JP6718156B2 - Water pressure transfer film and decorative molded product using the same - Google Patents

Description

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

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 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. In the hydraulic transfer method, a water-soluble or water-swellable water-soluble film is provided with a transfer film having a desired decorative layer printed thereon, and the decorative layer of the transfer film is coated with an activator composition comprising an organic solvent. , Swell and make the decorative layer sticky (this is called activation). Before or after that, the transfer film is floated on the water surface with the decorative layer (printing layer) side for transfer as the upper surface, and then an article to be a transfer target is pressed on the transfer film by water pressure. After the transfer film is brought into close contact with the transfer surface of the transfer target to be decorated, the water-soluble film is removed and the decorative layer is transferred.

Such a hydraulic transfer method is an excellent curved surface decoration method in terms of transfer processability on a three-dimensional surface, "depth" such as clear painting feeling, and designability such as high quality pattern expression. It has been known.

In recent years, an attempt has been made to impart a design showing an excellent three-dimensional effect to a resin molded product by using this hydraulic transfer method. For example, in Patent Document 1, a plurality of protrusions made of raised ink are formed on a printing layer (representing a wood grain pattern, a conduit, etc.) provided on a water-soluble film to give a three-dimensional pattern. Techniques for expressing have been proposed.

However, it is difficult to form a delicate concavo-convex shape by the technique of using the rising ink, because the required ink application amount is large. Therefore, the method disclosed in Patent Document 1 has a problem that it is difficult to express a delicate and highly stereoscopic pattern.

JP, 2007-203655, A

Under such circumstances, the present invention aims to provide a hydraulic transfer film capable of imparting a design showing a high stereoscopic effect to a resin molded product, a method for producing the same, and a decorative molded product using the film. And

The present inventors have conducted extensive studies to solve the above problems. As a result, in the hydraulic transfer film having a water-soluble film, a first protective layer, and a picture layer in this order, the first protective layer forms an uneven shape on the surface of the water-soluble film, Further, it has been found that the first protective layer contains an ionizing radiation-curable resin, so that the resin molded product can be provided with a design exhibiting a high three-dimensional effect. That is, the present invention provides the following hydraulic transfer film, a method for producing the same, and a decorative molded product using the film.

Item 1. A hydraulic transfer film having a water-soluble film, a first protective layer, and a pattern layer in this order,
The first protective layer forms an uneven shape on the surface of the water-soluble film,
A hydraulic transfer film, wherein the first protective layer contains an ionizing radiation curable resin.
Item 2. Item 2. The hydraulic transfer film according to Item 1, wherein the uneven shape is formed by a portion having the first protective layer on a surface of the water-soluble film and a portion not having the first protective layer.
Item 3. Item 3. The hydraulic transfer film according to Item 1 or 2, which has a second protective layer between the first protective layer and the pattern layer.
Item 4. Item 4. The hydraulic transfer film according to Item 3, wherein the second protective layer contains an ionizing radiation curable resin or an acrylic polymer polyol.
Item 5. Item 5. The hydraulic transfer film according to any one of Items 1 to 4, wherein the first protective layer contains a matting agent.
Item 6. Item 6. The hydraulic transfer film according to any one of Items 1 to 5, wherein the second protective layer contains a matting agent.
Item 7. Item 7. The hydraulic transfer film according to any one of Items 1 to 6, wherein the concavo-convex shape of the first protective layer is formed so as to match the pattern formed by the pattern layer.
Item 8. The manufacturing method of the hydraulic transfer film which has the following processes (A) and (B) in order.
Step (A) A step of laminating a first protective layer containing an ionizing radiation curable resin so as to form an uneven shape on the surface of the water-soluble film Step (B) On the first protective layer, Item 9 of stacking the picture layers The manufacturing method of the hydraulic transfer film which has the following processes (A), (A'), and (B) in order.
Step (A) A step of laminating a first protective layer containing an ionizing radiation curable resin so as to form an uneven shape on the surface of the water-soluble film Step (A′) On the first protective layer Step of stacking second protective layer Step (B) Step of stacking a pattern layer on the second protective layer Item 10. A method for producing a decorated molded article, which includes the following steps (a) to (e).
Step (a) Floating the water pressure transfer film according to any one of Items 1 to 7 on the water surface so that the water-soluble film side faces the water surface side Step (b) Activator composition on the picture layer side of the water pressure transfer film Activator applying step of applying an object Step (c) Press the transfer target on the hydraulic transfer film floating on the water surface through the steps (a) and (b), and transfer the pattern layer by hydraulic pressure. Step of adhering to the transferred surface of the body (d) Removal of water-soluble film adhered to the transferred surface of the transferred body Step (e) Irradiation with ionizing radiation from the first protective layer side Curing step of curing the first protective layer

ADVANTAGE OF THE INVENTION According to this invention, the hydraulic transfer film which can give the design which showed the high three-dimensional effect to a resin molded product, its manufacturing method, and the decorative molded product using this film can be provided.

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 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 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. 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.

The hydraulic transfer film of the present invention is a hydraulic transfer film having a water-soluble film, a first protective layer, and a pattern layer in this order, wherein the first protective layer has an uneven shape on the surface of the water-soluble film. And further, the first protective layer contains an ionizing radiation curable resin. Hereinafter, the hydraulic transfer film of the present invention, a method for producing the same, and a decorative molded product using the film will be described in detail.

[Water pressure transfer film]
Hereinafter, the hydraulic transfer film of the present invention will be described with reference to FIGS. 1 to 5 are schematic cross-sectional views showing an example of the structure of the hydraulic transfer film of the present invention. As shown in FIGS. 1 to 3, the hydraulic transfer film 1 of the present invention has a water-soluble film 10, a first protective layer 21, and a pattern layer 30 in order. The first protective layer 21 forms an uneven shape on the surface of the water-soluble film. As shown in FIGS. 1 and 2, for example, the concave-convex shape formed by the first protective layer 21 includes a portion (projection) having the first protective layer 21 on the surface of the water-soluble film 10 and a first protective layer 21. It may be formed by a portion (recess) having no protective layer 21. Further, the uneven shape may be formed by a thick portion (convex portion) and a thin portion (concave portion) of the first protective layer 21, as shown in FIG. 3, for example. Furthermore, the uneven shape of the first protective layer 21 may be formed by both of them.

