JP6721003B2 - 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.

BACKGROUND ART For building materials, automobile interior parts, home electric appliances, office automation equipment, and the like, molded products whose surface is decorated with wood grain or metal tone (metal luster) are used. Many of these molded products have a complicated three-dimensional shape, and conventionally, a method for easily applying a decoration with a high design property to the molded product having the complicated shape has been studied.
As such a decoration method, a water pressure transfer method using water pressure is known, and this water pressure transfer method enables transfer processability on a three-dimensional surface, "depth" such as clear painting feeling, and high quality pattern expression. It is known that it is an excellent curved surface decoration method in terms of designability.

In recent years, the demands on the designability of consumers have become strict, and particularly in the decoration of metallic tone (metallic luster), a high-grade feeling is required in addition to the 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-based transparent resin layer on a water-soluble film, 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 has been proposed (for example, Patent Document 1). ..

When the hydraulic transfer film described in Patent Document 1 is used, when the sheet is expanded during hydraulic transfer, minute cracks are generated in the vapor-deposited metal layer, so that the vapor-deposited metal layer is also extended to perform curved surface transfer. Is possible. However, there is a problem that a large difference in the crack width generated in the vapor-deposited metal layer at the time of hydraulic transfer causes a large difference in designability, and a wide crack width impairs the high-class feeling of the handle.

By the way, as the base material of the water pressure transfer film, a water-soluble film typified by a polyvinyl alcohol resin film has been generally used, as also used in Patent Document 1. However, the polyvinyl alcohol resin film is vulnerable to heat, and when embossing to impart an uneven shape to the water pressure transfer film, the uneven shape cannot be sufficiently imparted, and it is impossible to obtain a design property having a glitter and a high-class feeling. There was a problem. Furthermore, when a water-soluble resin film is used as a base material, for example, when the water pressure transfer film is stored for a long time, curling or blocking is likely to occur due to absorption of moisture in the air, and the influence of humidity in the air. There is also a problem that the design of the decorative layer is 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 substrate having excellent heat resistance, a decorative layer made of a metal thin film layer or the like is provided on the substrate, and embossing is applied to form an uneven shape There has been proposed a method for solving the problem that the uneven shape cannot be sufficiently imparted by producing a hydraulic transfer film by using (for example, Patent Document 2). By this method, the water pressure transfer film has a sufficient uneven shape. However, similar to the hydraulic transfer film described in Patent Document 1, problems such as a difference in design due to the size of the crack width generated in the metal thin film layer formed of the vapor-deposited metal during the hydraulic transfer are still solved. Was not done.

JP 2001-328398 A JP, 2013-000896, A

In Patent Documents 1 and 2, in order to obtain a design property having a glittering property and a high-class feeling, it was examined to use a glittering ink layer instead of the vapor-deposited metal layer, and to provide the glittering ink layer with an uneven shape. However, the glitter ink layer was excessively extended during the hydraulic transfer, and the unevenness disappeared, so that it was not possible to obtain a design property having excellent glitter and a high-grade feeling. This was the same when the method described in Patent Document 2 was used to form a sufficient uneven shape on the hydraulic transfer film.
Furthermore, in order to maintain the uneven shape of the glitter ink layer and prevent the sense of unevenness from disappearing, 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 investigated to suppress excessive extension of the ink layer. However, depending on the type of the resin forming the resin layer, the glitter ink layer may be peeled off during the production of the hydraulic transfer film, and thus it is not possible to form a good uneven shape on the glitter ink layer. In some cases, the quality and the sense of quality were lost.
Under such circumstances, the present invention provides a hydraulic transfer capable of giving a resin molded article a design property in which an uneven shape is satisfactorily shaped at the time of manufacturing a transfer foil, and which has excellent glitter and a high-class feeling. The challenge is to provide a film.

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the following invention can solve the problems. That is, the present invention provides the following hydraulic transfer film.

1. A water-soluble film, an extension suppressing resin layer, and a glitter ink layer are provided in this order, and at least the surface of the extension suppressing resin layer opposite to the glitter ink layer side has a concavo-convex shape, and the extension suppressing resin layer. The hydraulic transfer film in which the resin forming the resin contains the resin A having a glass transition temperature of 80 to 145°C.

