). It is conveyed on the circumferential surface of the cooling / electrode drum (122) at a predetermined speed via the roll (121). On the other hand, an oxygen gas, an inert gas, a monomer gas for vapor deposition such as an organosilicon compound, etc. are supplied from a gas supply device (125) and a raw material volatilization supply device (124) to prepare a mixed gas composition for vapor deposition. This is introduced into the first film forming chamber (120) through the raw material supply nozzle (127). The mixed gas composition for vapor deposition is supplied onto the substrate film (101) conveyed on the peripheral surface of the cooling / electrode drum (122), and plasma is generated and irradiated by glow discharge plasma (128) for oxidation. A deposited film of carbon-containing silicon oxide such as silicon is formed. Subsequently, the base film (101) on which the vapor-deposited film of carbon-containing silicon oxide such as silicon oxide is formed is transferred to the winding chamber (150) through the auxiliary roll (123), where the winding roll (151) is transferred. ), A film having a deposited film of carbon-containing silicon oxide by plasma chemical vapor deposition can be produced. The cooling / electrode drum (122) is applied with a predetermined power from a power source (160) disposed outside the first film forming chamber (120), and in the vicinity of the cooling / electrode drum (122), The generation of plasma is promoted by disposing a magnet (129). Since a predetermined voltage is applied from the power source to the cooling / electrode drum in this way, glow discharge plasma is generated in the vicinity of the opening of the raw material supply nozzle in the vacuum chamber and the cooling / electrode drum. This glow discharge plasma is derived from one or more gas components in the mixed gas. When the substrate film is conveyed in this state, the glow discharge plasma causes the substrate on the peripheral surface of the cooling / electrode drum to be conveyed. A vapor-deposited film of carbon-containing silicon oxide such as silicon oxide can be formed on the film. In FIG. 2, reference numeral (153) represents a vacuum pump.

In the present invention, a vapor deposition film of carbon-containing silicon oxide formed using a vapor deposition monomer gas such as an organosilicon compound chemically reacts with a vapor deposition monomer gas such as an organosilicon compound and oxygen gas. Is closely bonded to one surface of the base film to form a dense, flexible thin film, and is generally represented by the general formula SiO _x (where X represents a number from 0 to 2). Is a continuous thin film mainly composed of silicon oxide. The carbon-containing silicon oxide vapor-deposited film is a carbon-containing material represented by the general formula SiO _x (where X represents a number from 1.3 to 1.9) in terms of transparency, barrier properties, and the like. A thin film mainly composed of a silicon oxide vapor deposition film is preferable. The value of X varies depending on the molar ratio of vapor deposition monomer gas and oxygen gas, plasma energy, etc. Generally, the gas permeability decreases as the value of X decreases, and the film itself becomes yellowish. It becomes tinged and becomes less transparent.

In the present invention, the vapor-deposited film of carbon-containing silicon oxide is mainly composed of silicon oxide, and further, at least one compound of carbon, hydrogen, silicon or oxygen or at least one compound composed of two or more elements is formed by chemical bonding or the like. It consists of the vapor deposition film to contain. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Examples thereof include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. In addition to the above, the type, amount, etc. of the compound contained in the vapor-deposited film of carbon-containing silicon oxide may be varied by changing the conditions of the vapor deposition process. Under the present circumstances, as content which said compound contains in the vapor deposition film | membrane of carbon containing silicon oxide, it is 0.1-50 mass%, Preferably it is 5-20 mass%. When the content is less than 0.1% by mass, the impact resistance, spreadability, flexibility and the like of the vapor-deposited film of carbon-containing silicon oxide are insufficient, and scratches, cracks, etc. are likely to occur due to bending, etc. In some cases, it is difficult to stably maintain the barrier property. On the other hand, if it exceeds 50% by mass, the barrier property may be deteriorated.

  In the present invention, the surface of the base film is cleaned by SiOx plasma, and polar groups, free radicals, etc. are generated on the surface, so that the carbon-containing silicon oxide made of silicon oxide or the like to be formed into a film is formed. The tight adhesion between the membrane and the substrate film is high.

  Further, in the present invention, in the vapor-deposited film of carbon-containing silicon oxide, the content of the above compound may increase or decrease from the surface of the vapor-deposited film of carbon-containing silicon oxide in the depth direction. For example, in the case of decreasing from the surface in the depth direction, this improves the impact resistance and the like by the above compound on the surface of the carbon-containing silicon oxide vapor deposition film, and on the other hand, at the interface with the base film Since the content of the compound is small, the tight adhesion between the base film and the carbon-containing silicon oxide deposited film becomes strong. Such a vapor-deposited film of carbon-containing silicon oxide is not limited to the case where it is composed of one layer, and may be a multilayer film in which two or more layers are laminated, for example.

  In order to form the multilayer deposition layer, a vapor deposition film of carbon-containing silicon oxide having different compositions is formed by using a chemical vapor deposition apparatus (100) having a plurality of vacuum chambers as deposition chambers. be able to. FIG. 3 is used to illustrate the case of having a three-layer deposited film. The plasma chemical vapor deposition apparatus (100) of FIG. 3 includes a base film supply chamber (110), a first film forming chamber (120), a second film forming chamber (130), a third film forming chamber (140), And it is comprised from the winding chamber (150) which rolls up the film which formed the carbon-containing silicon oxide layer on the base film, and laminated | stacked it. In the base film supply chamber (110), the base film (101) is fed from the unwinding roll (111) to the first film forming chamber (120), and the base film (101) is further transferred to the auxiliary roll (121). ) On the circumferential surface of the cooling / electrode drum (122) at a predetermined speed. In the first film forming chamber (120), a raw material volatilization supply device (124), a gas supply device (125), etc. are used to form a film forming monomer gas, oxygen gas, inert gas, and the like. The above-mentioned mixed gas composition for film formation is introduced into the first film forming chamber (120) through the raw material supply nozzle (127) while supplying the others and adjusting the mixed gas composition for film formation comprising them. Then, a plasma is generated by glow discharge plasma (128) on the substrate film (101) conveyed on the peripheral surface of the cooling / electrode drum (122), and this is irradiated with silicon oxide. A first carbon-containing silicon oxide layer made of, for example, is formed.