The first protective layer 21 contains an ionizing radiation curable resin. As described below, the first protective layer 21 of the hydraulic transfer film of the present invention contains an uncured product of an ionizing radiation curable resin, and the first protective layer 21 is transferred after the hydraulic transfer film is transferred to a resin molded product. By irradiating the layer 21 with ionizing radiation, a decorative molded article having the cured first protective layer 21 is obtained.

The pattern layer 30 is formed on the uneven shape formed by the first protective layer 21. More specifically, for example, as shown in FIGS. 1 and 2, the uneven shape has a portion (convex portion) having the first protective layer 21 and a portion (protruding portion) having no first protective layer 21 ( And the concave portion), the pattern layer 30 is formed right above the convex portion formed by the first protective layer 21 and the concave portion where the first protective layer 21 is not formed. .. Further, for example, as shown in FIG. 3, in the case where the uneven shape is formed by a large-thickness portion (convex portion) and a small-thickness portion (concave portion) of the first protective layer 21, The pattern layer 30 is formed on the convex portion and the concave portion of the uneven shape. When the pattern layer 30 does not have a second protective layer, a primer layer, or the like, which will be described later, the pattern layer 30 is formed by printing the resin composition on the first protective layer, as described later, and thus is usually the first layer. The concave portion formed by the protective layer 21 is filled with the pattern layer 30.

The hydraulic transfer film of the present invention has a first protective layer 21 as shown in FIGS. 4 and 5 for the purpose of enhancing the scratch resistance of the decorative molded product, enhancing the design feeling due to the difference in gloss, and the like. And the pattern layer 30, the second protective layer 22 may be provided as necessary. When the second protective layer 22 is provided, the recess formed by the first protective layer 21 is normally filled with the second protective layer 22, so that the scratch resistance of the decorative molded product can be further enhanced. Yes (see, eg, Figure 7). Further, as will be described later, it is possible to enhance the design feeling by the gloss difference between the first protective layer 21 and the second protective layer 22.

Hereinafter, each layer constituting the hydraulic transfer film of the present invention will be described in detail.

(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 copolymers with maleic acid, vinyl acetate and itaconic acid, polyvinylpyrrolidone, acetyl cellulose, acetyl butyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, and various water-soluble polymers such as sodium alginate. 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 an equilibrium 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.

<First protective layer>
The first protective layer is a layer that forms an uneven shape on the surface of the water-soluble film and imparts a design showing a high three-dimensional effect to the decorative molded product together with a later-described pattern layer. Further, the first protective layer also functions as a surface protective layer that enhances the scratch resistance of the decorative molded product.

As described above, the concavo-convex shape due to the first protective layer is, for example, as shown in FIGS. 1 and 2, on the surface of the water-soluble film, a portion (convex portion) having the first protective layer, Of the first protective layer 21 having a large thickness (a convex portion) and a portion having a small thickness of the first protective layer 21, as shown in FIG. 3, for example. (Recessed portion). Further, the uneven shape may be formed by both of them. Moreover, the said uneven|corrugated shape should just be formed in at least one part of the surface of a water-soluble film (a part which wants to give a design which expresses a high three-dimensional effect to a decorative molded product). In particular, in the case where the first protective layer contains a matting agent described later, the difference in gloss between the concave and convex portions due to the concave-convex shape can be further increased, and a three-dimensional effect can be enhanced, and further, Since it becomes easy to visually recognize the concave portion and the convex portion expressed by the protective layer, it becomes easy to register when forming the pattern layer by printing, and the uneven shape of the first protective layer and the pattern of the pattern layer are synchronized. From the viewpoint of ease of production, the uneven shape formed by the first protective layer has a portion (projection) having the first protective layer and a portion not having the first protective layer on the surface of the water-soluble film. (Recessed portion).

The uneven shape of the first protective layer is preferably formed in a pattern. Furthermore, a higher three-dimensional effect can be expressed by synchronizing the uneven shape with the pattern of the pattern layer 30 described later. For example, as shown in FIGS. 1 and 3, the concave and convex portions of the first protective layer 21 are aligned with the dark color portion 31 of the pattern layer 30 (for example, a conduit portion if the pattern is a wood pattern), On the contrary, as shown in FIG. 2, a high stereoscopic effect can be obtained by synchronizing the convex and concave portions with the dark color portion 31 of the pattern layer 30. Which of the concave portion and the convex portion should be synchronized with the dark portion of the pattern layer depends on the kind of the ionizing radiation curable resin used for the first protective layer, the presence or absence of a matting agent described later and the content thereof, and the It can be selected according to the presence or absence of the formation of the protective layer 2 and the presence or absence of the matting agent, the content thereof, and the desired design.

The first protective layer contains an ionizing radiation curable resin. The ionizing radiation curable resin is an uncured product, at least a part of which is not cured. Since the first protective layer contains an uncured material of an ionizing radiation-curable resin, the hydraulic transfer film is transferred to a resin molded article, and then the first protective layer is irradiated with ionizing radiation to form the first protective layer. A decorative molded product in which is cured is obtained. Since the uncured product of the ionizing radiation curable resin has high flexibility, the hydraulic transfer film can be appropriately followed even in the complicated shape of the resin molded product when transferring the hydraulic transfer film of the present invention to the resin molded product. be able to. On the other hand, a cured product of an ionizing radiation curable resin formed after being transferred to a resin molded product is excellent in scratch resistance and the like. Therefore, in the hydraulic transfer film of the present invention, in the decorative molded article using the conventional hydraulic transfer film, even if the top coat layer that had to be formed after transfer of the hydraulic transfer film was not formed, The protective layer 1 can impart excellent surface properties such as scratch resistance to the decorative molded product. Hereinafter, the ionizing radiation curable resin contained in the first protective layer will be described in detail.

(Ionizing radiation curable resin)
The ionizing radiation curable resin is a resin that is crosslinked and cured by irradiation with ionizing radiation. Here, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are used. It also includes electromagnetic waves such as rays and γ rays, and charged particle rays such as α rays and ion rays. Among the ionizing radiation curable resins, the electron beam curable resin can be solvent-free, does not require a photopolymerization initiator, and can obtain stable curing characteristics. Therefore, in forming the first protective layer, It is preferably used.

The ionizing radiation curable resin forming the first protective layer of the present invention is not particularly limited, but preferably a polyfunctional polycarbonate (meth)acrylate is used. In addition, in this specification, (meth)acrylate shall mean an acrylate or a methacrylate, and other similar expressions are also the same.

