JP6264484B2 - Hydraulic transfer film - Google Patents

Description

  The present invention relates to a transfer foil for producing a hydraulic transfer film and a hydraulic transfer film.

For building materials, automobile interior products, home appliances, OA equipment, etc., molded products having decorations such as wood grain or metallic tone (metallic luster) on the surface are used. Many of these molded products have a complicated three-dimensional shape, and conventionally, a method of simply applying a highly designed decoration to a molded product having the complicated shape has been studied.
As such a decoration method, a water pressure transfer method using water pressure is known. This water pressure transfer method can perform transfer processing to a three-dimensional surface, “depth” such as a clear paint feeling, and high quality pattern expression. It is known that it is an excellent curved surface decorating method in terms of design properties.

  In recent years, the demand for design by consumers has become strict, and in particular, in the decoration of metallic tone (metallic luster), a high-class feeling has been demanded in addition to high glitter. For such a problem, for example, a method for solving the problem by a layer exhibiting glitter and an uneven shape by embossing, specifically, a nitrified cotton / alkyd transparent resin layer on a water-soluble film, There has been proposed a hydraulic transfer film comprising a vapor-deposited metal layer on a transparent resin layer and having the transparent resin layer embossed between the vapor-deposited metal layer and the transparent resin layer (for example, Patent Document 1). .

  When the hydraulic transfer film described in Patent Document 1 is used, when the sheet is stretched during hydraulic transfer, the vapor deposited metal layer is also stretched due to the occurrence of fine cracks in the vapor deposited metal layer, and the curved surface is transferred. Is possible. However, there is a problem in that a large difference in design is caused by the size of the crack width generated in the vapor deposition metal layer at the time of hydraulic transfer, and the high-quality feeling of the pattern is impaired when the crack width is wide.

  By the way, as a base material of a hydraulic transfer film, as used in Patent Document 1, a water-soluble film represented by a polyvinyl alcohol resin film has been generally used. However, the polyvinyl alcohol resin film is vulnerable to heat, and when embossing for imparting a concavo-convex shape to a hydraulic transfer film, the concavo-convex shape cannot be sufficiently imparted, and a design property with glitter and luxury cannot be obtained. There was a problem. In addition, when a water-soluble resin film is used as a base material, for example, when a hydraulic transfer film is stored for a long period of time, it easily absorbs moisture in the air and causes curling and blocking, and the influence of humidity in the air There was also a problem that the design of the decorative layer was adversely affected by the expansion and contraction of the film.

  Therefore, a transfer foil in which a polyethylene terephthalate resin (PET resin) film is used as a base material having excellent heat resistance, a decorative layer made of a metal thin film layer or the like is provided on the base material, and embossing is performed to form an uneven shape. There has been proposed a method for solving the problem that a concave-convex shape cannot be sufficiently imparted by producing a hydraulic transfer film using a film (for example, Patent Document 2). By this method, the hydraulic transfer film has a sufficient uneven shape. However, as with the hydraulic transfer film described in Patent Document 1, problems such as differences in design properties due to the size of the crack width generated in the metal thin film layer formed of vapor-deposited metal are still solved during hydraulic transfer. Was not.

JP 2001-328398 A JP2013-000896A

In Patent Documents 1 and 2, in order to obtain a design with a glitter and a high-class feeling, it was considered that a glitter ink layer was used instead of the vapor-deposited metal layer, and an uneven shape was provided on the glitter ink layer. However, since the glittering ink layer was excessively extended during the hydraulic transfer and the unevenness disappeared, it was not possible to obtain a design with excellent glitter and luxury. This was the same even when a sufficient uneven shape was formed on the hydraulic transfer film by using the method described in Patent Document 2.
Furthermore, in order to maintain the uneven shape of the glitter ink layer and prevent the disappearance of the uneven feeling, a resin layer is provided between the water-soluble film, which is the base material of the hydraulic transfer film, and the glitter ink layer. It was studied to suppress excessive extension of the ink layer. However, depending on the type of resin that forms the resin layer, the glitter ink layer cannot be formed into a glittering ink layer, for example, the glitter ink layer may be peeled off during the production of a hydraulic transfer film. In some cases, the quality and the sense of quality were impaired.
Under such circumstances, the present invention provides a hydraulic transfer in which a concavo-convex shape is satisfactorily shaped at the time of manufacturing a transfer foil, and can impart design properties with excellent glitter and high-class feeling to a resin molded product. It is an object to provide a transfer foil for producing a hydraulic transfer film suitable for production of a film, a hydraulic transfer film, a method for producing a hydraulic transfer film using the transfer foil, and a decorative molded product using the film.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the problem can be solved by the following invention. That is, the present invention provides the following transfer foil for producing a hydraulic transfer film, a hydraulic transfer film, a method for producing a hydraulic transfer film using the transfer foil, and a decorative molded product using the film.

1. It has a water-soluble film, a glitter ink layer, and an extension suppressing resin layer in this order, and has an uneven shape on at least the surface of the glitter ink layer opposite to the extension suppressing resin layer, and the extension suppressing resin layer A hydraulic transfer film in which the resin forming the resin contains a resin A having a glass transition temperature of 80 ° C. or higher, and the resin A is an acrylic polyol resin.

  The transfer foil for producing a hydraulic transfer film of the present invention has a well-shaped uneven shape at the time of producing the transfer foil, and the hydraulic transfer film can be easily produced before using the hydraulic transfer film. The hydraulic transfer film obtained by using the transfer foil of the present invention has a good concavo-convex shape, and can impart design properties with excellent glitter and high-class feeling to a resin molded product.

