JP2011005677A - Transfer sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a release sheet excellent in film thickness uniformity, comprising a release film provided with a release layer on a base film and a transfer layer provided on the release layer of the release film. The release layer has excellent adhesion to the base film, excellent surface smoothness, high water repellency, and uniform release between the release layer and the transfer layer during thermal transfer. And a very useful transfer sheet.
A release layer of a transfer sheet having a structure of base film / release layer / transfer layer uses a gas composition containing at least an organic silicon compound vapor and oxygen gas, and this is converted into plasma. It consists of a continuous thin film layer of silicon oxide formed by chemical vapor deposition using a plasma chemical vapor deposition method using a generator, and further, in the continuous thin film layer of silicon oxide, carbon, hydrogen, It was set as the structure which contains at least 1 or more types of the compound which consists of 1 type or 2 types or more in silicon and oxygen.
[Selection] Figure 1

Description

  The present invention relates to a transfer sheet comprising a release film provided with a release layer on a base film and a transfer layer provided on the release layer of the release film, and more specifically, a release layer at the time of thermal transfer. The present invention relates to a transfer sheet that is excellent in releasability between the transfer layer and the transfer layer and that has a high surface smoothness on which the transfer layer is transferred to a transfer target.

  Conventionally, a transfer sheet having a structure in which a transfer layer is provided on a substrate film having releasability, transfers the transfer layer of the transfer sheet to a transfer target, and the surface of the transfer target has a pattern, unevenness, etc. It is widely used to easily give designs. As described in Patent Document 1, such a transfer sheet usually uses a release film in which a release layer is provided on a base film such as a PET film, and the release layer of the release film. A transfer layer composed of a peeling layer (protective layer) such as a hard coat (hard coating film), a decorative layer such as picture printing, and an adhesive layer is laminated thereon.

  The release film is produced by applying a thermosetting resin such as a melamine resin or an epoxy resin as a release layer on a base film such as a PET film. In addition, the transfer sheet provided with the transfer layer has been studied for versatile use as described above. However, in recent years, with the development of IT-related fields, the use of transfer sheets has been diversified, and the types of release layers such as hard coat agents selected according to the use have been varied. Depending on the combination of the release coating agent and the release agent, the occurrence of defective peeling has been frequently observed, and improvement has been required.

  In addition, these thermosetting release coating agents are generally provided by wet coating, but in this case, it is difficult to control the thickness of the coating layer, and thermal drying changes from the wet state to the dry state. In this case, the surface smoothness is liable to decrease due to convection, and as a result, the uneven shape on the surface of the release layer is transferred to the release layer side, and further, the smoothness of the transferred object transferred by the transfer sheet is decreased. Especially in optical applications, it may be a fatal defect, which is a big problem.

  For example, Patent Document 2 discloses a thermosetting release coating agent containing a fluororesin and an amino resin on the support film, and the thermosetting property on the support film. Although a release film for a thermal transfer sheet having a release layer formed by using a release coating agent has been proposed, since these require a manufacturing method depending on the wet coating, There is a problem that it is difficult to maintain the smoothness of the layer surface uniformly.

Japanese Patent No. 2779590 JP 2007-2066 A

  Therefore, in order to solve the above problems, an object of the present invention is to provide a transfer film comprising a release film provided with a release layer on a base film and a transfer layer provided on the release layer of the release film. In the sheet, a release layer having excellent film thickness uniformity can be provided on one surface of the base film, and the release layer has excellent adhesion to the base film, and further its surface. The transfer sheet is excellent in smoothness, has high water repellency, has a uniform release property between the release layer and the transfer layer during thermal transfer, and provides an extremely useful transfer sheet.

  As a result of various studies to solve the above-described problems in the release film used for the transfer sheet in the transfer sheet (thermal transfer foil) represented by the heat roll method, the in-mold method, and the like, Attention was focused on a continuous thin film of silicon oxide obtained by chemical vapor deposition using a plasma chemical vapor deposition method in which a vapor of an organosilicon compound is used in a plasma generator. That is, first, a gas composition containing at least a monomer gas composed of an organic silicon compound vapor as a raw material, an inert gas composed of argon gas or helium gas as a carrier gas, and oxygen gas as an oxygen supply gas Next, the gas composition is subjected to chemical vapor deposition by a plasma chemical vapor deposition method using a plasma generator, and a continuous thin film layer of silicon oxide is formed on one surface of the base film. Furthermore, a release layer is formed in the silicon oxide continuous thin film layer containing at least one compound of one or more of carbon, hydrogen, silicon, and oxygen. Thus, the base film on which the release layer was formed was used as a release film for thermal transfer foil.