INDUSTRIAL APPLICABILITY The water pressure transfer film of the present invention has a good uneven shape, and can impart a design property having excellent glitter and a 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 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. 1 and 2 are schematic cross-sectional views showing an example of the structure 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, a glitter ink layer 12, and an extension suppressing resin layer 13 in order, and at least the side of the extension suppressing resin layer 13 on the glitter ink layer 12 side. Has a concavo-convex shape 14 on the opposite surface, and the resin forming the extension suppressing resin layer 13 contains a 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 a and b. doing. The transfer foil 10 for producing a hydraulic transfer film of the present invention has the uneven shape 14 formed at the stage before the water-soluble film, which is weak against heat, is laminated to obtain the hydraulic transfer film. The problem peculiar to the hydraulic transfer film that is inferior in property can be solved. Further, the hydraulic transfer film, by using a water-soluble resin film as a substrate, absorbs moisture in the air to cause curling or blocking when stored for a long period of time, or the film expands or contracts to improve the design. 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 can be stored in a state where it is separated from the water-soluble film used as the base material of the hydraulic transfer film, the hydraulic transfer film can be easily prepared immediately before use. , You can avoid these problems.

(Peeling film)
The release film is not particularly limited as long as it can be released even after contact with the glittering ink layer or a release layer which is preferably provided as necessary, and is not particularly limited, but it is water-insoluble. Also, from the viewpoint of forming a good uneven shape, one having high heat resistance is preferable. Specifically, in addition to a polyester resin film such as polyethylene terephthalate, or a polyolefin resin film such as a polyethylene film or a polypropylene film or a stretched polyolefin resin film, paper or a coating agent thereof such as a silicone with a mold release agent is used. 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, especially a polyethylene terephthalate resin film is preferable.
Further, from the viewpoint of selecting a material that is easily peeled from the glitter ink layer or the peeling layer, it is preferable to use a material that has been subjected to an easy peeling treatment.

The thickness of the release film is preferably 10 to 100 μm. Within the above range, good unevenness can be easily provided, and the production stability of the transfer foil can be improved. 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 glitter ink layer, and is preferably a layer provided to facilitate the release of the release film.
The material for forming the release layer is not particularly limited as long as it is a resin having excellent release properties, and examples thereof include acrylic resin, vinyl chloride resin (copolymer of vinyl chloride and vinyl acetate), olefin resin, silicone resin. Preferred examples thereof include fluororesins, polyvinylpyrrolidone resins, silicones, and various resins modified with fluorine.

Also, wax may be blended with these resins. The wax is not particularly limited as long as it melts and exhibits peelability at the time of transfer, and examples thereof include microcrystalline wax, carnauba wax, paraffin wax, Fischer-Tropsch wax, various low molecular weight polyethylene, wood wax, beeswax, and whale. Wax, ivorot wax, wool wax, shellac wax, candelilla wax, petrolactam, partially modified wax, fatty acid ester, fatty acid amide and the like are preferable. Among these, microcrystalline wax and carnauba wax, which have a relatively high melting point and are difficult to dissolve in a solvent, are preferable.

The thickness of the release layer is preferably 1 to 10 μm, more preferably 1 to 5 μm. When the thickness of the release layer is within the above range, good release performance can be obtained.

(Glittering ink layer)
The glitter ink layer is a layer that develops glitter and is a layer provided between the release film and a spread suppressing resin layer described later.

The glitter ink layer is preferably formed of a glitter ink containing a binder resin and a glitter pigment.
Examples of the binder resin include thermoplastic resins, and specific examples thereof include polyester resins such as acrylic resins and alkyd resins, unsaturated polyester resins, urethane resins (for example, polyester urethane resins), polycarbonate resins, vinyl chloride-vinyl acetate. Copolymer resins, polyvinyl acetal resins (butyral resins) such as polyvinyl butyral, and nitrocellulose resins such as nitrified cotton are preferably mentioned, and these can be used alone or in combination of two or more kinds. In the present invention, alkyd resins and nitrocellulose resins such as 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 glittering pigment is not particularly limited as long as it is a pigment capable of exhibiting a glittering property due to interference of light, and for example, a metal pigment, a pearl pigment, a luminous pigment and the like are preferably mentioned.
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 viewpoint, a metal pigment made of a flaky foil piece such as aluminum or brass is preferable. Preferable examples of the pearl pigment include a flake-shaped alumina pigment coated with titanium oxide or iron oxide, and a mica pigment coated with titanium oxide or iron oxide.

The average particle size of the bright pigment is preferably 1 to 20 μm, 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 combining 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 on the extension suppressing resin layer as described below, and the surface of rock such as a wood pattern or a marble pattern (for example, a travertine marble pattern) There is a stone pattern that imitates, a fabric pattern that imitates a texture or cloth-like pattern, a tile pasting pattern, a brickwork pattern, and the like, and a pattern such as parquet or patchwork that combines these. Further, 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 is obtained, and designability with excellent glitter and a high-grade feeling (hereinafter, sometimes simply referred to as designability) is obtained. In addition, excellent transfer processability (following property) can be obtained.