[Polyfunctional polycarbonate (meth)acrylate]
In the first protective layer of the present invention, the polyfunctional polycarbonate (meth)acrylate contained in the ionizing radiation-curable resin composition has a carbonate bond in the polymer main chain and has a (meth)acrylate in the terminal or side chain. There is no particular limitation as long as it has two or more. In addition, the number of functional groups per molecule of the (meth)acrylate is preferably 2 to 6 from the viewpoint of good crosslinking and curing. The polyfunctional polycarbonate (meth)acrylate may be used alone or in combination of two or more.

The polyfunctional polycarbonate (meth)acrylate is obtained, for example, by converting a part or all of the hydroxyl groups of the polycarbonate polyol into (meth)acrylate (acrylic acid ester or methacrylic acid ester). This esterification reaction can be performed by a usual esterification reaction. For example, 1) a method of condensing a polycarbonate polyol and an acrylic acid halide or a methacrylic acid halide in the presence of a base, 2) a method of condensing a polycarbonate polyol and an acrylic acid anhydride or a methacrylic acid anhydride in the presence of a catalyst, Alternatively, 3) a method of condensing a polycarbonate polyol and acrylic acid or methacrylic acid in the presence of an acid catalyst can be used.

The polycarbonate polyol is a polymer having a carbonate bond in the polymer main chain and having 2 or more, preferably 2 to 50, and more preferably 3 to 50 hydroxyl groups at the terminal or side chain. As a typical production method of the polycarbonate polyol, a method by a polycondensation reaction of a diol compound (A), a polyhydric alcohol having 3 or more valences (B), and a compound (C) serving as a carbonyl component can be mentioned.

Diol compound used as a raw material of the polycarbonate polyol (A) is represented by the general formula HO-R ¹ -OH. Here, R ¹ is a divalent hydrocarbon group having 2 to 20 carbon atoms and may contain an ether bond in the group. R ¹ is, for example, a linear or branched alkylene group, a cyclohexylene group, or a phenylene group.

Specific examples of the diol compound include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, 1 ,5-Pentanediol, 3-methyl-1,5pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis(2-hydroxyethoxy)benzene, 1,4-bis(2 -Hydroxyethoxy)benzene, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. These diols may be used alone or in combination of two or more.

Examples of trihydric or higher polyhydric alcohols (B) used as raw materials for polycarbonate polyols include alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin and sorbitol. Are listed. Further, the trihydric or higher polyhydric alcohol may be an alcohol having a hydroxyl group obtained by adding 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxide to the hydroxyl group of the polyhydric alcohol. Good. These polyhydric alcohols may be used alone or in combination of two or more.

The compound (C), which serves as a carbonyl component used as a raw material of the polycarbonate polyol, is any compound selected from carbonic acid diester, phosgene, and equivalents thereof. Specific examples of the compound include carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate and propylene carbonate; phosgene; halogenated formic acid such as methyl chloroformate, ethyl chloroformate and phenyl chloroformate. Examples thereof include esters. These compounds may be used alone or in combination of two or more.

The polycarbonate polyol is synthesized by subjecting the diol compound (A), the polyhydric alcohol having a valence of 3 or more (B), and the compound (C) serving as a carbonyl component to polycondensation reaction under general conditions. The charging molar ratio of the diol compound (A) and the polyhydric alcohol (B) may be set in the range of 50:50 to 99:1, for example. Further, the molar ratio of the compound (C) serving as a carbonyl component to the diol compound (A) and the polyhydric alcohol (B) is, for example, 0.2 to 2 with respect to the hydroxyl group of the diol compound and the polyhydric alcohol. It may be set within the equivalent range.

The number of equivalents of hydroxyl groups (eq./mol) present in the polycarbonate polyol after the polycondensation reaction at the above-mentioned charging ratio is, for example, 3 or more on average in one molecule, preferably 3 to 50, and further preferably 3 to 20 can be mentioned. When such an equivalent number is satisfied, a necessary amount of (meth)acrylate group is formed by the esterification reaction described later, and the polyfunctional polycarbonate (meth)acrylate resin is provided with appropriate flexibility. The terminal functional group of this polycarbonate polyol is usually an OH group, but a part thereof may be a carbonate group.

The method for producing the polycarbonate polyol described above is described, for example, in JP-A-64-1726. Further, this polycarbonate polyol can also be produced by a transesterification reaction between a polycarbonate diol and a trihydric or higher polyhydric alcohol, as described in JP-A-3-181517.

The molecular weight of the polyfunctional polycarbonate (meth)acrylate is not particularly limited, but examples thereof include a weight average molecular weight of 5,000 or more, preferably 10,000 or more. The upper limit of the weight average molecular weight of the polyfunctional polycarbonate (meth)acrylate is not particularly limited, but from the viewpoint of controlling so that the viscosity does not become too high, for example, 100,000 or less, preferably 50,000 or less. The weight average molecular weight of the polyfunctional polycarbonate (meth)acrylate is preferably 10,000 to 50,000, and more preferably 10,000 to 20,000.

In addition, the weight average molecular weight of the polyfunctional polycarbonate (meth)acrylate in this specification is the value measured by the gel permeation chromatography method using polystyrene as a standard substance.

The content of the polyfunctional polycarbonate (meth)acrylate in the ionizing radiation-curable resin composition used for forming the first protective layer is not particularly limited as long as the effects of the present invention are exhibited, but the decoration is not limited. From the viewpoint of imparting a delicate and highly three-dimensional design to the molded product, it is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 85% by mass or more.

The ionizing radiation curable resin composition used for forming the first protective layer further contains a polyfunctional urethane (meth)acrylate as an ionizing radiation curable resin in addition to the above-mentioned polyfunctional polycarbonate (meth)acrylate. You can leave. The polyfunctional urethane (meth)acrylate is not particularly limited as long as it has a urethane bond in the polymer main chain and has two or more (meth)acrylates at the terminal or side chain. Such a polyfunctional urethane (meth)acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or polyester polyol with a polyisocyanate with (meth)acrylic acid. The polyfunctional urethane (meth)acrylate preferably has 2 to 12 functional groups per molecule from the viewpoint of improving cross-linking and curing. The polyfunctional urethane (meth)acrylate may be used alone or in combination of two or more.