  Then, the release layer provided on the above-mentioned base film is excellent in uniformity with a constant film thickness, and in addition, it adheres extremely firmly to the base film and has excellent surface smoothness. In addition, the surface water repellency is high (poor wettability), and the mold release layer and the transfer layer at the time of thermal transfer have a uniform mold release property. For example, when the transfer sheet (thermal transfer foil) of the present invention is placed in a molding die of a simultaneous molding transfer machine by in-mold method, and a molten resin for forming a transfer object is injected into the molding die and molded. The release layer is peeled off at the interface with the release layer, and the release layer is transferred to the transfer medium via the adhesive layer. The release layer is stable and has excellent smoothness. The present invention has been completed by finding that it is possible to obtain the surface of the transferred body as a surface.

  That is, the present invention provides, as claim 1, a transfer sheet comprising a release film provided with a release layer on a base film and a transfer layer provided on the release layer of the release film. The mold layer is formed by using a gas composition containing at least an organic silicon compound vapor and oxygen gas, and performing chemical vapor deposition using a plasma chemical vapor deposition method using a plasma generator. It consists of a continuous thin film layer of silicon oxide, and in the continuous thin film layer of silicon oxide, at least one or more compounds of carbon, hydrogen, silicon, and oxygen are used. It is the structure to contain.

  According to a second aspect of the present invention, the transfer layer includes at least a release layer and an adhesive layer, and the release layer includes an ultraviolet curable resin. As a result, the surface on which the transfer layer is located in the transferred material onto which the transfer layer was transferred was a tough film, excellent in durability such as scratch resistance, and highly practical.

  The transfer sheet having the above structure can be provided with a release layer having excellent film thickness uniformity on one surface of the base film, and the release layer has good adhesion to the base film. In addition, it has excellent surface smoothness and high water repellency (poor wettability), so that the adhesion between the release layer and the transfer layer can be kept low, and the release layer during thermal transfer It has uniform releasability from the transfer layer. As a result, the transfer sheet of the present invention is extremely useful in various applications.

It is sectional drawing which shows one embodiment which is the transfer sheet of this invention. It is sectional drawing which shows other embodiment which is a transfer sheet of this invention. It is a schematic block diagram of the low temperature plasma chemical vapor deposition apparatus which shows the outline | summary about the formation method of the continuous thin film layer of the silicon oxide by the plasma chemical vapor deposition method.

Next, an embodiment of the invention will be described in detail.
FIG. 1 shows one embodiment which is a transfer sheet 1 of the present invention. It is the structure which laminated | stacked the release layer 3, the peeling layer 5, and the adhesive bond layer 6 in order on one surface of the base film 2, and is the lamination | stacking which consists of the base film 2 and the release layer 3 provided on it The body is a release film 4. Further, a laminate composed of two layers of the release layer 5 and the adhesive layer 6 is the transfer layer 8, and is heated and pressed under the condition that the transfer target and the adhesive layer 6 of the transfer sheet 1 are in contact with each other. The transfer layer 8 is transferred to the transfer body.

Moreover, FIG. 2 shows other embodiment which is the transfer sheet 1 of this invention. It is the structure which laminated | stacked the mold release layer 3, the peeling layer 5, the decoration layer 7, and the adhesive bond layer 6 in order on one surface of the base film 2, and the base film 2 and the mold release layer provided on it 3 is a release film 4. Further, a laminate composed of three layers of the release layer 5, the decoration layer 7, and the adhesive layer 6 is the transfer layer 8, and heating and heating are performed on the condition that the transfer target and the adhesive layer 6 of the transfer sheet 1 are in contact with each other. The transfer layer 8 is transferred to the transfer target.
Below, each layer which comprises the transfer sheet of this invention is demonstrated in detail.