  The base film (101) obtained by forming the carbon-containing silicon oxide film of the first layer in the first film forming chamber (120) is supplied to the second film forming chamber through the auxiliary rolls (123), (131) and the like. (130), and then, similarly to the above, the base film (101) formed by forming the first layer of carbon-containing silicon oxide film is cooled and transported onto the peripheral surface of the electrode drum (132) at a predetermined speed. To do. Thereafter, in the same manner as described above, from the raw material volatilization supply device (134), the gas supply device (135), etc., the monomer gas for film formation, oxygen gas, inert gas, etc. composed of one or more kinds of organosilicon compounds are added. Supplying the above-mentioned mixed gas composition for film formation into the second film forming chamber (130) through the raw material supply nozzle (137) while adjusting the mixed gas composition for film formation comprising them, and On the carbon-containing silicon oxide film of the first layer of the base film (101) obtained by forming the carbon-containing silicon oxide film of the first layer conveyed on the cooling / electrode drum (132) peripheral surface, Plasma is generated by glow discharge plasma (138) and irradiated to form a second-layer carbon-containing silicon oxide film made of silicon oxide or the like.

  Further, the first and second carbon-containing silicon oxide films are formed in the second film forming chamber (130), and the laminated base film (101) is added to the auxiliary rolls (133), (141), etc. Then, the substrate film (101) formed by forming the carbon-containing silicon oxide films of the first layer and the second layer at a predetermined speed is delivered to the third film-forming chamber (140) through It is conveyed on the circumferential surface of the cooling / electrode drum (142). Next, a monomer gas for film formation consisting of one or more organic silicon compounds, oxygen gas, inert gas, and the like are supplied from the raw material volatilization supply device (144), the gas supply device (145), and the like. The film-forming mixed gas composition is introduced into the third film-forming chamber (140) through the raw material supply nozzle (147) while adjusting the film-forming mixed gas composition. The carbon-containing silicon oxide film of the first layer and the second layer conveyed on the peripheral surface of the electrode drum (142) is formed into a film, and the second layer of the carbon-containing silicon oxide film of the base film 1 is laminated, Plasma is generated by glow discharge plasma (148) and irradiated to form a third-layer carbon-containing silicon oxide film made of silicon oxide or the like.

  Next, the carbon-containing silicon oxide films of the first layer, the second layer, and the third layer are formed as described above, and the base film (101) on which these layers are stacked is wound through the auxiliary roll (143). It takes out to a take-up chamber (150), and then winds up to a take-up roll (151).

  Each cooling / electrode drum (122), (132), (142) disposed in each of the first, second, and third film forming chambers (120), (130), (140). A predetermined power is applied from a power source (160) disposed outside each of the first, second, and third film forming chambers (120), (130), (140), and Magnets (129), (139), and (149) are arranged in the vicinity of the cooling / electrode drums (122), (132), and (142) to promote the generation of plasma. Although not shown, the plasma chemical vapor deposition apparatus is provided with a vacuum pump or the like, and it is needless to say that each film forming chamber can be prepared to be kept in vacuum. In addition, although the above is exemplified by three layers, a film forming chamber can be arbitrarily prepared to have a multilayer structure of four or more layers.

In the above, the inside of the vacuum chamber is depressurized by a vacuum pump and adjusted to a degree of vacuum of 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably a degree of vacuum of 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is desirable. Further, in the present invention, regardless of whether the vapor-deposited film of carbon-containing silicon oxide is composed of a single layer or a multilayer, the degree of vacuum when forming the vapor-deposited film of carbon-containing silicon oxide such as silicon oxide is Each vacuum chamber is decompressed by a vacuum pump and adjusted to 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. Since the degree of vacuum when forming a vapor-deposited film of carbon-containing silicon oxide such as silicon oxide by a conventional vacuum vapor deposition method is lower than 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr, It is possible to shorten the time for setting the vacuum state at the time of replacing the original film, and the degree of vacuum is easily stabilized, and the film forming process is also stabilized. When there are a plurality of film forming chambers, the degree of vacuum may be the same or different in each chamber.

  Moreover, it is desirable that the conveyance speed of the base film is adjusted to about 10 to 300 m / min, preferably about 50 to 200 m / min. In plasma chemical vapor deposition, since a predetermined voltage is applied to the cooling / electrode drum from the power source, glow discharge plasma is generated in the vicinity of the opening of the material supply nozzle in the film forming chamber and the cooling / electrode drum. Generated. The glow discharge plasma is derived from one or more gas components contained in the film-forming mixed gas composition. When the base film is transported at a constant speed within the above range, the glow discharge plasma causes the cooling to occur. A carbon-containing silicon oxide film made of silicon oxide or the like can be uniformly formed on the base film on the electrode drum peripheral surface.

In addition, in the mixed gas composition for film formation composed of the raw material organosilicon compound, oxygen gas, and inert gas, the gas mixing ratio of each gas component is the film formation monomer gas composed of one kind of organosilicon compound. The content is preferably adjusted in the range of 1 to 40% by mass, the oxygen gas content in the range of 0.1 to 70% by mass, and the inert gas content in the range of 1 to 60% by mass. When said deposited layer is a multilayer, in each deposited layer, the ratio of the film for monomer gas and oxygen gas as the raw material (O ₂₎ may be changed respectively. As a result, the amount of carbon in the carbon-containing silicon oxide film formed can be increased or decreased. When the amount of carbon increases, the number of C—C bonds and Si—CH ₃ bonds increases, and the flexibility is high. A water-repellent carbon-containing silicon oxide film having a high barrier property against water vapor can be formed. Further, when the carbon content in the formed carbon-containing silicon oxide layer is reduced, Si—CH ₃ bonds are reduced and flexibility is inferior, but high gas barrier properties against oxygen and the like can be maintained. .