The molecular weight of the polyfunctional urethane (meth)acrylate is not particularly limited, but examples thereof include a weight average molecular weight of 2,000 or more, preferably 5,000 or more. The upper limit of the weight average molecular weight of the polyfunctional urethane (meth)acrylate is not particularly limited, but from the viewpoint of controlling so that the viscosity does not become too high, for example, 30,000 or less, preferably 10,000 or less.

The weight average molecular weight of the polyfunctional urethane (meth)acrylate in the present specification is a value measured by gel permeation chromatography using polystyrene as a standard substance.

The content of the polyfunctional urethane (meth)acrylate in the ionizing radiation curable resin composition used for forming the first protective layer is not particularly limited as long as the effects of the present invention are exhibited, but is high. From the viewpoint of expressing a three-dimensional effect, it is preferably 50% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.

When the polyfunctional polycarbonate (meth)acrylate and the polyfunctional urethane (meth)acrylate are used in combination in the ionizing radiation-curable resin composition used for forming the first protective layer, their mass ratio (polyfunctional polycarbonate ( The (meth)acrylate: polyfunctional urethane (meth)acrylate) is preferably about 50:50 to 99:1, more preferably about 80:20 to 99:1, and further preferably about 85:15 to 99:1. Can be mentioned.

In addition to the polyfunctional polycarbonate (meth)acrylate and the polyfunctional urethane (meth)acrylate, the ionizing radiation curable resin composition forming the first protective layer further contains another ionizing radiation curable resin as described below. May be included. Other ionizing radiation curable resin, by irradiation with the above-mentioned ionizing radiation, cross-linking, is a resin that is cured, specifically, having a polymerizable unsaturated bond or an epoxy group in the molecule, a prepolymer, An appropriate mixture of at least one of an oligomer and a monomer may be used.

As the above-mentioned monomer used as another ionizing radiation curable resin, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth)acrylate monomer is particularly preferable. The polyfunctional (meth)acrylate monomer may be a (meth)acrylate monomer having two or more (two or more) polymerizable unsaturated bonds in the molecule, preferably three or more (three or more functional). As the polyfunctional (meth)acrylate, specifically, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di( (Meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di( (Meth)acrylate, ethylene oxide modified di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate , Dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl) isocyanurate , Propionic acid modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate and the like. These monomers may be used alone or in combination of two or more.

Further, as the above-mentioned oligomer used as another ionizing radiation curable resin, a (meth)acrylate oligomer having a radically polymerizable unsaturated group in the molecule is suitable, and among them, a polymerizable unsaturated bond in the molecule is A polyfunctional (meth)acrylate oligomer having at least one (bifunctional or more) is preferable. Examples of the polyfunctional (meth)acrylate oligomer include acrylic silicone (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polybutadiene (meth)acrylate, silicone (meth)acrylate. And oligomers having a cationically polymerizable functional group in the molecule (for example, novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.). Here, the acrylic silicone (meth)acrylate can be obtained by radically copolymerizing a silicone macromonomer with a (meth)acrylate monomer. Epoxy (meth)acrylate can be obtained by, for example, reacting (meth)acrylic acid with the oxirane ring of a bisphenol type epoxy resin or novolac type epoxy resin having a relatively low molecular weight to esterify. A carboxyl-modified epoxy (meth)acrylate obtained by partially modifying this epoxy (meth)acrylate with a dibasic carboxylic acid anhydride can also be used. Polyester (meth)acrylate is obtained by, for example, esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of polyvalent carboxylic acid and polyhydric alcohol with (meth)acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of the oligomer obtained by adding alkylene oxide with (meth)acrylic acid. The polyether (meth)acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth)acrylic acid. Polybutadiene (meth)acrylate can be obtained by adding (meth)acrylic acid to the side chain of a polybutadiene oligomer. Silicone (meth)acrylate can be obtained by adding (meth)acrylic acid to the terminal or side chain of silicone having a polysiloxane bond in the main chain. These oligomers may be used alone or in combination of two or more.

These other ionizing radiation curable resins may be used alone or in combination of two or more. Among these other ionizing radiation curable resins, acrylic silicone (meth)acrylate and the like are preferable from the viewpoint of further enhancing scratch resistance and the like.

Further, the first protective layer may contain a matting agent, if necessary, for the purpose of reducing the gloss of the first protective layer. When the first protective layer contains a matting agent, the pattern layer is formed by printing, and by synchronizing with the uneven shape of the first protective layer, an excellent design feeling due to having a high three-dimensional effect according to the pattern In addition to being obtained, the first protective layer becomes opaque or semi-transparent and can be visually recognized, which facilitates registration of printing, which is convenient in manufacturing.

(Matting agent)
Specific examples of the matting agent include inorganic fillers selected from silica, clay, heavy calcium carbonate, light calcium carbonate, precipitated barium sulfate, calcium silicate, synthetic silicate, and fine silica powder, and acrylic. Examples thereof include organic fillers or resin beads selected from resins, urethane resins, nylon resins, polypropylene resins, or urea resins. Any one of them may be used, or two or more thereof may be used in combination. .. Among these matting agents, resin beads are preferably used from the viewpoint of obtaining a decorative molded article having a delicate tactile feel in addition to a visual design feeling, and urethane beads made of a urethane resin are particularly preferably used. ..

The volume average particle diameter of the matting agent is preferably 0.5 to 25 μm, more preferably 1 to 15 μm, and further preferably 3 to 10 μm. If the volume average particle diameter of the matting agent is 25 μm or less, the interfacial area increases and stress during processing diffuses, so that voids generated at the interface absorb energy and the interparticle distance decreases. As a result, plastic deformation occurs between particles or voids, and whitening during stretching can be suppressed. Further, the volume average particle diameter of the matting agent is preferably 0.5 μm or more from the viewpoint of the matting effect. The volume average particle size mentioned here is a particle size at an integrated value of 50% in the particle size distribution obtained by the laser diffraction-scattering method.

The content of the matting agent in the first protective layer is preferably 0.5 to 50% by mass, from the viewpoint of the balance between the three-dimensional effect expressed in the decorative molded product and the moldability, and is 10 to 10. It is more preferably 50% by mass and even more preferably 25 to 50% by mass.