(Extension suppression resin layer)
The extension suppressing resin layer is provided on the glitter ink layer, has a concavo-convex shape on at least the surface opposite to the side of the glitter ink layer, and has a glass transition as a resin forming the extension suppressing resin layer. This layer is required to contain the resin A having a temperature of 80° C. or higher. By providing the extension suppressing resin layer having such a configuration, it is possible to obtain a moldability capable of appropriately shaping the uneven shape at the time of manufacturing the transfer foil, and also to prevent the glitter ink layer from being excessively expanded during the hydraulic transfer. Then, by forming the unevenness expressing portion corresponding to the uneven shape to maintain the unevenness, it is possible to obtain a design property having a glitter and a high-grade feeling. In addition, the unevenness expressing portion corresponding to the uneven shape will be described in detail in the description of the method for manufacturing the decorative molded product.

In the present invention, the extension suppressing resin layer is a layer positioned on the surface layer side of the glittering ink layer after being transferred to the resin molded product, and the glittering ink layer is visually recognized through the extension suppressing resin layer. It is preferable that the ink layer is transparent so that it can be seen more clearly. Here, the term “transparent” is a concept including colorless and transparent, as well as colored and translucent. The extension suppressing resin layer may have a single-layer structure or a multi-layer structure having two or more layers.

In the present invention, the uneven shape needs to exist at least on the surface of the extension suppressing resin layer opposite to the glitter ink layer side. The hydraulic transfer film of the present invention has an uneven shape, and at the time of water pressure transfer, by forming an unevenness expressing portion corresponding to the uneven shape to retain the unevenness, a high-grade feeling is exhibited in addition to the glitter. sell. As shown in FIG. 1, the concavo-convex shape may be such that the concave portion remains in the extension suppressing resin layer, or it may extend to the glitter ink layer or even the release film. Further, as shown in FIG. 2, when the extension suppressing resin layer has a multilayer structure of two or more layers, the concave portion may remain in the extension suppressing resin layer b, or the extension suppressing resin layer a, It may be a glittering ink layer or even a release film. In the present invention, it is preferable that the uneven shape extends to the glitter ink layer and the water-soluble film from the viewpoint of obtaining the depth of the uneven shape described later and obtaining excellent moldability and designability.

The depth of the uneven shape is preferably from 5 to 80%, more preferably from 10 to 70%, further preferably from the viewpoint of obtaining excellent moldability and designability. Is 20 to 60%. Here, in the present invention, the depth of the concave-convex shape means the depth of the concave-convex shape. 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 on which the glitter ink layer is provided is regarded as a substantially straight line.

The period width (pitch) of the uneven shape is preferably 10 to 100 μm, more preferably 20 to 40 μm. When the period width (pitch) of the uneven shape is within the above range, excellent moldability and designability can be obtained. Here, in the present invention, the periodic width (pitch) of the concavo-convex shape is the distance between the adjacent convex portions.
Further, the width of the uneven shape is preferably 10 to 100 μm, more preferably 20 to 40 μm. When the width of the uneven shape is within the above range, excellent moldability and designability can be obtained. Here, in the present invention, the width of the uneven shape refers to the width of the convex portion itself.
Further, the uneven shape can be preferably provided by embossing.

The concavo-convex shape may be in conformity with the glittering design expression, and may be appropriately selected depending on the combination with the pattern of the glittering ink layer, and for example, a linear groove, a wood grain conduit groove, a wood grain. Preferable examples include annual ring pattern, grain pattern, stone pattern, metal crystal surface pattern, cloth pattern, satin pattern, leather pattern, matte surface pattern, hairline pattern, spin tone pattern, letters, symbols and geometric figures.

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

In the present invention, the glass transition temperature is measured as follows.
A differential scanning calorimeter was used to raise the temperature to 200° C., and the sample cooled from that temperature to 0° C. at a temperature lowering rate of 10° C./min was measured at a temperature raising rate of 10° C./min. When a peak is observed at a temperature lower than the softening point by 20° C. or more, the temperature of the peak is observed. When a peak is observed at a temperature lower than the softening point by 20° C. or more and a step is observed, the step portion is The temperature at the intersection of the tangent line showing 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, but for example, acrylic resin, acrylic polyol resin, nitrocellulose resin, vinyl chloride-vinyl acetate copolymer resin and the like are preferably mentioned, and among them, Acrylic polyol resins are preferred. In the present invention, these resins may be used alone or in combination of two or more kinds.
In addition, as the resin A, it is preferable to use a water-insoluble resin from the viewpoint of suppressing excessive extension of the glittering ink layer during hydraulic transfer and satisfactorily forming an unevenness expressing portion 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 exemplified as the resin A.

