JP6245026B2 - Hydraulic transfer film and decorative molded product using the same - Google Patents

Description

  The present invention relates to a hydraulic transfer film and a decorative molded product using the same.

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

  When the hydraulic transfer sheet described in Patent Document 1 is used, when the sheet extends during hydraulic transfer, the vapor deposition metal layer also extends due to the occurrence of fine cracks in the vapor deposition metal layer, thereby transferring the curved surface. 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.

JP 2001-328398 A

Therefore, instead of the vapor-deposited metal layer, a glittering ink layer was used, and it was considered to provide a concavo-convex shape on the glittering ink layer. As a result, it was not possible to obtain a design with excellent glitter and luxury. 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 has a glittering ink layer, has a well-shaped uneven shape during the production of a hydraulic transfer film, and has a design property with excellent glitter and luxury. It is an object of the present invention to provide a hydraulic transfer film that can be applied to a resin molded product, a method for producing the same, 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, this invention provides the following hydraulic transfer film, its manufacturing method, and the decorative molded product using this 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 extension suppressing resin layer opposite to the glitter ink layer, and the extension suppressing resin layer A hydraulic transfer film in which the resin forming the resin contains resin A having a glass transition temperature of 80 ° C. or higher.
2. The manufacturing method of the hydraulic transfer film which has the following processes (A)-(C) in order.
Step (A) A step of laminating a glitter ink layer on a water-soluble film (B) A stretch suppression resin layer formed of a resin containing a resin A having a glass transition temperature of 80 ° C. or higher on the glitter ink layer Step (C): Embossing from the surface opposite to the glittering ink layer side of the stretch-inhibiting resin layer, and providing an uneven shape on at least the opposite surface of the stretch-inhibiting resin layer Step 3. The manufacturing method of the decorative molded product which has the following process (a)-(c) in order.
Step (a) It has a water-soluble film, a glitter ink layer, and a stretch-inhibiting resin layer in this order, and has an uneven shape on at least the surface of the stretch-inhibiting resin layer opposite to the glitter ink layer, Before or after the hydraulic transfer film containing the resin A containing the resin A having a glass transition temperature of 80 ° C. or higher is floated on the water surface so that the water-soluble film side faces the water surface, the stretch-inhibiting resin layer is active in the stretch-inhibiting resin layer Activator application process step (b) for applying the agent composition The transferred material is pressed onto the hydraulic transfer film floating on the water surface after the step (a), and the extension inhibiting resin layer is transferred by the hydraulic pressure. Step (c) for removing the water-soluble film in close contact with the transfer surface of the transferred body

  The hydraulic transfer film of the present invention has a well-shaped shape at the time of production, and can impart design properties with excellent glitter and luxury to the resin molded product. By using a transfer film, it is possible to provide a decorative molded product having a design with excellent luster and luxury.

It is a schematic sectional drawing which shows an example of a structure of the hydraulic transfer film of this invention. It is a schematic sectional drawing which shows an example of a structure of the hydraulic transfer film 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.

[Hydraulic transfer film]
Hereinafter, the present invention will be described with reference to the drawings. 1 and 2 are schematic cross-sectional views illustrating an example of the configuration of the hydraulic transfer film of the present invention.
The hydraulic transfer film 10 of the present invention has a water-soluble film 11, a glitter ink layer 12, and an extension suppressing resin layer 13 in this order, and the extension suppressing resin layer 13 has a surface opposite to the glitter ink layer 12. The resin having the concavo-convex shape 14 and the resin forming the extension suppressing resin layer 13 includes the resin A having a glass transition temperature of 80 ° C. or higher. Further, the extension suppressing resin layer 13 preferably has a multilayer structure of two or more layers, and the hydraulic transfer film 10 shown in FIG. 2 has two extension suppressing resin layers, ie, extension suppressing resin layers a and b. doing.

(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.

(Bright ink layer)
The glitter ink layer is a layer that exhibits glitter and is provided between the water-soluble film and the extension inhibiting resin layer.