The oil absorption measured according to JIS K 5101-13-1:2004 of the matting agent is preferably 150 to 400 mL/100 g, more preferably 180 to 350 mL/100 g, and more preferably 230 to 300 mL/100 g. It is more preferable that there is. It is preferable to use a matting agent having an oil absorption amount of 150 mL/100 g or more from the viewpoint of the matting effect, and it is preferable to use a matting agent having an oil absorption amount of 400 mL/100 g or less while maintaining an appropriate thixotropic property. It is preferable from the viewpoint of not impairing the coating suitability when forming the protective layer.

By surface-treating the matting agent, the adhesion between the ionizing radiation curable resin and the matting agent can be improved, and a strong coating film can be formed when cured. Such surface treatment is preferable because it can suppress cracks and whitening during molding. The treatment method is not particularly limited as long as it exhibits the above effects, and may be surface treatment with an organic material or surface treatment with an inorganic material. Particularly, silane coupling treatment and the like are preferable.

In the first protective layer, in addition to the above-mentioned polyfunctional polycarbonate (meth)acrylate, polyfunctional urethane (meth)acrylate, and a matting agent, various additives are added according to desired physical properties to be provided in the first protective layer. Agents can be added. Examples of the additives include weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, Examples include thixotropic agents, coupling agents, plasticizers, defoamers, fillers, solvents, colorants, and the like. These additives can be appropriately selected and used from commonly used additives. Further, as the ultraviolet absorber or the light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth)acryloyl group in the molecule can be used.

The thickness of the first protective layer is not particularly limited, but is, for example, about 0.1 to 20 μm, preferably about 0.5 to 10 μm, and more preferably about 1 to 5 μm. When the thickness in such a range is satisfied, high designability based on the uneven shape can be exhibited, and further, sufficient physical properties as a surface protective layer such as scratch resistance can be obtained. Further, since the ionizing radiation-curable resin composition forming the first protective layer can be uniformly irradiated with ionizing radiation, it can be uniformly cured, which is economically advantageous. .. Note that the thickness of the first protective layer means the thickness of the convex portion of the first protective layer having an uneven shape.

The formation of the first protective layer is carried out, for example, by preparing the above ionizing radiation-curable resin composition and applying it so that unevenness is formed on the surface of the water-soluble film. The ionizing radiation curable resin composition may have any viscosity as long as it can form an uncured resin layer on the surface of the water-soluble film by a coating method described later. In the present invention, the prepared coating solution is applied to a layer adjacent to the first protective layer so as to have the above-mentioned thickness, by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating and the like. Method, preferably by gravure coating to form an uncured resin layer. As will be described later, after the hydraulic transfer film of the present invention is transferred to a resin molded product, the first protective layer is irradiated with ionizing radiation to obtain a decorative molded product in which the first protective layer is cured. To be

<Second protective layer>
The second protective layer is a layer that is provided between the first protective layer and the picture layer, if necessary. In the case of having the second protective layer, the recess formed by the first protective layer is normally filled with the second protective layer, so that the scratch resistance of the decorative molded product can be further enhanced (for example, , See FIG. 7). Further, the design feeling can be enhanced by the gloss difference between the first protective layer and the second protective layer. Specifically, the first protective layer and the second protective layer are blended with the above-mentioned matting agent, and a delicate and high three-dimensional effect is expressed by providing a gloss difference depending on the difference in the blending amount of the matting agent. can do. For example, when the first protective layer has a relatively high gloss and the second protective layer has a relatively low gloss, the content ratio of the matting agent in the second protective layer is equal to that in the first protective layer. It may be about 1.5 to 5.0 times the content of the matting agent.

It is preferable that the second protective layer is formed on the entire surface of the portion where the uneven shape is formed by the first protective layer (the portion where the decorative molded article is to be given a design that gives a three-dimensional effect). May be partially formed, for example, on the concave portion of the first protective layer.

The second protective layer preferably contains an ionizing radiation curable resin or an acrylic polymer polyol. As the ionizing radiation curable resin, the same resin as the first protective layer can be exemplified. When the second protective layer contains an ionizing radiation-curable resin, it is possible to further enhance the scratch resistance of the decorative molded product. The ionizing radiation curable resin of the second protective layer is formed by transferring the hydraulic transfer film of the present invention to a resin molded article and then irradiating it with ionizing radiation from the first protective layer side. The ionizing radiation curable resin can also be cured together with the first protective layer.

When the second protective layer contains an acrylic polymer polyol, the second protective layer is formed of a resin composition containing the acrylic polymer polyol or a cured product thereof. Although the cured product may be a completely cured product, it is preferably in a semi-cured state in consideration of transfer processability and the like. A preferred embodiment is a mixture of a resin composition containing an acrylic polymer polyol and a cured product of the resin composition. When it is desired to increase the gloss of the second protective layer, it is preferable that the second protective layer contains an acrylic polymer polyol.

In addition to the acrylic polymer polyol, the resin composition forming the second protective layer may further contain a urethane resin or an isocyanate. Isocyanate is a curing agent for acrylic polymer polyol, and by containing isocyanate, at least a part of the resin composition is brought into a cured state or a semi-cured state. As a result, it is possible to suppress excessive stretching that is likely to occur due to the hydraulic transfer film being dissolved or swollen in the step of floating the hydraulic transfer film on the water surface during the production of the decorative molded product.

(Acrylic polymer polyol)
The acrylic polymer polyol preferably has a weight average molecular weight, calculated by standard polystyrene, of 1,000 to 100,000, determined by gel permeation chromatography (GPC) method, and preferably 5,000 to 80,000. Is more preferable, and it is particularly preferable that it is 20,000 to 50,000. When the molecular weight of the acrylic polymer polyol is 1,000 or more, solvent resistance is improved, and problems such as dissolution of the second protective layer when forming the pattern layer are less likely to occur, and 100,000 or less. When it is made into an ink, the workability is improved because the viscosity is lowered and gelation is less likely to occur.

As the acrylic polymer polyol, those having a hydroxyl value of 30 to 130 mgKOH/g are preferred, those of 50 to 130 mgKOH/g are more preferred, and those of 60 to 120 mgKOH/g are even more preferred. When the hydroxyl value of the acrylic polymer polyol is 30 mgKOH/g or more, it is preferable in that excessive spreading of the entire hydraulic transfer film can be suppressed, and when it is 130 mgKOH/g or less, flexibility of the second protective layer is obtained. Is good, and defects such as cracks do not occur. The hydroxyl value can be measured by an acetylation method using acetic anhydride.