Further, as the resin forming the extension suppressing resin layer, as long as the resin A is contained, another resin, for example, a resin B having a glass transition temperature of lower than 80° C. may be contained. 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 20° C. or lower is more preferable, and a resin having a glass transition temperature of 10° C. or lower is further 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 preferred. By combining the resin B having a low glass transition temperature, excellent transfer processability (following property) can be obtained. Among them, 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, further preferably 60 to 90% by mass, and particularly preferably 70 to It is 85 mass %. When the content of the resin A in the resin is within the above range, excellent moldability and designability are obtained, and also excellent transfer processability (following property) is obtained.

The extension suppressing resin layer preferably has a multilayer structure of two or more layers. By having a multi-layered structure, it is possible to further improve moldability and designability. Considering transfer processability (following property) in addition to moldability and designability, the number of layers is preferably 2 to 4 layers, more preferably 2 to 3 layers, and particularly preferably 2 layers. Further, it is possible to secure a time for applying the activator at the time of hydraulic transfer, to easily adjust the degree of penetration of the activator into the spread suppressing resin layer or the glitter ink layer, and it is possible to transfer to the transfer target more preferably. ..

When the extension suppressing resin layer has a multilayer structure, the resin forming the outermost extension suppressing resin layer preferably contains an alkyd resin and a nitrocellulose resin as the resin A. This is because excellent moldability, designability, and transfer processability (followability) can be obtained. Further, when the resin forming the outermost extension suppressing resin layer contains an alkyd resin and a nitrocellulose resin as the resin A, the resin forming the extension suppressing 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 extension suppressing resin layer on the outermost surface and the extension suppressing resin layer other than the outermost surface, extremely excellent moldability, designability, and transfer processability (following property) 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, still more 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 suppressing resin layer is within the above range, excellent moldability and designability are obtained, and also excellent transfer processability (following property) is obtained. Further, it is possible to secure a time for applying the activator at the time of hydraulic transfer, and it is possible to transfer to the transfer target more preferably.

(Method for manufacturing transfer foil for manufacturing hydraulic transfer film)
The transfer foil for producing a hydraulic transfer film of the present invention can be produced, for example, as follows.
First, a glitter ink layer is provided on the release film. 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.

When a release layer is provided, it is provided on the release film before forming the glitter ink layer. The release layer is preferably formed by a known coating method or printing method, which has been mentioned as the method for forming the glitter ink layer.

Next, the extension suppressing resin layer is formed. The spread suppressing resin layer is a known coating method or printing method exemplified in the method for forming the glittering ink layer, a coextrusion method with a water-soluble film provided with the glittering ink layer, or a glittering resin film. The water-soluble film provided with an ink layer is laminated on the glitter ink layer side to be laminated on the glitter ink layer. Of these, the known coating method or printing method is preferable.

Then, the uneven shape is formed. The uneven shape is preferably formed by embossing. The embossing is usually performed at a temperature of 80 to 130° C., a pressure of 20 to 100 ton/m ² , preferably 20 to 60 ton/m ² , and a pressing time of about 1 to 10 minutes by an embossing device or an embossing roll. The desired concavo-convex shape is formed by a continuous embossing process such as.
The embossing plate used here is not particularly limited as long as it has a depth, a periodic width (pitch), and a dimension capable of achieving the above-mentioned concavo-convex shape. Usually, the depth of the uneven shape of the embossing plate is about 10 to 80 μm, preferably 20 to 60 μm, and more preferably 30 to 45 μm.

[Water pressure transfer film]
The hydraulic transfer film of the present invention has a water-soluble film, an extension suppressing resin layer, and a glitter ink layer in order, and at least a concavo-convex shape on the surface of the extension suppressing resin layer opposite to the glitter ink layer side. The resin forming the extension suppressing resin layer contains the resin A having a glass transition temperature of 80° C. or higher. FIG. 3 is a schematic cross-sectional view showing an example of the structure of the hydraulic transfer film of the present invention.
The hydraulic transfer film 20 of the present invention shown in FIG. 3 has a water-soluble film 21, an extension suppressing resin layer 13, and a glitter ink layer 12 in order, and at least the glitter ink layer 12 of the extension suppressing resin layer 13 The surface on the side opposite to the side has an uneven shape 14. When the transfer foil has a release layer, it has the release 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 transfer foil for producing a hydraulic transfer film described above.