(Base film)
Since a release layer of a continuous thin film layer of silicon oxide is provided on the base film 2, it has excellent properties in mechanical, physical, chemical, etc., and in particular has a tough strength. In addition, a resin film or sheet having heat resistance can be used. Specifically, in the present invention, as the base film, for example, polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile- Butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate, polyethylene naphthalate, various nylons, etc. Polyamide resin, polyimide resin, polyamideimide resin, polyaryl phthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, aceter System resin, cellulose resin, various resins other such film or a sheet.

  In the present invention, among the above resins, it is particularly preferable to use a polyester resin or a polyamide resin film or sheet having a high function such as heat resistance. The above-mentioned various resin films or sheets use, for example, one or more of the above-described various resins, extrusion method, cast molding method, T-die method, cutting method, inflation method, etc. The above-mentioned film forming method is used to form the above-mentioned various resins alone, or a method in which two or more kinds of various resins are used for co-extrusion to form a film, and further, 2 Various types of resin films or sheets can be produced by a method of mixing and forming a film before using the resin of more than one kind and forming the film. Further, for example, various resin films or sheets stretched in a uniaxial or biaxial direction using a tenter system, a tubular system, or the like can be used. However, by using a biaxially stretched resin film or sheet, the tensile strength is relatively high in any of the longitudinal and lateral methods, which is preferably used. The thickness of said base film is 6-100 micrometers, for example, Preferably it is about 9-50 micrometers.

(Release layer)
A release layer 3 is provided on the base film described above, and a release film is prepared. The release layer is formed by using a gas composition containing at least an organic silicon compound vapor and oxygen gas, and subjecting this to chemical vapor deposition by a plasma chemical vapor deposition method using a plasma generator. Further, in the continuous thin film layer of silicon oxide, at least one compound composed of one or more of carbon, hydrogen, silicon, and oxygen is contained in the continuous thin film layer of silicon oxide. Contains more than one type.

  The silicon oxide continuous thin film layer as the release layer will be further described below. As the silicon oxide continuous thin film layer by the chemical vapor deposition method, for example, the chemical vapor deposition method of the plasma chemical vapor deposition method is used. (Chemical Vapor Deposition method, CVD method) or the like. In the present invention, specifically, a vapor deposition monomer gas such as an organosilicon compound is used as a raw material on one surface of a base film, and an inert gas such as argon gas or helium gas is used as a carrier gas. Further, a gas composition is prepared using oxygen gas or the like as an oxygen supply gas, and then this is continuously formed using a low temperature plasma chemical vapor deposition method utilizing a low temperature plasma generator or the like. A thin film layer can be formed. In the above, as the low-temperature plasma generator, for example, a generator such as high-frequency plasma, pulse wave plasma, microwave plasma can be used. In the present invention, in order to obtain highly active and stable plasma, It is desirable to use a plasma generator.

  Specifically, an example of the method for forming a continuous thin film layer of silicon oxide by the low temperature plasma chemical vapor deposition method will be described. FIG. 3 shows silicon oxidation by the plasma chemical vapor deposition method described above. It is a schematic block diagram of the low temperature plasma chemical vapor deposition apparatus which shows the outline | summary about the formation method of the continuous thin film layer of a thing. As shown in FIG. 2 above, the base film 2 is fed out from the unwinding roll 13 disposed in the vacuum chamber 12 of the plasma chemical vapor deposition apparatus 11, and the base film 2 is further connected to the auxiliary roll 14. Through the cooling / conveying surface of the electrode drum 15 at a predetermined speed. Then, vapor deposition monomer gas such as oxygen gas, inert gas, organosilicon compound, etc. are supplied from the gas supply devices 16 and 17 and the raw material volatilization supply device 18 and the like, and a mixed gas composition for vapor deposition composed of them is prepared. Without adjustment, the vapor deposition mixed gas composition is introduced into the vacuum chamber 12 through the raw material supply nozzle 19, and a glow is formed on the substrate film 2 conveyed on the cooling / electrode drum 15 peripheral surface. Plasma is generated by the discharge plasma 20 and irradiated to form a continuous thin film layer of silicon oxide. At that time, the cooling / electrode drum 15 is applied with a predetermined power from a power source 21 disposed outside the vacuum chamber 12, and a magnet 22 is disposed in the vicinity of the cooling / electrode drum 15. The generation of plasma is promoted.