(Isocyanate)
The isocyanate may be a polyvalent isocyanate having two or more isocyanate groups in the molecule, and examples thereof include 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate and 4,4′-. An aromatic isocyanate such as diphenylmethane diisocyanate, or an aliphatic isocyanate such as 1,6-hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate (or A polyisocyanate such as an alicyclic) isocyanate is used.

Further, if necessary, a blocked isocyanate in which the isocyanate group is protected by a suitable blocking agent to be inactivated and the isocyanate group is regenerated by heating may be used. As the blocking agent, for example, known blocking agents such as phenol, alcohol, active methylene such as dimethyl malonate, ethyl acetoacetate, and oxime may be used.

By using a blocked isocyanate, higher moldability can be imparted to the second protective layer, and after molding into a desired shape, the molded product is heat-treated to regenerate the isocyanate group, react with the polyol, and cure. Good adhesiveness with the first protective layer and the pattern layer can be exhibited.

The resin composition constituting the second protective layer includes urethane resin, (meth)acrylic resin, (meth)acrylic/urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, It is preferable to contain chlorinated polypropylene, chlorinated polyethylene and the like. This is because the second protective layer can be made flexible and the transfer processability at the time of manufacturing the decorative molded product can be improved. In addition, "(meth)acryl" means acryl or methacryl here. Of these, urethane resins are particularly preferred because they have high compatibility with acrylic polymer polyols. Further, a colorant may be added to the second protective layer within a range that does not impair the effects of the present invention. As the colorant, the same ones as those used in the later-described pattern layer can be used.

(Urethane resin)
As the urethane resin, a non-crosslinked type, that is, a thermoplastic resin having a linear molecular structure rather than a three-dimensionally crosslinked network having a three-dimensional molecular structure is selected. It is preferable. As such a non-crosslinking type urethane resin, as a polyol component, a polyol such as polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, polyethylene glycol or polypropylene glycol is used as a main component and is reacted with isocyanate to form a non-crosslinking type. A type urethane resin can be used, and from the viewpoints of moldability, heat resistance, weather resistance, adhesion to the first protective layer, and the like, those synthesized by combining polyester polyol and isocyanate such as hexamethylene diisocyanate are particularly preferable. preferable. Usually, the number of hydroxyl groups in one molecule of polyol and the number of isocyanate groups in one molecule of isocyanate are each 2 on average.

Further, as the urethane resin, a urethane urea resin synthesized from a combination of a polyol component, a polyamine component and an isocyanate is preferably used, and as the polyol component and the isocyanate, those described above can be used.

The urethane resin preferably has a glass transition point of 100° C. or lower, more preferably 20 to 100° C. When the glass transition point of the urethane resin is 100° C. or lower, the flexibility of the second protective layer at room temperature is excellent, and when it is 20° C. or higher, the cohesive force is significantly reduced by heating, or the second protective layer is It is preferable because it does not dissolve in water during hydraulic transfer.

The ratio of the acrylic polymer polyol in the resin composition constituting the second protective layer or the total amount of the isocyanate added as necessary to the acrylic polymer polyol to the urethane resin is usually 99:1 to 50:50 by mass. It is preferably 95:5 to 50:50, more preferably 90:10 to 60:40, and particularly preferably 80:20 to 68:32. When the ratio of the urethane resin is high, the transfer processability is improved, but when the ratio is too high, the designability may be deteriorated. In particular, when the content of isocyanate is high, it is preferable to increase the proportion of urethane resin from the viewpoint of transfer processability.

The second protective layer is formed by applying a coating solution prepared by dissolving the above-mentioned acrylic polymer polyol, isocyanate, urethane resin, and other resin in a solvent by a known method, drying it if necessary, and curing it. can do. The thickness of the second protective layer is usually about 0.5 to 20 μm, preferably 1 to 5 μm.

The second protective layer may include a matting agent. As the matting agent, the same ones as those exemplified for the first protective layer can be exemplified. When the second protective layer contains a matting agent, it is possible to enhance the design feeling by the difference in gloss between the first protective layer and the second protective layer. For example, by blending the above-mentioned matting agent in the first protective layer and the second protective layer, and providing a gloss difference depending on the difference in the blending amount of the matting agent, a delicate and high three-dimensional effect can be expressed. it can. Specifically, the concentration of the matting agent in the second protective layer is made higher than the concentration of the matting agent contained in the first protective layer, so that the second protective layer is more than the first protective layer. Have a relatively low gloss. As a result, the difference between the concave portion of the first protective layer (the visibility of the second protective layer is high and the gloss is lower than that of the convex portion) and the convex portion of the first protective layer is emphasized, and the delicate and high three-dimensional shape is achieved. The feeling can be expressed effectively. The gloss difference between the first protective layer and the second protective layer can be adjusted by the presence or absence of a matting agent and the concentration. Either the first protective layer or the second protective layer may be adjusted to have relatively low gloss.

In addition, when the second protective layer contains a matting agent, from the viewpoint of obtaining a decorative molded article having a delicate touch corresponding to the uneven shape of the first protective layer, in addition to the visual design, It is preferable that the type and particle diameter of the matting agent contained in the protective layer are different from those of the matting agent contained in the first protective layer. For example, when resin beads such as urethane beads are used as the matting agent in the first protective layer, it is preferable to use an inorganic filler such as silica as the matting agent contained in the second protective layer.

<Pattern layer>
The pattern layer is a layer that imparts decorative properties to the decorative molded product, and is formed by printing various patterns using ink and a printing machine. The pattern formed by the pattern layer is not particularly limited, and for example, a wood pattern, a marble pattern (for example, a travertine marble pattern), a stone pattern simulating the surface of rock, or a cloth pattern simulating a cloth or cloth-like pattern. , Tile pasting patterns, brickwork patterns, etc., and also composite patterns of these, such as patchwork patterns. These patterns are formed by multicolor printing using ordinary process colors of yellow, red, blue, and black, and also by multicolor printing using special colors prepared by preparing individual color plates that make up the pattern. It is formed.