(Water-soluble film)
The water-soluble film has a role of a base material in the hydraulic transfer film of the present invention, and is removed when a decorative molded article is obtained after hydraulic transfer. Any water-soluble or water-swellable film may be used as the water-soluble film, and it can be appropriately selected and used from the water-soluble films generally used as the 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 acid amide, sodium polyacrylate, polyvinyl methyl ether, methyl vinyl ether and anhydrous. Examples thereof include various copolymers of maleic acid, vinyl acetate and itaconic acid, polyvinylpyrrolidone, acetyl cellulose, acetyl butyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, sodium alginate, and various other water-soluble polymers. These resins may be used alone or in combination of two or more. A rubber component such as mannan, xanthan gum, or guar gum may be added to the water-soluble film.

Among the above water-soluble films, a polyvinyl alcohol (PVA) resin film is 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 required 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 blending amount of additives such as starch and rubber. Appropriate mechanical strength, moisture resistance during handling, speed of softening due to water absorption after floating on the water surface, time required for spreading or spreading in water, easiness of deformation during transfer process, etc. it can.

A suitable water-soluble film made of a polyvinyl alcohol resin film is as described in JP-A-54-92406. For example, PVA resin 80% by mass, polymer water-soluble resin 15% by mass. It is preferable that the mixture has a mixed composition of 5% by mass of starch and a balanced water content of about 3%.
Further, although the polyvinyl alcohol resin film is water-soluble, it is preferable that it remains as a film while swelling and softening in water before being dissolved in water. By performing hydraulic transfer while the film is still present, excessive flow and deformation of the transfer print layer during hydraulic transfer can be prevented.

The thickness of the water-soluble film is preferably 10 to 100 μm. 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 appropriate and the printability is excellent. From the above viewpoints, the thickness of the water-soluble film is more preferably in the range of 20 to 60 μm.

The water-soluble film may be used by laminating it with a water-permeable substrate such as paper, non-woven fabric, cloth or the like. When laminated with a water-soluble film having a swelling property, the water-permeable base material is separated from the water-soluble or water-swelling water-soluble film before being floated on the water surface of the water pressure transfer film, or on the water surface. It is preferable that the water-permeable base material is separated from the water-soluble or water-swellable water-soluble film by the action of water after floating.

[Production method of hydraulic transfer film]
The method for producing a hydraulic transfer film of the present invention has a step (A) release film, a glitter ink layer, and a spread suppressing resin layer in this order, and at least the side of the spread suppressing resin layer opposite to the glitter ink layer side. Has an uneven surface, and the resin forming the extension suppressing resin layer contains the resin A having a glass transition temperature of 80° C. or higher and is active in the extension suppressing resin layer and/or the water-soluble film of the transfer foil for producing a hydraulic transfer film. A step of applying an agent, a step (B) a step of laminating the water-soluble film on the extension suppressing resin 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 it can roughen the surface of the extension suppressing resin layer or the water-soluble film to facilitate the adhesion, and for example, the activator composition described later can be used. However, water can also be used. Water is preferably used as the activator because it is easy to use.

In the step (B), a water-soluble film may be laminated on the extension suppressing resin layer side of the transfer foil for producing a hydraulic transfer film, and pressure may be applied for lamination. More specifically, the water-soluble film and the transfer foil can be continuously laminated by introducing the water-soluble film and the transfer foil between the two roll cylinders.

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

[Manufacturing method of decorative molded product]
The method for producing a decorated molded article of the present invention comprises a step (a) a water-soluble film, an extension suppressing resin layer, and a glitter ink layer in order, and at least the side of the extension suppressing resin layer on the glitter ink layer side. Floating a water pressure transfer film having a concavo-convex shape on the opposite side and a resin forming the extension suppressing resin layer containing a resin A having a glass transition temperature of 80°C or higher on the water surface so that the water-soluble film side faces the water surface side. Before or after the actuation, an activator coating step of applying an activator composition to the glitter ink layer, step (b) pressing the transfer target on the hydraulic transfer film that has undergone the step (a), and applying the glitter to the glitter. Characterized in that it has a step of closely adhering the photosensitive ink layer to the transfer surface of the transfer body, and a step (c) a film removal step of removing the water-soluble film adhered to the transfer surface of the transfer body. Is.

FIG. 4 is a schematic cross-sectional view showing an example of the configuration of a decorative molded product obtained by the method for producing a decorative molded product of the present invention. The decorative molded product when the hydraulic transfer film shown in FIG. 3 is used. Is shown. The decorative molded product 30 obtained by the method for producing a decorative molded product of the present invention shown in FIG. 4 has a transferred material 31, a glitter ink layer 12, and an extension suppressing resin layer 13 in order. The unevenness feeling is maintained by having the concave-convex feeling-developing portion 33 corresponding to the uneven shape 14 of the extension suppressing resin layer 13, and thus the decorative molded article 30 has a glitter and a high-class feeling. It has a design property. Further, the decorative molded article 30 may be provided with a top coat layer 32 as required.