It is a schematic sectional drawing which shows an example of a structure of the transfer foil for hydraulic transfer film manufacture of this invention. It is a schematic sectional drawing which shows an example of a structure of the hydraulic transfer film obtained using the transfer foil for hydraulic transfer film manufacture of this invention. It is a schematic sectional drawing which shows an example of the decorative molded product obtained by the manufacturing method of the decorative molded product of this invention.

[Transfer foil for hydraulic transfer film production]
Hereinafter, the transfer foil for producing a hydraulic transfer film of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a transfer foil for producing a hydraulic transfer film of the present invention.
The transfer foil 10 for producing a hydraulic transfer film of the present invention has a release film 11, an extension suppressing resin layer 12, and a glittering ink layer 13 in this order, and at least the extension inhibiting resin layer 12 side of the glittering ink layer 13. Has a concavo-convex shape 14 on the opposite surface, and the resin forming the stretch-inhibiting resin layer 12 contains a resin A having a glass transition temperature of 80 ° C. or higher. Since the transfer foil 10 for producing a hydraulic transfer film of the present invention is formed with the concavo-convex shape 14 at the stage before obtaining the hydraulic transfer film by laminating a heat-sensitive water-soluble film as a base material, the concavo-convex shaping The problem peculiar to a hydraulic transfer film that is inferior in property can be solved. In addition, the hydraulic transfer film uses a water-soluble resin film as a base material, so that when stored for a long period of time, it absorbs moisture in the air and causes curling and blocking, and the film expands and contracts to make it designable. There is concern that it will have an adverse effect. However, since the transfer foil 10 for producing a hydraulic transfer film of the present invention is stored in a state separated from a water-soluble film used as a substrate of the hydraulic transfer film, the hydraulic transfer film can be easily produced immediately before use. These problems can also be avoided.

(Peeling film)
The release film is not particularly limited as long as it is a film that can be peeled off even after coming into contact with the extension suppressing resin layer or a release layer that is preferably provided as necessary. In addition, from the viewpoint of forming a good uneven shape, those having high heat resistance are preferable. Specifically, in addition to a polyester resin film such as polyethylene terephthalate, a polyolefin resin film such as a polyethylene film or a polypropylene film, or a stretched polyolefin resin film, paper, or coating them with a release agent such as silicone, Preferable examples include those subjected to a peeling treatment. Among these, a polyester resin film and a stretched polyolefin resin film are preferable, and a polyester resin film, particularly a polyethylene terephthalate resin film is preferable.
In addition, from the viewpoint of selecting a material that easily peels from the extension suppressing resin layer or the release layer, it is preferable to use a material that has been easily peeled off.

  As for the thickness of a peeling film, 10-100 micrometers is preferable. Within the above range, it is easy to provide a good concavo-convex shape, and the production stability of the transfer foil is increased. From the same viewpoint, the thickness of the release film is more preferably in the range of 20 to 60 μm.

(Peeling layer)
The release layer is a layer provided between the release film and the stretch-inhibiting resin layer, and is preferably a layer provided in order to facilitate peeling of the release film.
The material for forming the release layer is not particularly limited as long as it is a resin excellent in peelability. For example, an acrylic resin, a vinyl acetate resin (a copolymer of vinyl chloride and vinyl acetate), an olefin resin, a silicone resin. Fluorine resin, polyvinyl pyrrolidone resin, silicone, various resins modified with fluorine, and the like are preferable.

  Moreover, wax can also be mix | blended with these resin. The wax is not particularly limited as long as it melts at the time of transfer and exhibits releasability. For example, microcrystalline wax, carnauba wax, paraffin wax, Fischer-Tropsch wax, various low molecular weight polyethylene, wood wax, beeswax, whale Preferred examples include wax, ibota wax, wool wax, shellac wax, candelilla wax, petrolactam, partially modified wax, fatty acid ester, and fatty acid amide. Among these, microcrystalline wax and carnauba wax having a relatively high melting point and hardly soluble in a solvent are preferable.

  1-10 micrometers is preferable and, as for the thickness of a peeling layer, 1-5 micrometers is more preferable. When the thickness of the release layer is within the above range, good release performance can be obtained.

(Extension suppressing resin layer)
The extension suppressing resin layer is a layer that is provided between the release film and the glitter ink layer described later, and that requires the resin A having a glass transition temperature of 80 ° C. or higher as the resin that forms the extension suppressing resin layer. By providing a stretch-inhibiting resin layer, it is possible to obtain a moldability that allows the uneven shape to be satisfactorily shaped during the production of the transfer foil. By forming the corresponding uneven feeling expression portion to maintain the uneven feeling, design properties (hereinafter sometimes simply referred to as “design properties”) having glitter and high quality are obtained. In addition, about the uneven | corrugated feeling expression part corresponding to an uneven | corrugated shape, it explains in full detail in description about the manufacturing method of a decorative molded product.

  In the present invention, the extension suppressing resin layer is a layer located on the back side of the glitter ink layer after being transferred to the resin molded product, and the glitter ink layer is not visually recognized through the extension suppression resin layer. Therefore, it can be selected according to the desired design regardless of whether it is transparent, translucent, opaque, or colored. In addition, the extension suppressing resin layer may have a single layer structure or a multilayer structure of two or more layers.