  In the present invention, the vapor-deposited film of carbon-containing silicon oxide uses, for example, a surface analyzer such as an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS) or a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS). The above-mentioned physical properties can be confirmed by performing analysis by performing ion etching in the depth direction and performing elemental analysis of the deposited film of carbon-containing silicon oxide.

  In the present invention, the total film thickness of the carbon-containing silicon oxide vapor-deposited film is preferably about 60 to 4000 mm, more preferably 100 to 1000 mm. If it is thicker than 4000 mm, cracks or the like may occur in the film. On the other hand, if it is less than 60 mm, it may be difficult to achieve a barrier effect. The film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation. Further, as a means of changing the film thickness of the carbon-containing silicon oxide vapor deposition film, a method of increasing the volume velocity of the vapor deposition film, that is, a method of increasing the amount of monomer gas and oxygen gas, a method of slowing the vapor deposition rate, etc. Can be done by.

  In the case of the multilayer structure composed of the three layers described above, the thickness of the carbon-containing silicon oxide film constituting the first layer is desirably about 20 to 200 mm, preferably about 30 to 100 mm. The film thickness of the carbon-containing silicon oxide film constituting the two layers is preferably about 20 to 200 mm, preferably about 30 to 100 mm, and the film thickness of the carbon-containing silicon oxide film constituting the third layer is The range of 20 to 200 mm, preferably 30 to 100 mm is desirable. In the above, if it is 20 mm or less, its own barrier properties are not expressed, and if it exceeds 200 mm, cracks and the like are likely to occur in the film. In particular, the base film is wound during film formation. This is not preferable because cracks tend to be easily formed. Further, in the above, as a means for changing the film thickness of the carbon-containing silicon oxide layer, the volume velocity of the layer is increased, that is, a method for increasing the amount of monomer gas for film formation and oxygen gas, It can be performed by a method of slowing the film forming speed.

  In the present invention, as a monomer gas for vapor deposition of an organic silicon compound or the like that forms a vapor deposition film of carbon-containing silicon oxide such as silicon oxide, for example, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, Vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxy Silane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. can be used. Among these, it is particularly preferable to use 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material because of its handleability and the characteristics of the formed continuous film. In the above, as the inert gas, for example, argon gas, helium gas, or the like can be used.

(Iv) Gas barrier coating film The gas barrier coating film used in the present invention has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are organic having 1 to 8 carbon atoms). Represents a group, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. Contains the above alkoxide, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, and polycondensation by sol-gel method in the presence of sol-gel method catalyst, acid, water, and organic solvent A coating film comprising a gas barrier composition formed by coating the composition on a carbon-containing silicon oxide vapor deposition film on the base film to provide a coating film, 30 seconds at a temperature below the melting point of the base film It can be formed by heat treatment for 10 minutes.

  Further, the gas barrier composition is applied onto a carbon-containing silicon oxide vapor-deposited film on the base film, and two or more coating films are stacked, and the temperature of the base film is 20 ° C. to 180 ° C. You may heat-process for 30 second-10 minutes at the temperature below melting | fusing point, and may form the composite polymer layer which laminated | stacked two or more gas barrier coating films.

As the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , at least one of alkoxide partial hydrolyzate and alkoxide hydrolysis condensate can be used. The partial hydrolyzate is not limited to the one in which all of the alkoxy groups are hydrolyzed, and may be one in which one or more are hydrolyzed, or a mixture thereof, and further a hydrolysis condensate. As a dimer or more of a partially hydrolyzed alkoxide, specifically, a dimer or hexamer may be used.

In the general formula R ¹ _n M (OR ² ) _m , R ¹ is an alkyl group having 1 to 8, preferably 1 to 5, more preferably 1 to 4 carbon atoms which may have a branch. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group, etc. Can be mentioned.

In the general formula R ¹ _n M (OR ² ) _m , R ² is an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 5, and particularly preferably 1 to 4 which may have a branch. Yes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, and the like. When a plurality of (OR ² ) are present in the same molecule, (OR ² ) may be the same or different.

Examples of the metal atom represented by M in the general formula R ¹ _n M (OR ² ) _m include silicon, zirconium, titanium, aluminum, and the like.
In the present invention, silicon is preferable. In this case, as an alkoxide that can be preferably used in the present invention, when n = 0 in the general formula R ¹ _n M (OR ² ) _m , the general formula Si (ORa) ₄ (wherein Ra is Represents an alkyl group having 1 to 5 carbon atoms). In the above, Ra includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like. Specific examples of such an alkoxysilane include tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (0C ₃ H ₇ ) ₄ , tetrabutoxysilane Si ( OC ₄ H ₉₎ can be exemplified ₄ like.

In the case where n is 1 or more, the general formula RbnSi (ORc) _4-m (wherein m represents an integer of 1, 2, 3 and Rb and Rc are a methyl group, an ethyl group, An alkylalkoxysilane represented by n-propyl group, n-butyl group, etc.) can be used. Examples of such an alkylalkoxysilane include methyltrimethoxysilane CH ₃ Si (OCH ₃ ) ₃ , methyltriethoxysilane CH ₃ Si (OC ₂ H ₅ ) ₃ , dimethyldimethoxysilane (CH ₃ ) ₂ Si (OCH). _{3) 2,} dimethyl diethoxy silane _{(CH 3) 2 Si (OC} 2 H 5) 2, may use other like. In the present invention, the above alkoxysilane, alkylalkoxysilane and the like may be used alone or in combination of two or more.