The unevenness expressing portion corresponding to the uneven shape is formed by the hydraulic transfer film of the present invention being slightly stretched during the hydraulic transfer, whereby the uneven shape is formed to be a gentle shape as a whole. It retains a feeling of unevenness. The water pressure transfer film of the present invention is appropriately stretched during the water pressure transfer to form the unevenness-developing portion, thereby retaining the unevenness feeling, and with excellent transfer processability (following property), an excellent design. You can also get sex.

(Activator coating step (a))
The activator application step (a) is a step of applying the activator composition to the glitter ink layer before or after suspending the hydraulic transfer film on the water surface. In this step, by applying an activator to the glitter ink layer, the surface of the glitter ink layer is roughened and it becomes easy to adhere to the transferred material.
The water pressure 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 water pressure transfer film on the water surface, it is possible to float the sheet-by-sheet prints one by one, or water is flowed in one direction, and a continuous strip of water pressure transfer film is continuously supplied on the water surface. You may float it.

The activator composition is not particularly limited as long as it is a composition capable of roughening the glittering ink layer of the hydraulic transfer film, and having a function of dissolving the surface of the transfer target to be described later. It is preferable that the surface to be transferred has a property such that it does not evaporate until the glittering ink layer and the spread suppressing resin layer are transferred. Preferred examples of such activator compositions include compositions containing esters, acetylene glycols, ethers, and resins.

Preferred 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. To be
Preferable examples of the acetylene glycols include methoxybutyl acetate, ethoxybutyl acetate, ethyl carbitol acetate, propyl carbitol acetate and butyl carbitol acetate.
Preferred ethers include methyl cellosolve, butyl cellosolve and isoamyl cellosolve.
Examples of the resin include thermoplastic resins such as homopolymers or copolymers of acrylate-based monomers, polyamide resins, polyester resins, phenol resins, melamine resins, urea resins, epoxy resins, alkyd phthalates, and diallyl phthalates. Thermosetting resins such as resins, alkyd resins and polyurethane resins are preferred, and thermosetting resins are preferred.

The preferred content of each 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. It is about 20% by mass.

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

(Process (b))
The step (b) is a step of pressing the transfer target on the hydraulic transfer film subjected to the step (a) to bring the glitter ink layer into close contact with the transfer target surface of the transfer target by hydraulic pressure.
The water for applying the water pressure to float the water pressure transfer film is preferably adjusted to a suitable 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 to when the transfer to the transfer target is completed.

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

The shape of the transferred surface may be a two-dimensional shape that is a planar shape, or may be a three-dimensional shape such as an uneven shape or a curved shape. Of these, resin structures are often used. In this resin structure, a release agent may be attached during molding, and dust and oil may also be attached. In order to transfer the glitter ink layer of the hydraulic transfer film with good adhesiveness, a degreasing liquid is previously prepared. The surface to be transferred is preferably cleaned by.

In the step (b), the activator composition applied on the glitter ink layer is brought into contact with the transfer-receiving material, and the surface of the transfer-receiving material is dissolved to thereby obtain the adhesion between the transfer film of the present invention and the transfer-receiving material. Will be good.

(Film removal step (c))
The film removing step (c) is a step of removing the water-soluble film adhered to the transfer surface of the transfer target.
The water-soluble film can be removed, for example, by shower washing with water. By this step (c), the water-soluble film attached to the transfer surface is removed. The conditions for shower washing vary depending on the material forming the water-soluble film and the like, but normally, a water temperature of about 15 to 60° C. and a washing time of about 10 seconds to 5 minutes are preferable. Then, after the step (c), if the transferred material is sufficiently dried to evaporate the moisture, a desired design can be obtained by the glitter ink layer and the extension suppressing resin layer transferred onto the transferred surface of the transferred material. The applied resin molded product is obtained.

(Process (d))
The method for producing a decorative molded product of the present invention can further include a step (d) of forming a topcoat layer on the transferred extension suppressing resin layer after the step (c), if desired.
In the step (d), the glitter ink layer transferred to the transfer surface of the transfer material in the step (c) may be added, if necessary, for improving the surface strength, protecting the surface, adjusting the surface gloss, etc. A topcoat layer can be formed by applying a topcoat agent. As the top coat agent, for example, a resin composition containing a thermoplastic resin, a thermosetting resin, an ultraviolet curable resin, or the like, specifically, a urethane resin, an epoxy resin, an acrylic resin, a fluororesin, a silicon resin or the like is preferably mentioned. ..