  The resin forming the extension suppressing resin layer needs to contain a resin A having a glass transition temperature of 80 ° C. or higher. If the resin forming the extension suppressing resin layer does not contain the resin A having a glass transition temperature of 80 ° C. or higher, excellent moldability cannot be obtained, and excellent design properties cannot be obtained. The upper limit of the glass transition temperature is not particularly limited, but is preferably 145 ° C. or less, and more preferably 130 ° C. or less from the viewpoint of improving transfer processability (following property).

In the present invention, the glass transition temperature is measured as follows.
Using a differential scanning calorimeter, the temperature was raised to 200 ° C., and a sample cooled from the temperature to 0 ° C. at a temperature lowering rate of 10 ° C./min was measured at a temperature rising rate of 10 ° C./min. When a peak is observed at a temperature 20 ° C. or more lower than the softening point, the peak temperature is measured. When a peak is not observed at a temperature 20 ° C. or higher lower than the softening point, a step is observed. The temperature at the intersection of the tangent line indicating the maximum slope of the curve and the extension line of the base line on the high temperature side of the step was read as the glass transition temperature.

The resin A is not particularly limited as long as it has a glass transition temperature of 80 ° C. or higher. For example, acrylic resins, acrylic polyol resins, nitrocellulose resins, and vinyl chloride-vinyl acetate copolymer resins are preferable. Acrylic polyol resins are preferred. In this invention, these resin can be used individually or in combination of multiple types.
In addition, as the resin A, it is preferable to use a water-insoluble resin from the viewpoint of suppressing the excessive extension of the glitter ink layer at the time of hydraulic transfer and favorably forming the uneven appearance part corresponding to the uneven shape. . Here, the water-insoluble resin refers to a resin generally known as a water-insoluble resin, and specific examples thereof include those preferably exemplified as the resin A.

Moreover, as resin which forms an extension suppression resin layer, as long as the said resin A is included, you may contain other resin, for example, resin B with a glass transition temperature of less than 80 degreeC. As the resin B used in combination with the resin A, for example, a resin having a glass transition temperature of 60 ° C. or lower is preferable, a resin having a glass transition temperature of 10 ° C. or lower is more preferable, and a resin having a glass transition temperature of 10 ° C. or lower is more preferable.
Preferred examples of the resin B include polyolefin resins such as polyethylene and polypropylene, urethane resins, acetal resins, and alkyd resins, and urethane resins and alkyd resins are preferable. By combining the resin B having a low glass transition temperature, excellent transfer processability (followability) can be obtained. In particular, when an acrylic polyol resin is used as the resin A, it is preferably combined with a urethane resin, and when a nitrocellulose resin such as nitrified cotton is used as the resin A, it is preferably combined with an alkyd resin.

  The content of the resin A in the resin forming the extension suppressing resin layer is preferably 50% by mass or more, more preferably 50 to 95% by mass, still more preferably 60 to 90% by mass, and particularly preferably 70 to 90%. It is 85 mass%. When the content of the resin A in the resin is within the above range, excellent moldability and design properties are obtained, and excellent transfer processability (follow-up property) is also obtained.

  The thickness of the extension suppressing resin layer is preferably 0.5 to 10 μm, more preferably 0.5 to 5 μm, and further preferably 0.5 to 2.5 μm. When the thickness of the extension inhibiting resin layer is within the above range, excellent moldability and design properties can be obtained, and excellent transfer processability (followability) can be obtained. Further, it is possible to secure the time for applying the activator at the time of the hydraulic transfer, and to transfer it to the transfer target more suitably.

(Bright ink layer)
The glitter ink layer is a layer that expresses glitter and has a concavo-convex shape on at least the surface of the glitter ink layer opposite to the extension-suppressing resin layer to express a sense of quality.

  In the present invention, the concavo-convex shape needs to be present on at least the surface of the glittering ink layer on the side opposite to the extension suppressing resin layer side. The transfer foil of the present invention has a concavo-convex shape and can form a sense of quality in addition to the glitter by forming a concavo-convex sensation expressing part corresponding to the concavo-convex shape during hydraulic transfer. . As shown in FIG. 1, the concave / convex shape may be one in which the concave portion stays in the glittering ink layer, or may extend to the stretch suppressing resin layer and further to the release film. In the present invention, from the viewpoint of obtaining the depth of the concavo-convex shape to be described later and obtaining excellent moldability and designability, it is preferable that the concavo-convex shape extends to the stretch suppressing resin layer and the release film.

  The depth of the concavo-convex shape is preferably from 5 to 80%, more preferably from 10 to 70%, and still more preferably from the viewpoint of obtaining excellent moldability and design properties, with respect to the total thickness of the transfer foil. 20 to 60%. Here, the depth of the concavo-convex shape in the present invention is the depth of the concavo-convex concave portion. Here, the depth of the concave portion is the maximum value of the depth from the straight line when the surface of the glittering ink layer opposite to the side on which the extension suppressing resin layer is provided is regarded as a substantially straight line.

10-100 micrometers is preferable and, as for the periodic width (pitch) of uneven | corrugated shape, More preferably, it is 20-40 micrometers. When the uneven width (pitch) of the irregular shape is within the above range, excellent moldability and design properties can be obtained. Here, in the present invention, the period width (pitch) of the concavo-convex shape is a separation distance between adjacent convex portions.
Moreover, 10-100 micrometers is preferable and, as for the width | variety of an uneven shape, More preferably, it is 20-40 micrometers. When the width of the concavo-convex shape is within the above range, excellent moldability and design properties can be obtained. Here, in this invention, the width | variety of uneven | corrugated shape is the width | variety of convex part itself.
Further, the uneven shape can be suitably provided by embossing.