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), and nitrocellulose resins. These can be used alone or in combination. In the present invention, alkyd resins and nitrocellulose resins are preferred, and it is more preferred to use a mixture of these. 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 uneven shape provided in the following stretch-inhibiting resin layer, and the surface of the rock such as a wood grain pattern or a marble pattern (for example, a travertine marble pattern). There are stone patterns imitating fabrics, fabric patterns imitating fabrics and cloth-like patterns, tiled patterns, brickwork patterns, etc., and patterns such as marquetry and patchwork that combine these. 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 can be obtained, and design properties with excellent glitter and high-class feeling (hereinafter simply referred to as design properties) are obtained. In addition, excellent transfer processability (followability) is also obtained.

(Extension suppressing resin layer)
The stretch-inhibiting resin layer is provided on the glittering ink layer, has a concavo-convex shape on the surface opposite to the glittering ink layer, and forms a stretch-inhibiting resin layer as a glass transition temperature. It is a layer that needs to contain resin A at 80 ° C. or higher. By providing the stretch-inhibiting resin layer having such a structure, it is possible to obtain a moldability that allows the uneven shape to be satisfactorily shaped during the production of a hydraulic transfer film, and that the glitter ink layer is excessively stretched during the hydraulic transfer. Suppressing and forming an uneven feeling expression part corresponding to the uneven shape to maintain the uneven feeling can provide a design with both glitter and luxury. 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.

  In the present invention, the concavo-convex shape needs to be present on at least the surface of the extension suppressing resin layer on the side opposite to the glitter ink layer side. The hydraulic transfer film of the present invention has a concavo-convex shape and forms a concavo-convex sensation expressing portion corresponding to the concavo-convex shape at the time of hydraulic transfer to maintain a concavo-convex sensation, thereby expressing a high-class feeling in addition to glitter sell. As shown in FIG. 1, the concave / convex shape may be such that the concave portion stays in the extension suppressing resin layer, or may reach the glittering ink layer or even the water-soluble film. In addition, as shown in FIG. 2, when the extension suppressing resin layer has a multilayer structure of two or more layers, the recess may remain in the extension suppressing resin layer b, or the extension suppressing resin layer a, A glittering ink layer or even a water-soluble film may be used. 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, the concavo-convex shape preferably extends to the glitter ink layer and the water-soluble 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 hydraulic transfer film. Is 20-60%. 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 extension suppressing resin layer opposite to the side where the glittering ink 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 in accordance with the glitter design expression, and may be appropriately selected depending on the combination with the pattern of the glitter ink layer. 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. Further, the uneven shape may be patterned so as to exhibit a hologram effect in combination with the glitter ink layer.

  As the resin for forming the extension suppressing resin layer, it is necessary to include the resin A having a glass transition temperature of 80 ° C. or higher. If the resin forming the stretch-inhibiting 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 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 extension suppressing resin layer preferably has a multilayer structure of two or more layers. By setting it as a multilayer structure, a moldability and designability can further be improved. Considering transfer processability (followability) in addition to formability and design properties, it is preferably 2 to 4 layers, more preferably 2 to 3 layers, and particularly preferably 2 layers. In addition, the time for applying the activator during hydraulic transfer is ensured, and the degree of penetration of the activator into the extension-suppressing resin layer and the glitter ink layer can be easily adjusted, so that it can be more suitably transferred to the transfer target. .

  When the extension suppressing resin layer has a multilayer structure, the resin that forms the outermost extension suppressing resin layer preferably includes an alkyd resin and a nitrocellulose resin as the resin A. This is because excellent formability, designability, and transfer processability (follow-up property) can be obtained. Furthermore, when the resin that forms the outermost surface stretch-inhibiting resin layer contains an alkyd resin and a nitrocellulose resin as the resin A, the resin that forms the other stretch-inhibiting resin layer other than the outermost surface contains an acrylic polyol resin as the resin A. It is preferable. Due to the synergistic effect of the combination of the outermost stretch suppressing resin layer and the stretch suppressing resin layer other than the outermost surface, extremely excellent moldability, designability, and transfer processability (followability) can be 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. The thickness of the extension suppressing resin layer is the thickness of one extension suppressing resin layer when the extension suppressing resin layer has a multilayer structure. 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.