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. Further, as a method of curing, it may be appropriately selected depending on the resin composition to be used, when a thermoplastic resin is used, it may be aged for several days, and when a thermosetting resin is used, heat treatment may be performed, and ultraviolet curing When the resin is used, it may be irradiated with appropriate ultraviolet rays.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
(1) Evaluation of moldability Embossing (embossing conditions: temperature 120°C, pressure 40 ton/m ² , press time 5 minutes) was applied to the glitter ink layer of the transfer foil for producing a hydraulic transfer film in each example to emboss it. After the plate was peeled off, the appearance of the surface of the glitter ink layer was visually observed and evaluated according to the following criteria.
⊚: The brilliant ink layer was not peeled off, and the uneven shape was extremely deep and clearly imprinted.
◯: The uneven shape was satisfactorily imprinted without peeling off the glitter ink layer.
Δ: Although the glittering ink layer was slightly peeled off in a hot state, when the embossing plate was peeled off after cooling to room temperature, the glittering ink layer was not peeled off, and the uneven shape was shaped to such an extent that practical problems do not occur. ..
X: Even if the embossing plate was peeled off after cooling to room temperature, the glitter ink layer was peeled off, and the uneven shape could not be imprinted.
(2) Evaluation of design property 3 g/m ^{2 of} an activator composition having the following composition was applied to the extension suppressing resin layer of the hydraulic transfer film obtained in each example, and the activator composition was made uniform with a smoothing roll, A step (b) of pressing the transfer target against the hydraulic transfer film after the step (a) of applying the extension suppression resin layer activator to bring the extension suppression resin layer into close contact with the transfer surface of the transfer target by hydraulic pressure; A decorative molded product was obtained through the film removal step (c) by washing with water. The obtained decorative molded product was visually observed and its designability was evaluated according to the following criteria.
(Composition of activator composition)
Phthalic acid-based alkyd resin 6 parts by weight Micro silica (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 ◎: Corresponding to the uneven shape of the glitter ink layer The resulting unevenness was maintained very well, and very excellent glitter and high-grade feeling were obtained.
◯: The uneven feeling corresponding to the uneven shape of the glitter ink layer was well retained, and excellent glitter and high-grade feeling were obtained.
Δ: The unevenness corresponding to the uneven shape of the glitter ink layer was slightly lowered, but it was sufficiently visible, and the glitter and the high-grade feeling to the extent that problems did not occur in practical use were obtained.
X: Since the unevenness corresponding to the uneven shape of the glitter ink layer disappeared, glitter and high-grade feeling could not be obtained, or the uneven shape could not be imprinted at the time of manufacturing the hydraulic transfer film.
In addition, for example, although the evaluation is ◯, but slightly inferior, it is described by adding “-” such as “◯ ⁻ ”.
(3) Evaluation of transfer processability (following property) 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 transferred body, and a hydraulic transfer film was transferred to the side surface thereof. The transfer processability (following property) of the water pressure transfer film was evaluated by the following criteria by visual observation.
⊚: A decorated molded product was obtained which satisfactorily follows the transferred material and did not cause any cracks.
◯: Although the extensibility of the hydraulic transfer film was slightly poor and cracking and throwing power were slightly inferior, transfer processing could be performed with almost no effect on design.
Δ: Although the extensibility of the water pressure transfer film was slightly poor and cracking and throwing power were inferior, the effect on design was such that practical problems did not occur.
Poor: The extensibility of the hydraulic transfer film was poor, resulting in a decorated molded product with significant cracking, or the hydraulic transfer film was cracked during hydraulic transfer and could not be transferred to the transfer target.

Example 1
A stretched polypropylene film (thickness: 18 μm, heat resistant temperature: 140° C.) was used as a release film, and an acrylic resin was gravure-coated on one surface of the release film at a coating amount of 3 g/m ² to form a release layer having a thickness of 2 μm. Next, a bright ink (bright pigment: aluminum paste, average particle size: 10 μm, binder resin: mixture of nitrification cotton and alkyd resin mixed at 50:20) was applied onto the release layer at a coating amount of 2 g/m. ² is gravure coated to form a glittering ink layer having a thickness of 1 μm, and the resin forming the extension suppressing resin layer described in Table 1 is gravure coated at a coating amount of 3 g/m ² to give a thickness of 1 μm. An extension suppressing resin layer a is provided, and a mixture of nitrification cotton and alkyd resin (glass transition temperature Tg of nitrification cotton: 90° C., mixing ratio (mass ratio) of nitrification cotton and alkyd resin is 20:10). Was applied by gravure coating at a coating amount of 3 g/m ² to form an extension suppressing resin layer b having a thickness of 1 μm. Then, using an embossing device, embossing is performed from the surface side of the extension suppressing 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 transfer foil for producing a hydraulic transfer film. Obtained. The transfer foil thus obtained was evaluated for (1) moldability, and the evaluation results are 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 applied. Then, the transfer foil was superposed on the glitter ink layer side and pressed, and the stretched polypropylene film as the release film was released to obtain a hydraulic transfer film. Using the obtained hydraulic transfer film, (2) design property evaluation and (3) transfer processability (following property) evaluation were performed, and the evaluation results are shown in Table 1.