  The concavo-convex shape may be according to the glitter design expression, and may be appropriately selected according to the combination with the glitter ink layer pattern to be described later. For example, the line groove, the wood grain conduit groove, the grain Preferable examples include an annual ring pattern, a grain pattern, a stone pattern, a metal crystal surface pattern, a cloth pattern, a satin pattern, a leather pattern, a mat surface pattern, a hairline pattern, a spin tone pattern, characters, symbols, and geometrical figures.

The glitter ink layer is preferably formed of glitter ink containing a binder resin and a glitter pigment.
Examples of the binder resin include thermoplastic resins. Specific examples include polyester resins such as acrylic resins and alkyd resins, unsaturated polyester resins, urethane resins (for example, polyester urethane resins), polycarbonate resins, and vinyl chloride-vinyl acetate. Preferable examples include copolymer resins, polyvinyl acetal resins such as polyvinyl butyral (butyral resin), nitrocellulose resins such as nitrified cotton, and the like, and these can be used alone or in combination. In the present invention, nitrocellulose resins such as alkyd resins and nitrified cotton are preferable, and it is more preferable to use a mixture thereof. When these binder resins are used, excellent moldability can be obtained.

The luster pigment is not particularly limited as long as it is a pigment that can exhibit luster by light interference, and preferred examples thereof include metal pigments, pearl pigments, and phosphorescent pigments.
The metal pigment is made of a metal or alloy such as gold, silver, platinum, palladium, nickel, copper, aluminum, chromium, brass, tin, or a metal oxide thereof, and has high glitter and is inexpensive. From the point of view, metal pigments made of scaly foil pieces such as aluminum and brass are preferred. Further, preferred examples of the pearl pigment include a scale-shaped alumina pigment coated with titanium oxide or iron oxide, and a mica pigment coated with titanium oxide or iron oxide.

  The average particle diameter of the glitter pigment is preferably 1 to 20 μm, and more preferably 3 to 15 μm. When the average particle diameter of the glitter pigment is within the above range, excellent glitter can be obtained, and a high-class feeling can be easily obtained by combination with the uneven shape.

  Further, the pattern of the glitter ink layer may be appropriately selected according to the combination with the above-described uneven shape, and a grain pattern imitating the surface of a rock such as a wood grain pattern, a marble pattern (for example, a travertine marble pattern), There are fabric patterns imitating fabrics and cloth-like patterns, tiled patterns, brickwork patterns, etc., and patterns such as parquets and patchwork that combine these patterns. In addition, so-called solid printing in which the entire surface is uniformly colored may be used.

  The thickness of the glitter ink layer is preferably 0.5 to 5 μm, more preferably 0.5 to 3 μm, and further preferably 0.5 to 2 μm. When the thickness of the glitter ink layer is within the above range, excellent moldability and design properties are obtained, and excellent transfer processability (follow-up property) is also obtained.

(Method for producing transfer foil for hydraulic transfer film production)
The transfer foil for producing a hydraulic transfer film of the present invention can be produced, for example, as follows.
First, an extension suppressing resin layer is provided on the release film. The extension suppressing resin layer is laminated on the release film by a known coating method or printing method, a co-extrusion method with a release film, or by laminating a resin film on the release film. Among these, it is preferable to use a known coating method or printing method.
Known coating methods include gravure coating and reverse coating, and known printing methods include gravure printing.

  Moreover, when providing a peeling layer, it forms on a peeling film, before forming an extension suppression resin layer. The release layer is preferably formed by a known coating method or printing method mentioned as the method for forming the above-described extension suppressing resin layer.

  Next, a glitter ink layer is formed. The glitter ink layer is preferably formed by a known coating method or printing method mentioned as the method for forming the above-described stretch suppression resin layer using a glitter ink containing a binder resin and a glitter pigment.

Next, an uneven shape is formed. The formation of the concavo-convex shape is preferably performed by embossing. The embossing is usually performed at a temperature of 80 to 130 ° C., applying a pressure of 20 to 100 ton / m ² , preferably 20 to 60 ton / m ² , using an embossing apparatus with a press time of about 1 to 10 minutes, or an embossing roll Etc. is performed by a continuous embossing process to form a desired uneven shape.
There is no restriction | limiting in particular as an embossing plate used here if the dimension which can achieve the depth of the said uneven | corrugated shape, a period width (pitch), and a width | variety is comprised. Usually, the depth of the uneven shape of the embossed plate is about 10 to 80 μm, preferably 20 to 60 μm, more preferably 30 to 45 μm.

[Hydraulic transfer film]
The hydraulic transfer film of the present invention has a water-soluble film, a glitter ink layer, and an extension suppressing resin layer in this order, and has an uneven shape on the surface of the glitter ink layer opposite to the extension suppressing resin layer side. And the resin that forms the extension suppressing resin layer contains the resin A having a glass transition temperature of 80 ° C. or higher. FIG. 2 is a schematic cross-sectional view showing an example of the configuration of the hydraulic transfer film of the present invention.
The hydraulic transfer film 20 of the present invention shown in FIG. 2 has a water-soluble film 21, a glitter ink layer 13, and an extension suppressing resin layer 12 in order, and at least the extension suppressing resin layer 12 of the glitter ink layer 13. An uneven shape 14 is provided on the surface opposite to the side. Moreover, when a transfer foil has a peeling layer, it has a peeling layer on the outermost surface. Here, the details of the extension suppressing resin layer, the glitter ink layer, and the release layer are the same as those in the above-described transfer foil for producing a hydraulic transfer film.