[Method for producing hydraulic transfer film]
The method for producing a hydraulic transfer film of the present invention comprises a step (A) a step of laminating a glitter ink layer on a water-soluble film, a step (B) a resin having a glass transition temperature of 80 ° C. or higher on the glitter ink layer. A step of laminating an extension suppressing resin layer formed of a resin containing A, and a step (C) embossing from the surface of the extension suppressing resin layer opposite to the glittering ink layer, and at least the extension It has the process of providing uneven | corrugated shape in the surface of this other side of a suppression resin layer in order.

In the step (A), the glitter ink layer is preferably formed by a known coating method or printing method using a glitter ink containing a binder resin and a glitter pigment.
Known coating methods include gravure coating and reverse coating, and known printing methods include gravure printing.

  In the step (B), the stretch-inhibiting resin layer may be a co-extrusion method with a water-soluble film provided with a glittering ink layer, in addition to the known coating method or printing method exemplified in the method for forming the glittering ink layer. Alternatively, the resin film is laminated on the glitter ink layer by laminating the resin film on the glitter ink layer side of the water-soluble film provided with the glitter ink layer. Among these, it is preferable to use a known coating method or printing method.

The embossing performed in the step (C) for forming the irregular shape is usually at a temperature of 80 to 130 ° C., and a pressure of 20 to 100 ton / m ² , preferably 20 to 60 ton / m ² is applied for 1 to 10 minutes. A desired uneven shape is formed by an embossing apparatus or a continuous embossing process using an embossing roll or the like in a certain pressing time.
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.

[Method of manufacturing decorative molded product]
The method for producing a decorative molded product of the present invention comprises a step (a) a water-soluble film, a glitter ink layer, and a stretch-inhibiting resin layer in order, and at least the glitter ink layer side of the stretch-inhibiting resin 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) passing the step (a), a transferred object on the hydraulic transfer film floating on the water surface A step of pressing and adhering the stretch-suppressing resin layer to the transfer surface of the transferred body by water pressure, and a step (c) a film removal step of removing the water-soluble film adhering to the transferred surface of the transferred body in order It is characterized by having.

  FIG. 3 is a schematic cross-sectional view showing an example of the configuration of a decorative molded product obtained by the method for manufacturing a decorative molded product of the present invention, and the decorative molded product when the hydraulic transfer film shown in FIG. 1 is used. Is shown. The decorative molded product 20 obtained by the method of manufacturing a decorative molded product of the present invention shown in FIG. 3 has a transfer target 21, an extension suppressing resin layer 13, and a glittering ink layer 12 in this order. By having the concavo-convex sensation expressing portion 23 corresponding to the concavo-convex shape 14 of the extension suppressing resin layer 13, the concavo-convex sensation is maintained, whereby the decorative molded product has a design property with excellent radiance and luxury. It has become. Moreover, the top coat layer 22 can also be provided in a decorative molded product as needed.

  The unevenness-expressing portion corresponding to the uneven shape is formed as an overall gentle shape of the uneven shape by a slight extension of the hydraulic transfer film of the present invention during hydraulic transfer, and visually Also 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-controlling resin layer for transfer in the hydraulic transfer film and has a function of dissolving the surface of the transfer target described later. It is preferable that the material does not evaporate until the extension suppressing resin layer is transferred to the transfer surface of the transfer body. 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 in which the transferred body is pressed onto the hydraulic transfer film floating on the water surface after the step (a), and the extension suppressing resin layer is brought into close contact with the transferred surface of the transferred body by water pressure. is there.
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 is pre-greased with a degreasing solution in order to transfer the release inhibiting resin layer of the hydraulic transfer film with good adhesion as the mold release agent may adhere at the time of molding and dust and fat may also adhere. It is preferable to clean the surface to be transferred.