  In the present invention, a polycondensation product of the above alkoxysilane can also be used, and specifically, for example, polytetramethoxysilane, polytetraemethoxysilane, and the like can be used.

In the present invention, a zirconium alkoxide in which M is Zr can also be suitably used as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m . For example, tetramethoxy zirconium Zr (OCH _{3) 4,} tetraethoxy zirconium _{Zr (OC 2 H 5) 4} , tetra i propoxy zirconium _{Zr (iso-0C 3 H 7} ) 4, tetra-n-butoxy zirconium Zr (OC ₄ H _{9) 4} , etc. can be exemplified.

Further, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , a titanium alkoxide in which M is Ti can be preferably used. For example, tetramethoxytitanium Ti (OCH ₃ ) ₄ , tetra Examples thereof include ethoxytitanium Ti (OC ₂ H ₅ ) ₄ , tetraisopropoxytitanium Ti (iso-0C ₃ H ₇ ) ₄ , tetra n-butoxytitanium Ti (OC ₄ H ₉ ) ₄ , and the like.

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , an aluminum alkoxide in which M is Al can be used. For example, tetramethoxyaluminum Al (OCH ₃ ) ₄ , tetraethoxyaluminum _{Al (OC 2 H 5) 4} , tetraisopropoxy aluminum _{Al (is0-OC 3 H 7} ) 4, tetra-n-butoxy aluminum _{Al (OC 4 H 9) 4} , may use other like.

  In the present invention, two or more of the alkoxides may be used in combination. For example, when alkoxysilane and zirconium alkoxide are mixed and used, the toughness, heat resistance and the like of the resulting gas barrier laminate film can be improved, and a decrease in the retort resistance of the film during stretching can be avoided. Under the present circumstances, the usage-amount of a zirconium alkoxide is the range of 10 mass parts or less with respect to 100 mass parts of said alkoxysilanes. When the amount exceeds 10 parts by mass, the formed gas barrier coating film tends to gel, and the brittleness of the film increases, and the gas barrier coating film tends to peel off when the base film is coated. This is not desirable.

  In addition, when alkoxysilane and titanium alkoxide are mixed and used, the thermal conductivity of the resulting gas barrier coating film is lowered, and the heat resistance is remarkably improved. Under the present circumstances, the usage-amount of a titanium alkoxide is the range of 5 mass parts or less with respect to 100 mass parts of said alkoxysilane. When the amount exceeds 5 parts by mass, the brittleness of the formed gas barrier coating film increases, and the gas barrier coating film may be easily peeled off when the base film is coated.

  As the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer used in the present invention, a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer can be used alone, respectively, or polyvinyl alcohol A single resin and an ethylene / vinyl alcohol copolymer can be used in combination. In the present invention, physical properties such as gas barrier properties, water resistance, weather resistance, and the like can be remarkably improved by using a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer.

  When the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer are used in combination, the blending ratio of each is polyvinyl alcohol resin: ethylene / vinyl alcohol copolymer = 10: 0. It is preferable that the position is from 05 to 10: 6.

  The content of the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer is in the range of 5 to 500 parts by mass, preferably 20 to 200 parts by mass with respect to 100 parts by mass of the total amount of the alkoxide. The blending ratio of When it exceeds 500 parts by mass, the brittleness of the gas barrier coating film becomes large, and the water resistance and weather resistance of the resulting barrier film may be lowered. On the other hand, if it is less than 5 parts by mass, the gas barrier property may be lowered.

  In the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, as the polyvinyl alcohol resin, one obtained by saponifying polyvinyl acetate can be generally used. Polyvinyl alcohol resins include partially saponified polyvinyl alcohol resins in which several tens of percent of acetate groups remain, completely saponified polyvinyl alcohols in which no acetate groups remain, and modified polyvinyl alcohol resins in which OH groups have been modified. Well, not particularly limited. Examples of such a polyvinyl alcohol resin include “RS-110 (degree of saponification = 99%, degree of polymerization = 1,000)” manufactured by Kuraray Co., Ltd., and “Kuraray Poval LM-20SO ( “Saponification degree = 40%, polymerization degree = 2,000)”, “GOHSENOL NM-14 (degree of saponification = 99%, polymerization degree = 1,400)” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Can do.

  As the ethylene / vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer can be used. For example, it is not particularly limited, and includes a partially saponified product in which several tens mol% of acetic acid groups remain to a complete saponified product in which only several mol% of acetic acid groups remain or no acetic acid groups remain. However, it is preferable to use a saponification degree that is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. In addition, the content of the repeating unit derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. It is preferable. Examples of such an ethylene / vinyl alcohol copolymer include “Eval EP-F101 (ethylene content; 32 mol%)” manufactured by Kuraray Co., Ltd., “Soarnol D2908 (ethylene content; 29 mol) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.” %) "And the like.

The gas barrier composition used in the present invention has the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M is Represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.) And a polycondensation by a sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent. Gas barrier composition. In preparing the gas barrier composition, a silane coupling agent or the like may be added.

  As the silane coupling agent that can be suitably used in the present invention, known organic reactive group-containing organoalkoxysilanes can be widely used. For example, an organoalkoxysilane having an epoxy group is suitable. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- (3,4-epoxy). (Cyclohexyl) ethyltrimethoxysilane or the like can be used. Such silane coupling agents may be used alone or in combination of two or more. In addition, the usage-amount of a silane coupling agent exists in the range of 1-20 mass parts with respect to 100 mass parts of said alkoxysilanes. If 20 parts by mass or more is used, the gas barrier coating film to be formed has increased rigidity and brittleness, and the insulation and workability of the gas barrier coating film may be lowered.