(Water-soluble film)
The water-soluble film has a role of a substrate in the hydraulic transfer film of the present invention, and is removed when obtaining a decorative molded product after the hydraulic transfer. The water-soluble film is not particularly limited as long as it has water-solubility or water-swelling property, and can be appropriately selected from water-soluble films generally used as a conventional hydraulic transfer film.
Examples of the resin constituting the water-soluble film include polyvinyl alcohol resin, dextrin, gelatin, glue, casein, shellac, gum arabic, starch, protein, polyacrylic amide, sodium polyacrylate, polyvinyl methyl ether, methyl vinyl ether and anhydrous Various water-soluble polymers such as copolymers with maleic acid, copolymers of vinyl acetate and itaconic acid, polyvinylpyrrolidone, acetylcellulose, acetylbutylcellulose, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, sodium alginate and the like can be mentioned. These resins may be used alone or in combination of two or more. In addition, rubber components, such as mannan, xanthan gum, and guar gum, may be added to the water-soluble film.

Among the above water-soluble films, a polyvinyl alcohol (PVA) resin film is particularly preferable from the viewpoints of production stability, solubility in water and economy. The polyvinyl alcohol resin film may contain additives such as starch and rubber in addition to PVA.
Polyvinyl alcohol resin film is necessary when forming a printing layer for transfer on a water-soluble film by changing the degree of polymerization of polyvinyl alcohol, the degree of saponification, and the amount of additives such as starch and rubber. The mechanical strength, moisture resistance during handling, speed of softening due to water absorption after floating on the water surface, time required for spreading or diffusion in water, ease of deformation in the transfer process, etc. can be adjusted as appropriate. it can.

A suitable water-soluble film comprising a polyvinyl alcohol resin film is as described in JP-A-54-92406, for example, 80% by mass of PVA resin, 15% by mass of polymer water-soluble resin. A composition having a mixed composition of 5% by mass of starch and having an equilibrium water content of about 3% is preferable.
Further, although the polyvinyl alcohol resin film is water-soluble, it is preferable that the film remains as a film while being swollen and softened in water at a stage before being dissolved in water. This is because, by performing the hydraulic transfer while the film is still alive, it is possible to prevent an excessive flow and deformation of the printing layer for transfer during the hydraulic transfer.

  As thickness of a water-soluble film, 10-100 micrometers is preferable. When it is 10 μm or more, the uniformity of the film is good and the production stability is high. On the other hand, when it is 100 μm or less, the solubility in water is moderate and the printability is excellent. From the above viewpoint, the thickness of the water-soluble film is more preferably in the range of 20 to 60 μm.

  The water-soluble film can be used by being laminated with a water-permeable base material such as paper, nonwoven fabric, and cloth, for example. When laminating a water-soluble film having swellability, before the hydraulic transfer film floats on the water surface, the substrate having water permeability is separated from the water-soluble or water-soluble film having water swellability, or on the water surface. It is preferable that the substrate having water permeability is separated from the water-soluble film having water solubility or water swellability by the action of water after floating.

[Method for producing hydraulic transfer film]
The method for producing a hydraulic transfer film of the present invention comprises a step (A) a release film, an extension suppressing resin layer, and a glittering ink layer in this order, and at least the side of the glittering ink layer opposite to the extension suppressing resin layer side. The surface of the film has an uneven shape, and the resin forming the stretch-inhibiting resin layer is active in the glitter ink layer and / or water-soluble film of the transfer foil for producing a hydraulic transfer film containing the resin A having a glass transition temperature of 80 ° C. or higher. It comprises a step of applying an agent, a step (B) a step of laminating the water-soluble film on the glitter ink layer side of the transfer foil, and a step (C) a step of peeling the release film. is there.

  The activator used in the step (A) is not particularly limited as long as the surface of the glittering ink layer or the water-soluble film can be roughened and easily adhered, and for example, an activator composition described later can also be used. However, water can also be used. As the activator, it is easy to use water, which is preferable.

  A process (B) can be laminated | stacked by superposing | stacking and pressing a water-soluble film on the glittering ink layer side of the transfer foil for hydraulic transfer film manufacture. More specifically, in a state where the water-soluble film and the transfer foil are superposed, they can be continuously laminated by introducing them between two roll cylinders.

  Further, by peeling the release film in the step (C), the hydraulic transfer film of the present invention, that is, the water-soluble film, the glitter ink layer, and the stretch-inhibiting resin layer are sequentially provided, and at least the glitter ink layer A hydraulic transfer film having a concavo-convex shape on the surface opposite to the side of the stretch-inhibiting resin layer and containing the resin A having a glass transition temperature of 80 ° C. or higher is obtained.

[Method of manufacturing decorative molded product]
The method for producing a decorative molded product of the present invention includes a step (a) a water-soluble film, a glittering ink layer, and an extension suppressing resin layer in this order, and at least the extension inhibiting resin layer side of the glittering ink layer. The opposite surface has a concavo-convex shape, and the resin that forms the stretch-inhibiting resin layer floats on the water surface such that the water-soluble film side faces the water surface side, with the water transfer film containing resin A having a glass transition temperature of 80 ° C. or higher. Before or after the activator, an activator application step of applying an activator composition to the stretch-inhibiting resin layer, step (b) pressing the transferred object onto the hydraulic transfer film that has undergone the step (a), and the extension by water pressure A step of closely attaching the suppression resin layer to the transfer surface of the transferred body, and a step (c) a film removal step of removing the water-soluble film adhered to the transfer surface of the transferred body. It is.