  In the step (b), the activator composition applied on the glitter ink layer is in contact with the transferred body, and the surface of the transferred body is dissolved, whereby the adhesiveness between the transfer film of the present invention and the transferred body. 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 extension suppression resin layer and the glitter ink layer which were transcribe | transferred to the to-be-transferred surface of a 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 , press time 5 minutes) was applied to the glittering ink layer of the hydraulic transfer film in each example, and the embossed plate was peeled off. The appearance of the surface of the glitter ink layer later was visually observed and evaluated according to the following criteria.
A: The uneven shape was shaped very well 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 designability 3 g / m ^{2 of} an activator composition having the following composition was applied to the glittering ink layer of the hydraulic transfer film obtained in each example, and the activator composition was made uniform with a smoothing roll. After undergoing the activator application step (a) of the glitter ink layer, the transferred object is pressed against the hydraulic transfer film floating on the water surface, and the glitter ink layer is brought into close contact with the transferred surface of the transferred object by water pressure. A decorative molded product was obtained through the step (b) and the 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 As a result, it was possible to obtain an excellent glitter and a high-class feeling.
(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.

Example 1
As a water-soluble film, a PVA film (thickness 30 μm) is used, and glitter ink (brightness pigment: aluminum paste (type, etc.), average particle size: 10 μm, binder resin: nitrocellulose resin and alkyd resin on one side. The mixture obtained at a mass ratio of 50:20 was gravure coated at a coating amount of 2 g / m ² to form a glittering ink layer having a thickness of 1 μm. Next, the resin for forming the stretch-inhibiting resin layer described in Table 1 was gravure coated at a coating amount of 3 g / m ² to provide an extension-inhibiting resin layer having a thickness of 1 μm. Next, using an embossing apparatus, embossing was performed from the surface side of the stretch-inhibiting resin 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 to obtain a hydraulic transfer film. Table 1 shows the evaluation results of the moldability of the obtained hydraulic transfer film, the evaluation of the design of the decorative molded product obtained using the hydraulic transfer film, and the evaluation results of the transfer processability (followability). Show.

Examples 2-6, Comparative Examples 1 and 2
In Example 1, a hydraulic transfer film was obtained in the same manner as in Example 1 except that the resin forming the extension suppressing resin layer was a resin shown in Table 1. Table 1 shows the evaluation results of the moldability of the obtained hydraulic transfer film, the evaluation of the design of the decorative molded product obtained using the hydraulic transfer film, and the evaluation results of the transfer processability (followability). Show.

Comparative Example 3
In Example 1, a hydraulic transfer film was obtained in the same manner as in Example 1 except that the stretch suppressing resin layer was not provided and the glitter ink layer was embossed. Table 1 shows the evaluation results of the moldability of the obtained hydraulic transfer film, the evaluation of the design of the decorative molded product obtained using the hydraulic transfer film, and the evaluation results of the transfer processability (followability). Show.

＊１，カッコ内のＴｇはガラス転移温度を示す。
＊２，アクリルポリオール樹脂とウレタン樹脂との混合比（質量比）は８０：２０である。
＊３，ニトロセルロース樹脂とアルキッド樹脂との混合比（質量比）は２０：１０である。
＊４，アクリル樹脂と塩化ビニル−酢酸ビニル共重合樹脂との混合比（質量比）は５０：５０である。

* 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 nitrocellulose resin 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.

Example 7
As a water-soluble film, a PVA film (thickness 30 μm) is used, and glitter ink (brightness pigment: aluminum paste (type, etc.), average particle size: 10 μm, binder resin: nitrocellulose resin and alkyd resin on one side. A glittering ink layer having a thickness of 1 μm and a solid printing with a gravure coat was formed at a coating amount of 2 g / m ² . Next, the resin for forming the stretch-inhibiting resin layer described in Table ² is gravure-coated at a coating amount of 3 g / m ² , and an extension-inhibiting resin layer a having a thickness of 1 μm is provided. Further, a nitrocellulose resin and an alkyd resin are provided. And a gravure coat with a coating amount of 3 g / m ² (glass transition temperature Tg of nitrocellulose resin: 90 ° C., mixing ratio (mass ratio) of nitrocellulose resin and alkyd resin is 20:10), An extension suppressing resin layer b having a thickness of 1 μm was provided. Next, using an embossing apparatus, embossing was performed from the surface side of the stretch-inhibiting resin 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 to obtain a hydraulic transfer film. Table 2 shows the evaluation results of the moldability of the obtained hydraulic transfer film, the evaluation of the design properties of the decorative molded product obtained using the hydraulic transfer film, and the evaluation results of the transfer processability (followability). Show.