  The sol-gel catalyst is a catalyst mainly used as a polycondensation catalyst, and a basic substance such as a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. . For example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, etc. can be used. In the present invention, N, N-dimethylbenzylamine is particularly preferred. The usage-amount is 0.01-1.0 mass part per 100 mass parts of total amounts of an alkoxide and a silane coupling agent.

  The “acid” used in the gas barrier composition is mainly used as a catalyst for hydrolysis of an alkoxide, a silane coupling agent or the like in the sol-gel method. For example, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, organic acids such as acetic acid and tartaric acid, and the like can be used. The amount of the acid used is preferably 0.001 to 0.05 mol based on the total molar amount of the alkoxide and the alkoxide content of the silane coupling agent (for example, silicate moiety).

  Furthermore, in the gas barrier composition, water can be used in a proportion of 0.1 to 100 mol, preferably 0.8 to 2 mol, relative to 1 mol of the total molar amount of the alkoxide. When the amount of water exceeds 2 mol, the polymer obtained from the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles are three-dimensionally crosslinked to form a porous polymer having a low density, Such a porous polymer cannot improve the gas barrier property of the gas barrier laminate film. Moreover, when the amount of the water is less than 0.8 mol, the hydrolysis reaction may hardly proceed.

  Furthermore, as an organic solvent used in said gas-barrier composition, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc. can be used, for example. The polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is preferably handled in a state of being dissolved in a coating solution containing the alkoxide, silane coupling agent, or the like. It can be selected appropriately. For example, when a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer are used in combination, it is preferable to use n-butanol. An ethylene / vinyl alcohol copolymer solubilized in a solvent can also be used. For example, trade name “Soarnol” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be preferably used. The amount of the organic solvent used is usually 30 with respect to 100 mass of the total amount of the alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, acid and sol-gel method catalyst. It is -500 mass parts.

In the present invention, the gas barrier laminate film can be produced by the following method.
First, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel method catalyst, an acid, water, an organic solvent, and, if necessary, A metal alkoxide or the like is mixed to prepare a gas barrier composition. By mixing, the gas barrier composition (coating liquid) starts and proceeds with a polycondensation reaction.

  Next, the above gas barrier composition is applied onto the vapor-deposited film of carbon-containing silicon oxide on the base film and dried by a conventional method. By this drying step, polycondensation of the alkoxide such as alkoxysilane, metal alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer further proceeds, and a coating film is formed. . On the first coating film, the above coating operation may be further repeated to form a plurality of coating films composed of two or more layers.

  Next, the base film coated with the gas barrier composition is heated at 20 ° C. to 180 ° C. and below the melting point of the base film, preferably at a temperature in the range of 50 ° C. to 160 ° C. for 10 seconds to 10 minutes. To process. Thus, a gas barrier laminated film in which one or more gas barrier coating films of the gas barrier composition are formed on the carbon-containing silicon oxide vapor deposition film can be produced.

  A gas barrier laminate film obtained using an ethylene / vinyl alcohol copolymer alone or both a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer is excellent in gas barrier properties after hydrothermal treatment. On the other hand, when a gas barrier laminate film is produced using only a polyvinyl alcohol-based resin, a first coating film is formed by previously applying a gas barrier composition using a polyvinyl alcohol-based resin, A gas barrier composition containing an ethylene / vinyl alcohol copolymer is applied onto the coating film to form a second coating film, and a composite layer thereof is formed. A gas barrier laminate film with improved properties can be produced.

  Further, a coating film is formed by the gas barrier composition containing the ethylene / vinyl alcohol copolymer, or the gas barrier composition containing a combination of the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer is applied. Even if a film is formed and a plurality of these films are laminated, it becomes an effective means for improving the gas barrier property of the gas barrier laminated film according to the present invention.

The production method of the gas barrier laminate film used in the present invention will be described in more detail using alkoxysilane as the alkoxide.
The alkoxysilane and metal alkoxide blended as the gas barrier composition are hydrolyzed by the added water. During the hydrolysis, the acid acts as a hydrolysis catalyst. Next, protons are taken from the hydroxyl groups generated by hydrolysis by the action of the sol-gel method catalyst, and the hydrolyzed products undergo dehydration polycondensation. At this time, the silane coupling agent is simultaneously hydrolyzed by the acid catalyst, and the alkoxy group becomes a hydroxyl group.

  In addition, the opening of the epoxy group also occurs due to the action of the base catalyst, generating a hydroxyl group. In addition, a polycondensation reaction between the hydrolyzed silane coupling agent and the hydrolyzed alkoxide also proceeds. In the reaction system, polyvinyl alcohol resin, ethylene / vinyl alcohol copolymer, or polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer are present, so polyvinyl alcohol resin and ethylene / vinyl alcohol copolymer are present. Reaction with the hydroxyl group of the polymer also occurs. In addition, the polycondensate to be generated includes, for example, an inorganic part composed of a bond such as Si—O—Si, Si—O—Zr, Si—O—Ti, and the like, and an organic part resulting from the silane coupling agent. It is a composite polymer containing.

  In the above reaction, for example, a linear polymer having a partial structural formula represented by the following formula (III) and further having a portion derived from a silane coupling agent is first formed.