  FIG. 3 is a schematic cross-sectional view showing an example of the configuration of a decorative molded product obtained by the method of manufacturing a decorative molded product of the present invention, and a decorative molded product when using the hydraulic transfer film shown in FIG. Is shown. The decorative molded product 30 obtained by the method for manufacturing a decorative molded product of the present invention shown in FIG. 3 has a transfer target 31, an extension suppressing resin layer 12, and a glittering ink layer 13. And the uneven | corrugated feeling expression part 33 corresponding to the uneven | corrugated shape 14 of the glittering ink layer 13 is hold | maintained, and the uneven | corrugated feeling is hold | maintained by this, and the decorative molded product 30 has glossiness and a high-class feeling. It has the design characteristics to be provided. Moreover, the topcoat layer 32 can also be provided in the decorative molded product 30 as needed.

  The unevenness-expressing portion corresponding to the uneven shape is formed so that the uneven shape becomes a gentle shape as a whole when the hydraulic transfer film of the present invention is slightly stretched during the hydraulic transfer. It retains the feeling of unevenness. The hydraulic transfer film of the present invention is moderately stretched during hydraulic transfer and forms an uneven feeling expression part to maintain the uneven feeling, and has an excellent design with excellent transfer processability (following property). Sex is also obtained.

(Activator application process (a))
The activator application step (a) is a step of applying the activator composition to the extension inhibiting resin layer before or after the hydraulic transfer film is floated on the water surface. In this step, by applying the activator to the extension suppressing resin layer, the surface of the extension suppressing resin layer is roughened, and it becomes easy to adhere to the transfer target.
The hydraulic transfer film is floated on the water surface so that the water-soluble film side faces the water surface side. In order to float the hydraulic transfer film on the surface of the water, it is possible to float one sheet of printed matter at a time, or to flow water in one direction and continuously supply a continuous belt-like hydraulic transfer film on the surface of the water. May be suspended.

  The activator composition is not particularly limited as long as it is a composition that can roughen the extension-suppressing resin layer of the hydraulic transfer film and has a function of dissolving the surface of the transfer target described later. It is preferable to have such a property that it does not evaporate until the extension suppressing resin layer and the glitter ink layer are transferred to the transfer surface. As such an activator composition, the composition containing ester, acetylene glycol, ethers, and resin is mentioned preferably, for example.

Preferred examples of esters include ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, dibutyl oxalate, dibutyl phthalate, dimethyl phthalate, dioctyl phthalate, and diisooctyl phthalate. It is done.
Preferred examples of acetylene glycols include methoxybutyl acetate, ethoxybutyl acetate, ethyl carbitol acetate, propyl carbitol acetate, and butyl carbitol acetate.
Preferred examples of ethers include methyl cellosolve, butyl cellosolve, and isoamyl cellosolve.
In addition, as resins, thermoplastic resins such as acrylate monomers alone or copolymers, polyamide resins, polyester resins, phenol resins, melamine resins, urea resins, epoxy resins, alkyd phthalate resins, diallyl phthalates Preferred examples include thermosetting resins such as resins, alkyd resins, and polyurethane resins, and among these, thermosetting resins are preferred.

  The content of each preferable composition of the activator composition used in the present invention is 5 to 40% by mass for esters, 40 to 80% by mass for acetylene glycols, 5 to 30% by mass for ethers, and 1 for resin. About 20% by mass.

The activator composition may be applied by spray coating or the like, and the application amount is usually 1 to 50 g / m ² , preferably 3 to 30 g / m ² , more preferably 10 to ²⁰ g / m ^{2. 2} .

(Process (b))
The step (b) is a step of pressing the transferred body onto the hydraulic transfer film that has undergone the step (a), and bringing the extension suppressing resin layer into close contact with the transferred surface of the transferred body by the hydraulic pressure.
The water for applying the floating water pressure to the hydraulic transfer film should be adjusted to an appropriate water temperature according to the type of the water-soluble film, and is preferably about 25 to 50 ° C, more preferably 25 to 35 ° C. .
The transfer time between the hydraulic transfer film of the present invention and the transfer target is preferably about 20 to 120 seconds, more preferably about 30 to 60 seconds. Here, the transfer time is the time from when the transfer film of the present invention is suspended in water until the transfer to the transfer target is completed.

(Transfer material)
Examples of the material to be transferred include polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate resin, melamine resin, phenol resin, urea resin, fiber resin, polyethylene, polypropylene, and the like. In addition to the mixed resin, a structure made of a material such as a metal such as iron, aluminum, or copper, ceramics such as ceramics, glass, or wood, or wood can be used.

  The shape of the transfer surface may be a two-dimensional shape that is a planar shape, or a three-dimensional shape such as an uneven shape or a curved shape. Of these, resin structures are usually used frequently. This resin structure has a release agent attached at the time of molding, and dust and fat may also adhere. In order to transfer the glitter ink layer of the hydraulic transfer film with good adhesion, a degreasing liquid is used in advance. It is preferable to clean the surface to be transferred.

  In the step (b), the activator composition applied on the stretch-inhibiting resin layer is in contact with the member to be transferred, and the surface of the member to be transferred is dissolved, whereby the adhesion between the transfer film of the present invention and the member to be transferred is obtained. Will be good.