Examples 8-12, Comparative Examples 4 and 5
In Example 7, a hydraulic transfer film was obtained in the same manner as in Example 7 except that the resin for forming the extension suppressing resin layer a was a resin shown in Table 2. Table 2 shows the evaluation results of the moldability of the obtained hydraulic transfer film, the evaluation of the design properties of the decorative molded product obtained using the hydraulic transfer film, and the evaluation results of the transfer processability (followability). Show.

＊１，カッコ内のＴｇはガラス転移温度を示す。
＊２，アクリルポリオール樹脂とウレタン樹脂との混合比（質量比）は８０：２０である。
＊３，ニトロセルロース樹脂とアルキッド樹脂との混合比（質量比）は２０：１０である。
＊４，アクリル樹脂と塩化ビニル−酢酸ビニル共重合樹脂との混合比（質量比）は５０：５０である。

* 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 nitrocellulose resin 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.

  The hydraulic transfer film of the present invention can provide a decorative molded product having a design with excellent luster and luxury. The obtained decorative molded product can be suitably used as a building material, automobile interior material, building material, furniture, electrical product housing, and the like.

DESCRIPTION OF SYMBOLS 10 Hydraulic transfer film 11 Water-soluble film 12 Glossy ink layer 13 Extension suppression resin layer 13a Extension suppression resin layer a
13b Extension inhibiting resin layer b
14 Concavity and convexity 20 Decorative decorative product 21 Transfer object 22 Topcoat layer 23 Concavity and convexity expression part

Claims (11)

  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 extension suppressing resin layer opposite to the glitter ink layer, and the extension suppressing resin layer A hydraulic transfer film in which the resin forming the resin contains resin A having a glass transition temperature of 80 ° C. or higher.   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 the resin A is a water-insoluble resin.   The hydraulic transfer film according to any one of claims 1 to 3, wherein the resin A is at least one selected from an acrylic resin, an acrylic polyol resin, a nitrocellulose resin, and a vinyl chloride-vinyl acetate copolymer resin.   The hydraulic transfer film according to claim 1, wherein the extension suppressing resin layer has a multilayer structure of two or more layers.   The hydraulic transfer film according to claim 5, wherein the resin forming the outermost surface extension suppressing resin layer contains an alkyd resin and a nitrocellulose resin as the resin A.   The hydraulic transfer film according to claim 5 or 6, wherein the extension suppressing resin layer other than the outermost surface contains an acrylic polyol resin as the resin A.   The hydraulic transfer film according to any one of claims 1 to 7, 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 any one of claims 1 to 8, wherein the binder resin forming the glitter ink layer is a mixture of a nitrocellulose resin and an alkyd resin. The manufacturing method of the hydraulic transfer film which has the following processes (A)-(C) in order.
Step (A) A step of laminating a glitter ink layer on a water-soluble film (B) A stretch suppression resin layer formed of a resin containing a resin A having a glass transition temperature of 80 ° C. or higher on the glitter ink layer Step (C): Embossing from the surface opposite to the glittering ink layer side of the stretch-inhibiting resin layer, and providing an uneven shape on at least the opposite surface of the stretch-inhibiting resin layer Process The manufacturing method of the decorative molded product which has the following process (a)-(c) in order.
Step (a) It has a water-soluble film, a glitter ink layer, and a stretch-inhibiting resin layer in this order, and has an uneven shape on at least the surface of the stretch-inhibiting resin layer opposite to the glitter ink layer, Before or after the hydraulic transfer film containing the resin A containing the resin A having a glass transition temperature of 80 ° C. or higher is floated on the water surface so that the water-soluble film side faces the water surface, the stretch-inhibiting resin layer is active in the stretch-inhibiting resin layer. Activator application process step (b) for applying the agent composition The transferred material is pressed onto the hydraulic transfer film floating on the water surface after the step (a), and the extension inhibiting resin layer is transferred by the hydraulic pressure. Step (c) for removing the water-soluble film in close contact with the transfer surface of the transferred body

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