  Next, the base film 2 on which the continuous thin film layer of silicon oxide is formed is wound on the winding roll 24 via the auxiliary roll 23, and the plasma chemical vapor deposition method according to the present invention is used. A continuous thin film layer of silicon oxide can be formed. In addition, in the figure, 25 represents a vacuum pump, The above illustration is an example, and the present invention is not limited thereby. Although not shown in the drawings, in the present invention, the continuous thin film layer of silicon oxide is not limited to one continuous thin film layer of silicon oxide, but may be a multilayer film in which two or more layers are laminated, The materials used may be used alone or in a mixture of two or more, and a continuous thin film layer of silicon oxide mixed with different materials may be formed.

In the above, the inside of the vacuum chamber 12 is depressurized by the vacuum pump 25 and the degree of vacuum is about 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably the degree of vacuum is 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is desirable to prepare. Further, in the raw material volatilization supply device 18, the organic silicon compound as the raw material is volatilized and mixed with oxygen gas, inert gas, etc. supplied from the gas supply devices 16, 17. Through the vacuum chamber 12. In this case, the contents of the organosilicon compound, oxygen gas, inert gas, and the like in the mixed gas can be changed with any composition. On the other hand, since a predetermined voltage is applied to the cooling / electrode drum 15 from the power source 21, the glow discharge plasma 20 is located in the vicinity of the opening of the raw material supply nozzle 19 in the vacuum chamber 12 and the cooling / electrode drum 15. The glow discharge plasma 20 is derived from one or more gas components in the mixed gas. In this state, the base film 2 is conveyed at a constant speed, and the glow discharge plasma 20 The continuous thin film layer of silicon oxide can be formed on the base film 2 on the circumferential surface of the cooling / electrode drum 15. The degree of vacuum in the vacuum chamber at this time is adjusted to about 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably about 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. Desirably, the conveying speed of the base film 2 is adjusted to about 10 to 500 m / min, preferably about 50 to 350 m / min.

In the plasma chemical vapor deposition apparatus 11 described above, the continuous thin film layer of silicon oxide is formed on the base film 2 by oxidizing the plasma-formed source gas with oxygen gas while maintaining the general formula SiO _x . Therefore, the formed silicon oxide vapor-deposited film is a dense, flexible gap-free continuous layer, and thus a continuous thin film layer of silicon oxide. Is excellent in adhesion with the base film, and also has a high uniformity of film thickness, and since it is formed into a film in a vacuum, there is no adhesion of dust etc. to the surface, and uniform mold release A film having excellent properties and excellent properties is formed. Further, in the present invention, the surface of the base film 2 is cleaned by plasma, and polar groups, free radicals, etc. are generated on the surface of the base film 2, so that a continuous thin film layer of silicon oxide is formed. It has the advantage that the adhesiveness with the base film 2 becomes high. Furthermore, as described above, the degree of vacuum when forming the continuous thin film layer of silicon oxide is about 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably about 1 × 10 ⁻¹ to 1 × 10 −2 Torr. Since the degree of vacuum when forming a silicon oxide deposited film by a conventional vacuum deposition method is about 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr, the degree of vacuum is low. The setting time of the vacuum state at the time of exchanging the base film 2 can be shortened, the degree of vacuum is easily stabilized, and the film forming process is stabilized.

In the present invention, a continuous thin film layer of 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, and the reaction product. However, it is in close contact with one surface of the base film to form a dense, flexible thin film, usually with the general formula SiO _x (where X represents a number from 0 to 2). This is a continuous thin film mainly composed of silicon oxide. Thus, the above-described continuous thin film layer of silicon oxide is represented by the general formula SiO _x (where X represents a number of 1 to 2) in terms of transparency, releasability, and the like. A thin film mainly composed of a continuous thin film layer of silicon oxide is preferable.

The continuous thin film layer of silicon oxide is mainly composed of silicon oxide, and at least one compound of carbon, hydrogen, silicon or oxygen, or a compound composed of two or more elements thereof. It consists of a continuous thin film layer containing a kind by a chemical bond or the like. For example, when a compound having a C—H bond, a compound having a Si—H bond, a compound having a Si—C bond, or a carbon unit is in the form of graphite, diamond, fullerene, etc., An organosilicon compound or a derivative thereof may be contained by a chemical bond or the like. Specific examples 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 continuous thin film layer of silicon oxide can be changed by changing the conditions of the vapor deposition process. And as said content which the said compound contains in the continuous thin film layer of a silicon oxide, about 0.1 to 80%, Preferably about 5 to 60% is desirable. In the above, if the content is less than 0.1%, the releasability of the continuous thin film layer of silicon oxide decreases, or the impact resistance, spreadability, flexibility, etc. become insufficient, Bending and the like tend to cause scratches, cracks and the like, and it is difficult to maintain the stability. When the content exceeds 80%, the releasability and the like are lowered, and the adhesion of the film The properties are also lowered, which is not preferable.