このポリマーは、ＯＲ基（エトキシ基などのアルコキシ基）を、直鎖状のポリマーから分岐した形で有する。このＯＲ基は、存在する酸が触媒となって加水分解されてＯＨ基となり、ゾル−ゲル法触媒（塩基触媒）の働きにより、まず、ＯＨ基が、脱プロトン化し、次いで、重縮合が進行する。すなわち、このＯＨ基が、下記の式（Ｉ）に示されるポリビニルアルコール系樹脂、または、下記の式（ＩＩ）に示されるエチレン・ビニルアルコール共重合体と重縮合反応し、Ｓｉ−Ｏ−Ｓｉ結合を有する、例えば、下記の式（ＩＶ）に示される複合ポリマー、あるいは、下記の式（Ｖ）及び（ＶＩ）に示される共重合した複合ポリマーを生じると考えられる。

This polymer has an OR group (an alkoxy group such as an ethoxy group) branched from a linear polymer. This OR group is hydrolyzed to become an OH group using the existing acid as a catalyst. The OH group is first deprotonated by the action of a sol-gel method catalyst (base catalyst), and then polycondensation proceeds. To do. That is, this OH group undergoes a polycondensation reaction with a polyvinyl alcohol-based resin represented by the following formula (I) or an ethylene / vinyl alcohol copolymer represented by the following formula (II) to form Si—O—Si. For example, it is considered that a composite polymer represented by the following formula (IV) or a copolymerized composite polymer represented by the following formulas (V) and (VI) is formed.

上記の反応は常温で進行し、ガスバリア性組成物は、調製中に粘度が増加する。このガスバリア性組成物を、基材フィルム上の炭素含有酸化珪素の蒸着膜の上に塗布し、加熱して溶媒および重縮合反応により生成したアルコールを除去すると重縮合反応が完結し、基材フィルム上の炭素含有酸化珪素の蒸着膜の上に透明な塗布膜が形成される。なお、上記の塗布膜を複数層積層する場合には、層間の塗布膜中の複合ポリマー同士も縮合し、層と層との間が強固に結合する。

The above reaction proceeds at room temperature, and the viscosity of the gas barrier composition increases during preparation. When this gas barrier composition is applied on the vapor-deposited film of carbon-containing silicon oxide on the base film and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation reaction is completed. A transparent coating film is formed on the deposited carbon-containing silicon oxide film. In addition, when laminating | stacking two or more said coating films, the composite polymer in the coating film of an interlayer is also condensed, and a layer couple | bonds firmly between layers.

  Furthermore, the organic reactive group of the silane coupling agent or the hydroxyl group generated by hydrolysis is bonded to the hydroxyl group on the surface of the base film or the vapor-deposited film of carbon-containing silicon oxide on the base film. The adhesion between the material film or the surface of the carbon-containing silicon oxide vapor deposition film and the coating film is also good. Thus, in the present invention, the vapor-deposited film of carbon-containing silicon oxide and the gas barrier coating film form, for example, a chemical bond, a hydrogen bond, or a coordinate bond by a hydrolysis / co-condensation reaction. The adhesion between the vapor-deposited film of carbon-containing silicon oxide and the gas barrier coating film is improved, and a better gas barrier effect can be exhibited by the synergistic effect of the two layers.

In the present invention, when the amount of water added is adjusted to 0.8 to 2 mol, preferably 1.0 to 1.7 mol, relative to 1 mol of alkoxides, the above linear polymer is used. Is formed. Such a linear polymer has crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous part. Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (OH group) is partially present in the molecule, and the molecular aggregation energy is high. Since the rigidity is also high, it is particularly excellent in gas barrier properties (blocking and blocking permeation of O ₂ , N ₂ , H ₂ O, CO ₂ , etc.). In particular, when used for so-called gas-filled packaging filled with N ₂ , CO ₂ gas, etc., the excellent gas barrier property is extremely effective for holding the filled gas. Furthermore, the gas barrier laminate film according to the present invention is excellent in hot water treatment, particularly high-pressure hot water treatment (retort treatment), and exhibits extremely excellent gas barrier properties.

  Examples of the method for applying the gas barrier composition of the present invention include, for example, once by a roll coater such as a gravure roll coater, spray coat, spin coat, dipping, brush, bar code, applicator or the like. A coating film having a dry film thickness of 0.01 to 30 μm, preferably about 0.1 to 10 μm, can be formed by applying a plurality of times. Further, under a normal environment, 50 to 300 ° C., preferably The gas barrier coating film of the present invention is formed by performing condensation at a temperature of 70 to 200 ° C. by heating and drying for 0.005 to 60 minutes, preferably 0.01 to 10 minutes. Can do.

(3) Release layer In the present invention, the release layer laminated with the gas barrier laminate film is a curable silicone resin layer. As such a curable silicone resin, for example, an addition reaction type silicone resin, a condensation polymerization type silicone resin, an ultraviolet curable silicone resin, or the like can be suitably used.

  Specific examples of the addition reaction type silicone resin include KS-774, KS843, KS847, KS847H and KS838 (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd., SD7226, SD7236 and SRX211 manufactured by Toray Dow Corning Co., Ltd. (Both are trade names).

Specific examples of the condensation polymerization type silicone resin include SRX290 and SYLOFF23 (both trade names) manufactured by Toray Dow Corning Co., Ltd.
Moreover, as an ultraviolet curable silicone resin, Shin-Etsu Chemical Co., Ltd. X62-5039 and X62-5040 (all are brand names), Toray Dow Corning Co., Ltd. BY24-510 (brand name), as a specific example, GE Toshiba Silicone Co., Ltd. product TPR6501, UV9300 and XS56-A2775, Toyo Ink Co., Ltd. product, Y184 full shade U311 (brand name), etc. are mentioned.

  As a method for forming these curable silicone resins on a base film, a general coating method can be used. For example, coating methods such as gravure coating, gravure reverse coating, lip coating, die coating, micro gravure coating, Meyer bar coating, and multi-stage reverse coating can be used.

  The coating thickness of the mold release curable silicone resin layer is preferably 0.02 to 1.0 μm, more preferably 0.1 to 0.5 μm in terms of the coating thickness after drying. When the coating thickness is less than 0.02 μm, the peeling performance is poor and there are many variations, and when it exceeds 1.0 μm, the drying property is poor and the silicone migration property may be lowered.

  In order to improve the adhesion between the curable silicone resin layer and the gas barrier laminate film, the surface of the gas barrier laminate film may be subjected to corona treatment before applying the curable silicone resin.