The pattern layer usually contains a binder resin and a colorant. Examples of the binder resin for the pattern layer include thermoplastic resins, and specific examples thereof include polyester resins such as acrylic resins and alkyds, unsaturated polyester resins, urethane resins (for example, polyester urethane-based resins), polycarbonate resins, vinyl chloride- Examples thereof include vinyl acetate copolymer, polyvinyl acetal (butyral resin) such as polyvinyl butyral, and nitrocellulose resin such as nitrified cotton. The binder resin may be used alone or in combination of two or more.

Examples of colorants include carbon black (black ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, cobalt blue, and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine. Organic pigments or dyes such as blue, metallic pigments composed of flaky foil pieces such as aluminum and brass, titanium dioxide-coated mica, and pearlescent pigments composed of flaky foil pieces such as basic lead carbonate are used.

In the present invention, a design having a higher three-dimensional effect can be expressed by synchronizing the pattern formed by the uneven shape of the first protective layer and the pattern of the pattern layer. Specifically, the pattern layer is formed in a pattern having a dark color portion having a relatively low lightness, and the concave portion or the convex portion of the first protective layer and the dark color portion of the pattern layer (portion 31 in FIGS. 1 to 5). For example, in the case of a wood grain pattern, a high stereoscopic effect can be expressed by synchronizing with the conduit portion). For example, in the water pressure transfer film shown in FIG. 1 or FIG. 3, the concave portions formed by the uneven shape of the first protective layer containing the matting agent and the dark color portion of the pattern layer are synchronized with each other, or vice versa. In the water pressure transfer film shown in Fig. 3, when the convex portion formed by the concave-convex shape of the first protective layer containing the matting agent and the dark color portion of the pattern layer are synchronized, a design having a high three-dimensional effect is exhibited. You can Further, for example, as shown in FIG. 4 or FIG. 5, a second protective layer is provided, and the concentration of the matting agent in the second protective layer is made higher than that in the first protective layer to make the first protective layer. When the concave portion formed by the uneven shape of the layer (the portion that is less glossy than the convex portion due to the influence of the second protective layer) and the dark portion of the pattern layer are synchronized, the three-dimensional effect is higher and the delicate design is achieved. Can be expressed.

When the pattern layer is formed in a pattern having a dark color portion having a relatively low lightness, the color of the dark color portion is not particularly limited as long as it is a color having a lightness degree relatively lower than that of the other portion, but may be black. Particularly preferred.

[Method for manufacturing hydraulic transfer film]
The hydraulic transfer film 1 of the present invention having the water-soluble film 10, the first protective layer 21, and the pattern layer 30 as shown in FIGS. 1 to 3 has, for example, unevenness on the surface of the water-soluble film. A step (A) of laminating the first protective layer 21 containing an ionizing radiation curable resin so as to form a shape (pattern), and laminating the pattern layer 30 on the first protective layer 21. It can be manufactured by a manufacturing method including the step (B). Further, as shown in FIGS. 4 and 5, the hydraulic transfer film 1 of the present invention having the water-soluble film 10, the first protective layer 21, the second protective layer 22, and the pattern layer 30, For example, a step (A) of laminating a first protective layer containing an ionizing radiation curable resin so as to form an uneven shape on the surface of a water-soluble film, and a second step on the first protective layer. It can be manufactured by a manufacturing method including a step (A′) of laminating the protective layer and a step (B) of laminating the pattern layer 30 on the second protective layer 22.

As the method of forming the first protective layer containing the ionizing radiation-curable resin in the step (A) so as to form the uneven shape on the surface of the water-soluble film, for example, a known method such as gravure printing. Are listed. The uneven shape formed by the first protective layer can be made into a delicate uneven shape by controlling the thickness of the first protective layer formed by printing.

In the step (A′) provided when forming the second protective layer, the second protective layer is formed by a known coating method or printing method, or a resin film is laminated on the first protective layer. Can be formed. Examples of the coating method include gravure coating and reverse coating, and examples of the printing method include gravure printing. The second protective layer is preferably solid-printed on the entire surface.

The method of forming the pattern layer 30 in the step (B) is the same as the coating method and the printing method in the step (A′). The pattern layer 30 may be solid printing on the entire surface.

[Manufacturing method of decorative molded product]
By using the water pressure transfer film of the present invention, a decorative molded article can be manufactured by the following steps (a) to (e). The decorative molded product 2 manufactured using the hydraulic transfer film 1 shown in FIG. 1 corresponds to FIG. 6, and the decorative transfer product 1 having the second protective layer 22 shown in FIG. The decorative molded product 2 manufactured by using this corresponds to FIG. 7.

Step (a) Floating the water pressure transfer film on the water surface so that the water-soluble film side faces the water surface step (b) Activator application step of applying an activator composition to the pattern layer side of the water pressure transfer film ( c) The transfer target 40 is pressed onto the hydraulic transfer film floating on the water surface through the steps (a) and (b), and the pattern layer is brought into close contact with the transfer target surface of the transfer target 40 by hydraulic pressure. Step (d) Film removal step for removing the water-soluble film adhered to the transferred surface of the transferred body 40 Step (e) Irradiating ionizing radiation from the side of the first protective layer to perform the first protection Curing process to cure the layer

Further, the following step (f) may be provided after the above step (e).
Step (f): a step of forming a top coat layer on the transfer surface of the transfer body 40.

<Step (a)>
Step (a) can be performed before or after step (b). The water pressure transfer film 1 is floated on the water surface so that the water-soluble film 10 side faces the water surface side. In order to float the water pressure transfer film 1 on the water surface, it is possible to float the sheet-by-sheet prints one by one, or let the water flow in one direction, and continuously form the continuous belt-shaped water pressure transfer film 1 on the water surface. It may be supplied and suspended.

<Step (b)>
The step (b) can be performed before or after the step (a), and is a step of applying the activator composition to the pattern layer side of the hydraulic transfer film. By applying the activator composition in this step, at least a part of the pattern layer is dissolved or swelled to be softened (activated), and it becomes easy to adhere to the transferred material.

(Activator composition)
The activator composition applied to the pattern layer is not particularly limited as long as it is a composition having a function of activating the pattern layer and transferring it to the transfer surface of the transfer target, and the transfer surface of the transfer target is not limited. It is preferable to have a property of not evaporating until each layer is transferred to. 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 resins. It is about 20% by mass.

The activator composition may be applied by a gravure printing method, 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 It is 20 g/m ² .