Examples 2-6, and Comparative Examples 1 and 2
A transfer foil for producing a hydraulic transfer film and a hydraulic transfer film were obtained in the same manner as in Example 1 except that the resin forming the extension suppressing resin layer was changed to the resin shown in Table 1. The transfer foil thus obtained was evaluated for (1) moldability, and the evaluation results are shown in Table 1. Further, using the obtained hydraulic transfer film, (2) designability evaluation and (3) transfer processability (following property) evaluation were performed, and the evaluation results are shown in Table 1.

Comparative Example 3
A transfer foil for producing a hydraulic transfer film and a hydraulic transfer film were obtained in the same manner as in Example 1 except that the extension suppressing resin layer was not provided. The transfer foil thus obtained was evaluated for (1) moldability, and the evaluation results are shown in Table 1. Further, using the obtained hydraulic transfer film, (2) designability evaluation and (3) transfer processability (following property) evaluation were performed, 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 7-12 and Comparative Examples 4-6
In Examples 1 to 6 and Comparative Examples 1 to 3, Examples 1 to 6 and Comparative Examples 1 to 1 except that the release film was changed to a stretched polyethylene terephthalate resin film (thickness: 25 μm, heat resistance temperature: 200° C.). In the same manner as in Example 3, transfer foils for producing hydraulic transfer films and hydraulic transfer films of Examples 7 to 12 and Comparative Examples 4 to 6 were obtained. The transfer foil thus obtained was evaluated for (1) moldability, and the evaluation results are shown in Table 2. Further, using the obtained hydraulic transfer film, (2) designability evaluation and (3) transfer processability (following property) evaluation were performed, and the evaluation results are shown in Table 2.

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

Examples 13-18 and Comparative Examples 7 and 8
In Examples 7 to 12 and Comparative Examples 4 and 5, the resin forming the extension suppressing resin layer shown in Table 3 was gravure-coated at a coating amount of 3 g/m ² to form an extension suppressing resin layer a having a thickness of 1 μm. For the production of hydraulic transfer films of Examples 13 to 18 and Comparative Examples 7 and 8, respectively, in the same manner as in Examples 7 to 12 and Comparative Examples 4 and 5, except that the extension suppressing resin layer b was not provided. A transfer foil and a hydraulic transfer film were obtained. With respect to the obtained transfer foil, the above-mentioned (1) moldability was evaluated, and the evaluation results are shown in Table 3. Further, using the obtained hydraulic transfer film, (2) designability evaluation and (3) transfer processability (following property) evaluation were performed, and the evaluation results are shown in Table 3.

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

The transfer foil for producing a hydraulic transfer film of the present invention has an uneven shape that is satisfactorily shaped at the time of producing the transfer foil, and a hydraulic transfer film can be easily produced before using the hydraulic transfer film, and thus, The water pressure transfer film thus obtained has a good uneven shape, and can give a resin molded product a design property having excellent glitter and a high-grade feeling. Further, the resin molded product obtained by the manufacturing method of the present invention can be suitably used as a building material, an automobile interior material, a building material, furniture, a housing for electric products, and the like.

10 Transfer Foil for Production of Hydraulic Transfer Film 11 Release Film 12 Glittering Ink Layer 13 Extension Suppression Resin Layer 13a Extension Suppression Resin Layer a
13b Extension suppressing resin layer b
14 Concavo-convex shape 20 Water pressure transfer film 21 Water-soluble film 30 Decorative molded product 31 Transferred material 32 Top coat layer 33 Concavo-convex feeling developing part

Claims (6)

A water-soluble film, an extension suppressing resin layer, and a glitter ink layer are provided in this order, and at least the surface of the extension suppressing resin layer opposite to the glitter ink layer side has a concavo-convex shape, and the extension suppressing resin layer. The hydraulic transfer film in which the resin forming the resin contains a resin A having a glass transition temperature of 80 to 145° C. (excluding a cured product of an ionizing radiation curable resin). The hydraulic transfer film according to claim 1, wherein the resin A is a water-insoluble resin. The hydraulic transfer film according to claim 1, 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 any one of claims 1 to 4, wherein the 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 nitrification cotton and an alkyd resin.