(4) Manufacturing method of medical release film The medical release film of the present invention is provided with a vapor deposition film of carbon-containing silicon oxide in advance on one surface of a base film, and further vapor deposition of the carbon-containing silicon oxide. A gas barrier laminated film provided with the gas barrier coating film on the surface of the film can be produced, and then a curable silicone resin layer can be coated using a gravure coater. In addition, when the said gas-barrier laminated | multilayer film is marketed, a commercial item can also be used.

The medical release film of the present invention prepared as described above has a thickness of 25 to 100 μm, more preferably 50 to 75 μm.
On the other hand, in this invention, at the time of manufacture of a medical release film, it can further emboss and can form the uneven | corrugated pattern of a specific pattern. In order to form such an embossing on a medical release film, for example, an embossing provided with an embossing roll having an uneven pattern mold on the surface and a paper roll or a metal roll that receives the unevenness of the embossing roll. The medical release film is poured into an embossing machine or an embossing machine provided with an embossing roll and a metal roll having surface irregularities corresponding to the uneven shape of the embossing roll, and pressure is applied by the heated embossing roll. Then, an uneven pattern is formed on the medical release film. Usually, the heating temperature of the embossing roll is 80 to 150 ° C., and the pressure is 40 to 100 kgf / cm. In addition, you may emboss by a flat press using a flat embossing plate, without using an embossing roll.

According to this invention, even if it is a case where such embossing is performed, the gas barrier property of the medical release film obtained is maintained.
In addition, when arbitrary uneven | corrugated shape is formed in a medical release film by embossing, it is preferable that the thickness of the thinnest part of an uneven | corrugated pattern is 20 micrometers or more. If the thickness is less than 20 μm, the improvement in peelability is small and the embossing effect may be small.

  The release film for medical use of the present invention is an anti-inflammatory analgesic (plaster agent, poultice), a tape agent for skin diseases, a transdermal agent using an adhesive containing a medicinal agent, regardless of the type of natural rubber or water-based adhesive. It can be suitably used for medical release films such as skin drugs and adhesive bandages.

EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, these Examples do not restrict | limit this invention at all.
(Example 1)
(1) On the other hand, a biaxially stretched polyethylene terephthalate film with a corona-treated surface and a thickness of 50 μm is used, and this is attached to a plasma chemical vapor deposition apparatus consisting of three film forming chambers (chambers) as shown in FIG. did. Next, the pressure in the chamber of the plasma chemical vapor deposition apparatus was reduced.

  On the other hand, hexamethyldisiloxane (hereinafter referred to as HMDSO), which is an organic silicon compound as a raw material, is volatilized in a raw material volatilization supply device (124, 134, 144) and supplied from a gas supply device (125, 135, 145). The mixed gas was mixed with oxygen gas and helium, which was an inert gas, to obtain a raw material gas.

As a raw material gas used in the first film forming chamber (120), the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1.0: 5.0: 3.0: 0.4 (unit; slm, standard liter minute)), film forming output: 11 kW, and as a raw material gas used in the second film forming chamber (130), the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1. 0.0: 3.0: 4.0: 0.4 (unit: slm), film forming output: 10 kW, and further, as a raw material gas used in the third film forming chamber (140), a mixing ratio of raw material gases Was set to HMDSO: O ₂ : He: Ar = 1.0: 3.0: 4.0: 0.4 (unit: slm) and film forming output: 10 kW.

  Using the source gas as described above, the source gas is introduced into the first film-forming chamber, the second film-forming chamber, and the third film-forming chamber, respectively. While transporting the biaxially stretched polyethylene terephthalate film at a line speed of 150 m / min, the film thicknesses of the first layer, the second layer, and the third layer on the corona-treated surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm. Were formed into three layers of carbon-containing silicon oxide layers each having a total thickness of 15 nm.

Next, a glow discharge plasma generator is used on the vapor-deposited film surface of carbon-containing silicon oxide, and power is 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: slm) And the oxygen / argon mixed gas plasma treatment is performed at a mixed gas pressure of 6 × 10 ⁻⁵ Torr and a treatment speed of 420 m / min, and the surface tension of the deposited film surface of carbon-containing silicon oxide is 54 dyne / cm or more. A plasma-treated surface was formed by improving.

  (2) On the other hand, a preliminarily prepared hydrolyzate of composition b was added to the mixture of composition a prepared according to the composition shown in Table 1 and stirred to obtain a colorless and transparent barrier coating solution.

上記で製造したバリア性塗工液を使用し、これをグラビアロールコート法により前記（１）のプラズマ処理面上にコーティングし、次いで、２００℃で６０秒間、加熱処理して、厚さ０．３μｍ（乾操状態）のガスバリア性塗布膜を形成した。

Using the barrier coating solution produced above, this was coated on the plasma-treated surface of (1) above by a gravure roll coating method, and then heat-treated at 200 ° C. for 60 seconds to obtain a thickness of 0. A gas barrier coating film of 3 μm (dry operation state) was formed.

  (3) A curable silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KS847”) is applied to the gas barrier coating film surface of (2) above using a roll coating method, and the thickness is set to 0. A 5 μm curable silicone resin layer was formed to produce the medical release film of the present invention.

Example 2
The same operation as in Example 1 (1) and (2) was performed.
(3) A curable silicone resin (manufactured by Toray Down Corning Co., Ltd., trade name “SD7236”) is applied to the gas barrier coating film surface of (2) above using a roll coating method, and a thickness of 0. A 5 μm curable silicone resin layer was formed, and irregularities were formed with an embossing roll to produce the medical release film of the present invention.