Further, in the continuous thin film layer of silicon oxide, the content of the above-mentioned compound is preferably decreased from the surface of the continuous thin film layer of silicon oxide in the depth direction. On the surface of the layer, the impact resistance and the like are enhanced by the above compound and the like. On the other hand, at the interface with the base film, the content of the above compound is small, so that the base film and the silicon oxide are continuous. There is an advantage that adhesion (adhesiveness) with the thin film layer becomes strong. In addition, when the above compound is contained in the silicon oxide continuous thin film layer constituting the release layer, the silicon oxide continuous thin film layer has a carbon atom content of 5 atomic% or more, Specifically, it is desirable to contain in the range of about 5 atomic% to 70 atomic%, preferably about 10 atomic% to 50 atomic%. In the above, if the carbon atom content is less than 5 atomic%, and more preferably less than 10 atomic%, the presence of methyl groups (CH ₃ ) that are water repellent groups decreases, and the peelability and the like decrease. It is not preferable, and if the carbon atom content exceeds 50 atomic%, and further exceeds 70 atomic%, the film hardness, strength, etc. are reduced, and the phenomenon of peeling off from the base film occurs. Absent.

  In the present invention, the continuous thin film layer of silicon oxide constituting the release layer is, for example, an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS) or a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS). It is possible to confirm the above physical properties by conducting elemental analysis of a continuous thin film layer of silicon oxide using a method of analyzing by ion etching in the depth direction using a surface analyzer such as it can. In the present invention, the film thickness of the continuous thin film layer of silicon oxide is preferably about 20 to 4000 mm, and specifically about 50 to 2000 mm. In the above, if it is thicker than 2000 mm, or more than 4000 mm, it is not preferable because cracks or the like are likely to occur in the film, and if it is less than 50 mm, further less than 20 mm, there is an effect of releasability. This is undesirable because it becomes difficult. In the above, the film thickness can be measured using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation. In the above, as a means for changing the film thickness of the silicon oxide continuous thin film layer, the volume velocity of the continuous thin film layer is increased, that is, a method of increasing the amount of monomer gas and oxygen gas or vapor deposition. This can be done by slowing the speed.

(Peeling layer)
A transfer layer 8 that can be peeled off by thermal transfer is provided on the release film described above. The transfer layer is composed of at least a release layer and an adhesive layer. The release layer 5 is in contact with the release layer of the release film described above, and becomes the outermost surface layer when the transfer layer is transferred to the transfer target. Therefore, the release layer is preferably formed as a protective layer by a hard coat (hard coating film). The release layer is formed from an ionizing radiation curable paint. Particularly preferred ionizing radiation curable paints are electron beam curable paints and ultraviolet curable paints. The electron beam curable paint and the ultraviolet curable paint are similar in composition except that the latter contains a photopolymerization initiator and a sensitizer. Mainly composed of polymers, oligomers, monomers, etc. having radically polymerizable double bonds or epoxy groups in the structure, and other non-reactive polymers, organic solvents, waxes and other additives as necessary. is there.

  Particularly preferred in the present invention are those in which the film-forming component has an acrylate functional group, for example, a relatively low molecular weight polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiro resin. Acetal resin, polybutadiene resin, polythiol polyene resin, oligomers or prepolymers of polyfunctional compounds such as polyhydric alcohols such as (meth) acrylates, and reactive diluents such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methyl Monofunctional monomers such as styrene and N-vinylpyrrolidone as well as polyfunctional monomers such as trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate Contains a relatively large amount of diethylene glycol (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) acrylate, etc. Is. By using such a polyfunctional (meth) acrylate-based ionizing radiation curable coating, a hard coat layer excellent in surface hardness, transparency, friction resistance, scratch resistance, and the like can be formed.