(Film removal step (c))
The film removal step (c) is a step of removing the water-soluble film adhered to the transfer surface of the transfer object.
The water-soluble film can be removed by, for example, shower cleaning using water. By this step (c), the water-soluble film adhering to the transfer surface is removed. The shower cleaning conditions vary depending on the material forming the water-soluble film, but usually a water temperature of about 15 to 60 ° C. and a cleaning time of about 10 seconds to 5 minutes are preferable. And after a process (c), if a to-be-transferred body is fully dried and a water | moisture content is evaporated, a desired design will be carried out by the glittering ink layer and the extension suppression resin layer which were transcribe | transferred to the to-be-transferred surface of the to-be-transferred body. The assigned resin molded product is obtained.

(Process (d))
The method for producing a decorative molded product of the present invention may further include a step (d) of forming a topcoat layer on the transferred glittering ink layer, if desired, after the step (c).
In the step (d), for the glitter ink layer transferred to the transfer surface of the transfer body in the step (c), for the purpose of improving the surface strength, protecting the surface, adjusting the surface gloss, etc., as necessary A topcoat agent can be applied to form a topcoat layer. As the top coat agent, for example, a thermoplastic resin, a thermosetting resin, an ultraviolet curable resin, and the like, specifically, a resin composition containing a urethane resin, an epoxy resin, an acrylic resin, a fluororesin, a silicon resin, and the like are preferable. .

  The top coat layer can be formed by coating and curing these resin compositions. As a coating method, known methods such as spray coating, electrostatic coating, brush coating, and dip coating can be used. In addition, the curing method may be appropriately selected depending on the resin composition to be used. If a thermoplastic resin is used, it may be cured for several days. If a thermosetting resin is used, heat treatment may be performed. In the case of using a functional resin, it may be performed by irradiating with an appropriate ultraviolet ray.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
(1) Evaluation of formability Embossing (embossing conditions: temperature 120 ° C., pressure 40 ton / m ² , pressing time 5 minutes) was performed on the glittering ink layer of the transfer foil for producing a hydraulic transfer film in each example, and embossed. The state of the surface of the glitter ink layer after peeling off the plate was visually observed and evaluated according to the following criteria.
(Double-circle): The uneven | corrugated shape was very deep and it was shape | molded clearly, without the glittering ink layer peeling.
○: The uneven shape was satisfactorily shaped without peeling off the glitter ink layer.
Δ: The glittering ink layer peeled off slightly in the hot state, but when the embossed plate was peeled off after cooling to room temperature, the glittering ink layer was not peeled off, and the uneven shape was shaped to the extent that no problem occurred in practical use .
X: Even if the embossed plate was peeled off after cooling to room temperature, the glittering ink layer was peeled off, and the uneven shape could not be formed.
(2) Evaluation of design properties 3 g / m ^{2 of} an activator composition having the following composition was applied to the stretch-suppressing resin layer of the hydraulic transfer film obtained in each example, and the activator composition was made uniform with a smoothing roll. (B) after passing through the activator application step (a) of the stretch-inhibiting resin layer, pressing the transferred body against the hydraulic transfer film, and bringing the stretch-inhibiting resin layer into close contact with the transferred surface of the transferred body by water pressure; A decorative molded product was obtained through a film removal step (c) by washing with water. The obtained decorative molded product was observed visually, and its design property was evaluated according to the following criteria.
(Composition of activator composition)
Phthalic acid-based alkyd resin 6 parts by weight Microsilica (pigment) 2 parts by weight Dibutyl phthalate 17 parts by weight Solvent (butyl carbitol acetate) 60 parts by weight Solvent (butyl cellosolve) 15 parts by weight ◎: Corresponds to the uneven shape of the glitter ink layer The feeling of unevenness is maintained very well, and very excellent glitter and luxury are obtained.
○: The unevenness corresponding to the uneven shape of the glitter ink layer was well maintained, and excellent glitter and luxury were obtained.
(Triangle | delta): Although the uneven | corrugated feeling corresponding to the uneven | corrugated shape of a glittering ink layer was somewhat reduced, it was able to visually recognize enough and the glossiness and high-grade feeling of the grade which does not produce a problem in practical use were obtained.
X: Since the unevenness | corrugation corresponding to the uneven | corrugated shape of a glittering ink layer lose | disappeared, glossiness and a high-class feeling were not obtained, or the uneven | corrugated shape could not be shaped at the time of manufacture of a hydraulic transfer film.
(3) Evaluation of transfer processability (followability) In the production of a decorative molded product, a cylindrical resin molded body having a diameter of 35 mm and a length of 250 mm was used as a transfer target, and a hydraulic transfer film was transferred to the side surface. The transfer processability (followability) of the hydraulic transfer film was evaluated by visual observation based on the following criteria.
(Double-circle): The decorative molded product was obtained, following the transferred material well and without causing any cracks.
○: Although the extensibility of the hydraulic transfer film was slightly poor and cracking and throwing power were slightly inferior, the transfer process could be performed with almost no influence on the design.
Δ: Although the extensibility of the hydraulic transfer film was slightly poor and inferior in cracking and throwing power, the influence on the design feeling was such that no problem occurred in practical use.
X: The hydraulic transfer film had poor extensibility and became a decorative molded product with remarkable cracks, or the hydraulic transfer film was cracked during the hydraulic transfer and could not be transferred to the transfer target.