Comparative Example 1
(1) On the other hand, a biaxially stretched polyethylene terephthalate film having a corona-treated surface and having a thickness of 50 μm is mounted on a feeding roll of a take-up vacuum deposition apparatus and fed out, and aluminum is used as a deposition source for the corona-treated layer of the film. While supplying oxygen gas, an aluminum oxide vapor deposition film having a thickness of 200 mm was formed under the following vapor deposition conditions by a vacuum vapor deposition method using an electron beam (EB) heating method.

(Deposition conditions)
Deposition source: Aluminum Degree of vacuum in the deposition chamber: 2 × 10 ^-4 mbar
Degree of vacuum in the take-up chamber: 2 × 10 ^-2 mbar
Electron beam power: 25kw
Film transport speed: 240 m / min
Vapor deposition surface: on corona-treated layer (2) A curable silicone resin (trade name “KS847” manufactured by Shin-Etsu Chemical Co., Ltd.) is applied onto the aluminum oxide vapor deposition film using a roll coating method. A curable silicone resin layer having a thickness of 0.5 μm was formed to produce a comparative medical release film.

Comparative Example 2
The same operation as in (1) of Comparative Example 1 was performed.
(2) A curable silicone resin (manufactured by Toray Down Corning Co., Ltd., trade name “SD7236”) is applied on the aluminum oxide vapor-deposited film of (1) above by using a roll coating method. A curable silicone resin layer having a thickness of 0.5 μm was formed, and irregularities were formed with an embossing roll to produce a comparative medical release film.

Evaluation Method The following evaluation was performed on the above-described medical release film.
(1) Gas barrier property evaluation:
(I) Measurement of oxygen permeability:
The measurement was performed with a measuring instrument (model name, OX-TRAN 2/20) manufactured by MOCON, USA under the conditions of a temperature of 23 ° C. and a humidity of 90% RH.

(Ii) Measurement of water vapor permeability:
The measurement was performed with a measuring instrument (model name, Permatran 3/31) manufactured by MOCON, USA, under conditions of a temperature of 40 ° C. and a humidity of 90% RH. The results are shown in Table 2. In Table 2, the unit of oxygen permeability is [cc / m ² / day · 23 ° C./90% RH], and the unit of water vapor permeability is [g / m ² / day · 40 ° C. · 90 % RH].

(2) Peelability evaluation:
Nichiban cellophane tape (24 mm wide) was applied to the release layer of the medical release film of Examples 1, 2, Comparative Example 1 and Comparative Example 2, and lightly pressed with a finger and then peeled off ( ◎, ○, △, ×) were evaluated in four stages. As Comparative Example 3, the releasability of a biaxially stretched polyethylene terephthalate film having a thickness of 50 μm was also evaluated. In the peelability from the pressure-sensitive adhesive tape, ◎ indicates that there is no resistance, ○ indicates that there is a slight resistance but no problem, Δ indicates that there is resistance, and × indicates that resistance is strong.

(結果)
（１） 実施例２と比較例２に示すように、エンボス加工により離型性が向上することが判明した。

(result)
(1) As shown in Example 2 and Comparative Example 2, it was found that the releasability was improved by embossing.

  (2) A medical release film of Example 1 in which a vapor-deposited film of carbon-containing silicon oxide is formed by CVD and a gas-barrier coating film of a predetermined gas-barrier composition is formed, and a vapor-deposited film of aluminum oxide is formed by EB Comparison with Comparative Example 1 revealed that the medical film of Example 1 was 2-3 times higher in oxygen permeability and water vapor permeability.

  (3) When Example 2 and Comparative Example 2 are compared, in Comparative Example 2, the oxygen permeability is greatly reduced from 1.03 to 7.13 by embossing, and the water vapor permeability is also 1.16 to 4.86. On the other hand, in Example 2, the decrease in oxygen permeability and water vapor permeability due to embossing was very slight. Therefore, by forming a vapor-deposited film of carbon-containing silicon oxide by CVD and forming a gas barrier coating film with a predetermined gas barrier composition, it is possible to ensure both releasability by embossing and high gas barrier properties. found.

  The medical release film of the present invention is excellent in gas barrier properties and release properties.

It is a schematic sectional drawing which shows an example of the laminated constitution of the medical release film which concerns on this invention. It is a schematic block diagram which shows an example of a low temperature plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows an example of the low temperature plasma chemical vapor deposition apparatus which has a some film forming chamber.

Explanation of symbols

20 ... Gas barrier laminate film,
21 ... Base film,
23 ... deposited film of carbon-containing silicon oxide,
25 ... Gas barrier coating film,
30 ... curable silicone resin layer,
100: Plasma chemical vapor deposition apparatus,
101 ... substrate film,
110 ... Base film supply chamber,
111 ... unwinding roll,
120 ... first film forming chamber,
121, 123, 131, 133, 141, 143 ... auxiliary rolls,
122, 132, 142 ... cooling / electrode drum,
124, 134, 144 ... Raw material volatilization supply device,
125, 135, 145 ... gas supply device,
127, 137, 147 ... Raw material supply nozzle 128, 138, 148 ... Glow discharge plasma,
129, 139, 149 ... magnets,
130: second film forming chamber,
140: Third film forming chamber,
150 ... take-up chamber,
153 ... Vacuum pump,
160: Power supply.

Claims (2)

A medical release film comprising at least a gas barrier laminate film and a release layer,
The gas barrier laminated film is formed by supplying an organic silicon compound as a vapor deposition monomer by chemical vapor deposition and providing a vapor deposition film of carbon-containing silicon oxide on one surface of the base film, On the surface of the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n represents An integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.), a polyvinyl alcohol-based resin and / or ethylene vinyl. A laminated film comprising an alcohol copolymer and further provided with a gas barrier coating film by a gas barrier composition obtained by polycondensation by a sol-gel method,
The release layer is a medical release film, which is a curable silicone resin layer.   The medical release film according to claim 1, wherein an embossed pattern is formed.

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