  Furthermore, when such a hard coat layer is required to have high flexibility and shrinkage resistance, an appropriate amount of a thermoplastic resin such as a non-reactive acrylic resin or various waxes is contained in the curable paint. These requirements can be met by adding, etc. Moreover, in order to make said curable coating material into an ultraviolet curable coating material, acetophenones, benzophenone, Michler benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, thioxanthones are used as photopolymerization initiators. As a photosensitizer, n-butylamine, triethylamine, tri-n-butylphosphine and the like can be mixed and used.

  As described above, ionizing radiation curable coating materials such as electron beam or ultraviolet curable coating materials are known in various grades, and all are readily available from the market and can be used in the present invention. In addition, those curing methods can be used as they are. For example, in the case of electron beam curing, Cockloft Walton type, Bande graph type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, high frequency type In the case of ultraviolet curing, an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, carbon, and the like are used. Ultraviolet light emitted from a light source such as an arc, a xenon arc, or a metal halide lamp is used.

  The curable paint as described above can be obtained by any of the above-described release methods such as blade coating method, gravure coating method, rod coating method, knife coating method, reverse roll coating method, spray coating method, offset gravure coating method, etc. A gravure coating method, a gravure reverse coating method, a reverse roll coating method, an offset gravure coating method and the like excellent in accuracy of coating thickness, smoothness of the coated surface, etc. are particularly suitable. Also, if the coating amount of the curable coating is too small, a hard coat layer having sufficient surface hardness and scratch resistance cannot be obtained, and if too large, the curing rate is lowered, the curling of the base film during curing, etc. Therefore, a thickness in the range of 1 to 50 μm, particularly 1.5 to 20 μm (thickness when dried) is preferable.

  The release layer described above is preferably formed from an ionizing radiation curable coating, and is used in combination with a release layer that is a continuous thin film layer of silicon oxide formed by the plasma chemical vapor deposition method. Thus, a uniform release property between the release layer and the transfer layer at the time of thermal transfer can be provided. For example, when the transfer sheet (thermal transfer foil) of the present invention is installed in a molding die of a molding simultaneous transfer machine by an in-mold method, and a molten resin that forms a transfer object is injected into the molding die and molded, The release layer is peeled off at the interface with the release layer, and the release layer is transferred to the transfer medium via the adhesive layer. The release layer surface is stable and has excellent smoothness. It is possible to obtain the surface of the transferred material.

(Decoration layer)
A decorative layer 7 can be provided on the surface of the release layer in order to add an arbitrary decorative pattern, coloring, or the like. Examples of the decorative layer include a pattern layer and a metal thin film layer. The pattern layer is formed by printing or painting ink (or paint). As the ink or the coating material, a vehicle can be used which is appropriately mixed with a colorant such as a pigment or a dye, an extender pigment, or a solvent as required. The vehicle is appropriately selected from thermoplastic resins, thermosetting resins, ionizing radiation curable resins, and the like according to the application, required physical properties, printability, and the like. The pattern in the pattern layer is arbitrary, such as a wood grain pattern, a stone pattern, a character, a figure, a whole surface solid layer, or a combination thereof. In addition, when the purpose is simply to provide a surface protective layer, the pattern layer can be omitted.

  As the metal constituting the metal thin film layer, aluminum, chromium, gold, silver, copper, or the like is used. The film thickness may be selected according to the desired metallic luster and physical properties, and is usually about 100 to 10000 mm. As a method for forming the metal thin film layer, known methods such as vacuum deposition, sputtering, and electroless plating are applied. The metal thin film layer may be either the entire surface or a partial pattern. A known method is used to form the partial pattern.

(Adhesive layer)
The adhesive layer 6 in the transfer layer is composed mainly of an adhesive. As the adhesive, any adhesive such as a heat sensitive adhesive, a pressure sensitive adhesive, a solvent active adhesive, and an ionizing radiation curable adhesive can be used, but a preferable adhesive is not sticky at room temperature, A heat-sensitive adhesive that exhibits adhesiveness when heated is preferable, and by using such a heat-sensitive adhesive, even if a transfer sheet having a release layer and an adhesive layer is continuously produced, it is wound into a roll or the like. This is preferable from the viewpoint of productivity.