Reference example 1
A stretched polypropylene film (thickness: 18 μm, heat-resistant temperature: 140 ° C.) was used as the release film, and an acrylic resin was gravure coated on the one side with a coating amount of 3 g / m ² to form a release layer with a thickness of 2 μm. Next, on the release layer, a resin for forming the stretch-inhibiting resin layer described in Table 1 is gravure-coated at a coating amount of 3 g / m ² to provide a 1 μm-thick stretch-inhibiting resin layer. Glossy pigment: aluminum paste, average particle size: 10 μm, binder resin: mixture of nitrified cotton and alkyd resin mixed at 50:20), and gravure coated at a coating amount of 2 g / m ² to give a thickness of 1 μm An ink layer was formed. Further, using an embossing apparatus, embossing is performed from the surface side of the glitter ink layer at a pressure of 40 ton / m ² and a temperature of 120 ° C. to form a concavo-convex shape having a depth of 20 μm, thereby producing a transfer foil for producing a hydraulic transfer film. Obtained. About the obtained transfer foil, said (1) moldability evaluation is performed and the evaluation result is shown in Table 1.

  Next, the obtained transfer foil for producing a hydraulic transfer film was stored for 1 hour in an environment of an air temperature of 25 ° C. and a relative humidity of 70%, and then a polyvinyl alcohol resin film (thickness: 30 μm) coated with water on the surface was used. Then, the transfer foil was superposed on the extension suppressing resin layer side and pressed, and the stretched polypropylene film as a release film was peeled off to obtain a hydraulic transfer film. Using the obtained hydraulic transfer film, (2) designability evaluation and (3) transfer workability (followability) are evaluated, and the evaluation results are shown in Table 1.

Examples 2 and 3, Reference Examples 2 to 4, and Comparative Examples 1 and 2
In Reference Example 1, a transfer foil for producing a hydraulic transfer film and a hydraulic transfer film were obtained in the same manner as in Reference Example 1 except that the resin forming the extension suppressing resin layer was changed to the resin shown in Table 1. About the obtained transfer foil, said (1) moldability evaluation is performed and the evaluation result is shown in Table 1. Moreover, (2) evaluation of design property and (3) evaluation of transfer workability (follow-up property) are performed using the obtained hydraulic transfer film, and the evaluation results are shown in Table 1.

Comparative Example 3
In Reference Example 1, a transfer foil for producing a hydraulic transfer film and a hydraulic transfer film were obtained in the same manner as in Reference Example 1 except that the extension suppressing resin layer was not provided. About the obtained transfer foil, said (1) moldability evaluation is performed and the evaluation result is shown in Table 1. Moreover, (2) evaluation of design property and (3) evaluation of transfer workability (follow-up property) are performed using the obtained hydraulic transfer film, and the evaluation results are shown in Table 1.

* 1, Tg in parentheses indicates glass transition temperature.
* 2. The mixing ratio (mass ratio) of the acrylic polyol resin and the urethane resin is 80:20.
* 3 The mixing ratio (mass ratio) of nitrified cotton and alkyd resin is 20:10.
* 4 The mixing ratio (mass ratio) of the acrylic resin and the vinyl chloride-vinyl acetate copolymer resin is 50:50.

Examples 8 and 9, Reference Examples 5 to 8, and Comparative Examples 4 to 6
In Examples 2 and 3, Reference Examples 1 to 4 and Comparative Examples 1 to 3, Examples 2 and 3 were used except that the release film was changed to a stretched polyethylene terephthalate resin film (thickness: 25 μm, heat-resistant temperature: 200 ° C.). In the same manner as in Reference Examples 1 to 4 and Comparative Examples 1 to 3, the transfer foils for producing hydraulic transfer films of Examples 8, 9, Reference Examples 5 to 8, and Comparative Examples 4 to 6, and hydraulic transfer films, respectively. Got. About the obtained transfer foil, said (1) moldability evaluation is performed and the evaluation result is shown in Table 2. Moreover, using the obtained hydraulic transfer film, (2) designability evaluation and (3) transfer workability (followability) are evaluated, and the evaluation results are shown in Table 2.

* 1 to 4, the same as * 1 to 4 in Table 1.

  The transfer foil for producing a hydraulic transfer film of the present invention has a well-shaped uneven shape at the time of producing the transfer foil, and can easily produce a hydraulic transfer film before using the hydraulic transfer film. The obtained hydraulic transfer film has a good concavo-convex shape, and can impart design properties with excellent glitter and high-class feeling to the resin molded product. Moreover, the resin molded product obtained by the manufacturing method of this invention can be utilized suitably as a vehicle interior material, a building material, furniture, a housing of an electric product etc. besides a building material.

DESCRIPTION OF SYMBOLS 10 Transfer foil for hydraulic transfer film manufacture 11 Release film 12 Extension suppression resin layer 13 Bright ink layer 14 Uneven shape 20 Hydraulic transfer film 21 Water-soluble film 30 Decorated product 31 Transfer object 32 Top coat layer 33 Unevenness expression part

Claims (4)

  It has a water-soluble film, a glitter ink layer, and an extension suppressing resin layer in this order, and has an uneven shape on at least the surface of the glitter ink layer opposite to the extension suppressing resin layer, and the extension suppressing resin layer A hydraulic transfer film in which the resin forming the resin contains a resin A having a glass transition temperature of 80 ° C. or higher, and the resin A is an acrylic polyol resin.   The hydraulic transfer film according to claim 1, wherein the glass transition temperature of the resin A is 80 to 145 ° C.   The hydraulic transfer film according to claim 1 or 2, wherein a content of the resin A in the resin forming the extension suppressing resin layer is 50% by mass or more.   The hydraulic transfer film according to claim 1, wherein the binder resin forming the glitter ink layer is a mixture of nitrified cotton and alkyd resin.