  The heat-sensitive adhesive exhibits adhesiveness when heated, and a thermoplastic resin, an ionomer, or the like that is usually melted by heat and exhibits adhesive force is used. Examples of the thermoplastic resin include cellulose derivatives such as cellulose nitrate and cellulose acetate, styrene resins or styrene copolymers such as polystyrene and poly α-methylstyrene, methyl poly (meth) acrylate, and poly (meth) ethyl acrylate. Acrylic resin such as, vinyl polymer such as vinyl chloride vinyl acetate copolymer, ethylene vinyl alcohol copolymer, rosin ester resin such as rosin, rosin modified maleic acid resin, natural such as polyisoprene rubber, styrene butadiene rubber, or Synthetic rubbers and various ionomers are used. In addition, thermosetting resins that cause cross-linking polymerization, addition polymerization, etc. by heat to cure and develop an adhesive force are also used as heat-sensitive adhesives. As the thermosetting resin, for example, an epoxy resin, a polyurethane resin, a phenol resin, or the like is used. Such an adhesive layer can be formed by applying and drying a coating solution obtained by dissolving or dispersing the above adhesive in a solvent in the same manner as the coating method described in the above release layer. . The thickness of the adhesive layer is preferably about 0.5 to 3 μm when dried.

(Transfer)
The transfer sheet of the present invention described above is used by thermally transferring a transfer layer to a transfer target. The transfer material is not limited as long as the transfer layer can be normally transferred by the transfer sheet of the present invention, such as a synthetic resin molded product, metal, wood, ceramics, glass, and the like.

Next, the present invention will be described more specifically with reference to examples. Hereinafter, unless otherwise specified, parts or% is based on mass.
Example 1
Using a winding PE-CVD apparatus (see FIG. 3), a release layer 3 was formed on one surface of the PET film as the base film 2 under the following conditions, and a release film 4 was produced. .
Base film: F99 (Toray Industries, Inc., thickness 38 μm)
Vapor deposition material: HMDSO (hexamethyldisiloxane), oxygen, helium winding type PE-CVD apparatus:
Line speed 30m / min
Power 8kW
The reaction gas mixing ratio is hexamethyldisiloxane: helium: oxygen gas = 1.0: 0.5: 1.0 (unit: slm).

  The surface of the release layer of the release film produced above is coated with melamine acrylate UV curable resin (Mitsubishi Yuka Fine Co., Ltd., trade name Iupimer LZ-075) diluted with methyl ethyl ketone by gravure coating. And dried with hot air at 100 ° C. to solidify the film (thickness: 6 μm) to form a release layer 5, followed by an acrylic heat-sensitive adhesive (R-5, manufactured by Showa Ink Co., Ltd.), gravure It was coated with a coating and dried to form an adhesive layer 6 having a thickness of 3 μm when dried. The transfer sheet of Example 1 was produced by irradiating the obtained transfer sheet with ultraviolet light having an integrated light amount of 800 mj from the release layer side.

(Example 2)
Using a winding PE-CVD apparatus (see FIG. 3), a release layer 3 was formed on one surface of the PET film, which is the base film 2, under the following conditions, and a release film 4 was produced. .
Base film: F99 (Toray Industries, Inc., thickness 38 μm)
Vapor deposition material: HMDSO (hexamethyldisiloxane), oxygen, helium winding type PE-CVD apparatus:
Line speed 50m / min
Power 8kW
The reaction gas mixing ratio is hexamethyldisiloxane: helium: oxygen gas = 1.0: 0.5: 1.0 (unit: slm).
Next, under the same conditions as in Example 1, a release layer and an adhesive layer were formed in this order on the surface of the release layer to produce a transfer sheet of Example 2.

(Example 3)
Example 3 is the same as the condition described in Example 1, except that the decorative layer 7 is provided between the release layer and the adhesive layer in the transfer sheet prepared in Example 1 under the following conditions. A transfer sheet was prepared.
(Decoration layer) On the surface of the release layer provided on the release film, a pattern is printed by gravure printing using an ink made of acrylic resin as a vehicle (manufactured by Showa Ink Industries Co., Ltd., GG). A decorative layer having a dry thickness of 2 μm was formed.

(Comparative Example 1)
Using a winding PE-CVD apparatus (see FIG. 3), a release layer 3 was formed on one surface of the PET film as the base film 2 under the following conditions, and a release film 4 was produced. .
Base film: F99 (Toray Industries, Inc., thickness 38 μm)
Vapor deposition material: HMDSO (hexamethyldisiloxane), nitrogen, helium winding type PE-CVD apparatus:
Line speed 30m / min
Power 8kW
The reaction gas mixing ratio is hexamethyldisiloxane: helium: nitrogen gas = 1.0: 0.5: 5.0 (unit: slm).
Next, a transfer layer of Comparative Example 1 was produced by sequentially forming a release layer and an adhesive layer on the surface of the release layer under the same conditions as in Example 1.

(Comparative Example 2)
A liquid mixture of 20 parts of epoxy resin, 50 parts of methyl ethyl ketone and 30 parts of urea resin is coated on a base film by the gravure reverse method under the following conditions, and then heat-dried and thermally cured to form a release layer. A film was prepared.
Base film: F99 (Toray Industries, Inc., thickness 38 μm)
Line speed 30m / min
Next, a transfer layer of Comparative Example 2 was produced by sequentially forming a release layer and an adhesive layer on the surface of the release layer under the same conditions as in Example 1.

The adhesive layer of each transfer sheet of the above Examples and Comparative Examples and the transfer target (ABS resin molded product) were stacked, the roll was pressed at 220 ° C. from the base film side, and the peelability was evaluated under the following conditions. .
(Peelability)
From the state in which the transfer sheet and the transfer target were heated and pressurized, the peelability when the release film was manually peeled from the transfer target was evaluated. The evaluation criteria are as follows.
A: Peelability and no abnormality at all.
○: There is no practical problem in peelability. The resistance at the time of peeling is a little larger than the case of “」 ”.
Δ: When peeling, resistance is large and peeling is difficult. However, the release film can be removed with time.
X: The release film cannot be peeled off from the transfer target or the transfer sheet is broken at the time of peeling.

(Surface property of transferred object)
Under the conditions for evaluating the above-described peelability, the surface property of the surface of the release layer transferred to the transfer medium was visually confirmed and evaluated under the following conditions.
◯: The surface of the release layer transferred to the transfer medium is excellent in smoothness.
Δ: Slight irregularities are observed on the surface of the release layer transferred to the transfer medium.

(productivity)
Productivity (in consideration of production speed, whether the release layer is a dry process or a wet process, etc.) in producing each of the above transfer sheets was evaluated under the following conditions.
A: Production speed is high, production is very efficient, and productivity is very high.
○: Can be manufactured efficiently and has high productivity.
X: The mold release layer is not a vapor deposition process (dry process), but employs a wet process by a printing method using a coating liquid, resulting in poor productivity.

The evaluation results are shown in Table 1.

  Examples 1 to 3 exhibit good performance in any of the above evaluations. However, the transfer sheet of Example 2 had a higher line speed when forming the release layer and higher productivity than the transfer sheet of Example 1. In addition, in the transfer sheet of Example 3, compared to the transfer sheets of Examples 1 and 2, the transferred material onto which the transfer layer was transferred had a decorative layer having a pattern and a design property.

  Moreover, in Comparative Example 1, the releasability was insufficient and did not function as a release film. In Comparative Example 2, the adhesion between the release layer and the release layer was increased after the transfer with the high-temperature hot roll, and as a result, the release property was lowered. Further, the surface unevenness caused by fine coating unevenness at the time of wet coating when forming the release layer is transferred to the release layer formed thereon, and thus the release layer transferred to the obtained transfer target The surface became uneven, resulting in the loss of surface smoothness.

DESCRIPTION OF SYMBOLS 1 Transfer sheet 2 Base film 3 Release layer 4 Release film 5 Release layer 6 Adhesive layer 7 Decoration layer 8 Transfer layer

Claims (2)

  In a transfer sheet comprising a release film provided with a release layer on a base film and a transfer layer provided on the release layer of the release film, the release layer comprises at least an organic silicon compound vapor It comprises a continuous thin film layer of silicon oxide formed by chemical vapor deposition using a gas composition containing oxygen gas and plasma chemical vapor deposition using a plasma generator. The transfer sheet, wherein the continuous thin film layer of silicon oxide contains at least one compound of one kind or two or more kinds of carbon, hydrogen, silicon, and oxygen. The transfer sheet according to claim 1, wherein the transfer layer comprises at least a release layer and an adhesive layer, and the release layer comprises an ultraviolet curable resin.

Images