<Step (c)>
In the step (c), the transferred body is pressed onto the hydraulic transfer film floating on the water surface after the steps (a) and (b), and the pattern layer is brought into close contact with the transferred surface of the transferred body by water pressure. It is the process of making. The water for applying the water pressure to the water pressure transfer film is preferably adjusted to an appropriate water temperature according to the type of the water-soluble film of the water pressure transfer film, preferably about 25 to 50° C., and more preferably 25. ~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.

(Transfer material)
As the transferred material, for example, polystyrene resin, acrylonitrile-butadiene-styrene copolymer (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 a three-dimensional shape such as an uneven shape or a curved shape. Of these, resin structures are often used. This resin structure may have dust and oil on it as well as release agent during molding. In order to transfer each layer of the hydraulic transfer film with good adhesiveness, transfer with a degreasing liquid in advance. It is preferable to clean the surface.

In step (c), the activator composition applied to the pattern layer is brought into contact with the transferred material to dissolve the surface of the transferred material, thereby further improving the adhesion between the hydraulic transfer film of the present invention and the transferred material. It can be good.

<Film removal step (d)>
The film removing step (d) is a step performed after the step (c) to remove the water-soluble film adhered to the transfer surface of the transfer target. The water-soluble film 10 adhering to the transfer surface of the transfer target can be removed by, for example, shower washing with water. The shower cleaning conditions vary depending on the material forming the water-soluble film 10 and the like, but normally a water temperature of about 15 to 60° C. and a cleaning time of about 10 seconds to 5 minutes are preferable. Then, after the step (d), the transferred material is sufficiently dried to evaporate the water content.

<Curing step (e)>
The curing step (e) is a step performed after the step (d) and irradiating with ionizing radiation from the first protective layer side to cure the first protective layer. When the second protective layer contains an ionizing radiation curable resin, the second protective layer can also be cured by irradiation with ionizing radiation from the first protective layer side in the curing step (e).

As described above, the first protective layer containing the ionizing radiation curable resin is formed of the uncured resin layer formed of the ionizing radiation curable resin composition. Therefore, the first protective layer formed on the hydraulic transfer film has high flexibility and excellent moldability, and is excellent in the decorative molded product when it is cured in the curing step (e). The three-dimensional effect can be maintained.

When an electron beam is used as the ionizing radiation, the accelerating voltage can be appropriately selected according to the resin used and the thickness of the layer, but the accelerating voltage is usually about 70 to 300 kV.

Note that in electron beam irradiation, the higher the accelerating voltage, the higher the transmissivity. Therefore, when using a resin that is easily deteriorated by electron beam irradiation under the first protective layer, the penetration depth of the electron beam and the The accelerating voltage is selected so that the protective layers of No. 1 have substantially the same thickness. Thereby, the irradiation of the extra electron beam to the layer located under the first protective layer can be suppressed, and the deterioration of each layer due to the excess electron beam can be minimized. The irradiation dose is preferably such that the crosslinking density of the first protective layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). Further, the electron beam source is not particularly limited, and for example, various electron beam accelerators such as Cockloft-Walton type, Van de Graft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type, etc. Can be used. When ultraviolet rays are used as the ionizing radiation, light rays containing ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet source is not particularly limited, and examples thereof include a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, and a carbon arc lamp.

Through the above steps (a) to (e), the decorative molded product of the present invention can be obtained in which the resin molded product has a design that gives a high three-dimensional effect.

<Step (f)>
The step (f) is a step of forming a top coat layer on the transfer surface of the transfer object, if necessary. Since a cured product of an ionizing radiation curable resin is excellent in scratch resistance and the like, in the hydraulic transfer film of the present invention, a decorative molded article using a conventional hydraulic transfer film is formed after the transfer of the hydraulic transfer film. Even if the required top coat layer is not formed, excellent surface characteristics such as scratch resistance can be imparted to the decorative molded product. When the top coat layer is provided, the delicate design feeling expressed by the first protective layer and the second protective layer may be impaired, but according to the hydraulic transfer film of the present invention, the top coat layer is formed. Since it is possible to produce a decorative molded article having excellent surface properties without using the top coat layer, it is possible to achieve both design and surface properties by not providing the top coat layer.

When the step (f) is carried out, in the step (f), the cured first protective layer is coated as necessary to improve the surface strength, protect the surface, adjust the gloss of the surface, etc. Or to form a semitransparent topcoat layer.

As a material for forming the top coat layer, for example, a thermoplastic resin, a thermosetting resin, an ultraviolet curable resin or the like is selected, and specifically, a urethane resin, an epoxy resin, an acrylic resin, a fluorine resin, a silicon A resin or the like is used. The top coat layer can be formed by a known coating method such as spray coating, electrostatic coating, brush coating or dip coating using a coating obtained by dissolving the above resin in a known organic solvent. The thickness of the top coat layer is preferably 1 to 25 μm, more preferably 1 to 10 μm.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, the thickness of the first protective layer means the thickness of the convex-concave portion formed by the first protective layer.

<Example 1>
A polyvinyl alcohol (PVA) film (thickness 40 μm) is used as the water-soluble film, and the following resin composition containing an ionizing radiation-curable resin is used on one side of the film to form a first protective layer (thickness 3 μm) by gravure printing. Formed. Further, the first protective layer was printed in a pattern so that a portion (convex portion) laminated on the water-soluble film and a portion (concave portion) not laminated were formed to form an uneven shape. Next, a pattern layer (2 μm) having a wood grain pattern was formed by gravure printing using the following ink containing nitrified cotton and alkyd resin in a mass ratio of 80:20, and a water-soluble film/first protective layer/ A hydraulic transfer film having a pattern layer laminated thereon was obtained. The wood grain pattern of the pattern layer is formed by using three types of ink, black ink, dark brown ink and light brown ink, in this order, and printing the light brown ink on the entire surface with black ink and dark brown ink in a pattern. The black ink was used to represent the conduit portion, and the conduit portion was aligned with the recesses in the uneven shape of the first protective layer.
(Resin composition forming the first protective layer)
Bifunctional polycarbonate acrylate (weight average molecular weight 10,000, 95 parts by mass), tetrafunctional urethane acrylate (weight average molecular weight 6,000, 5 parts by mass), urethane beads (particle diameter 3 μm, 10 parts by mass)
(Ink that forms the pattern layer)
Colored ink containing nitrified cotton and alkyd resin in a mass ratio of 80:20 and using stalk and carbon black as coloring agents in a predetermined mixing ratio.

<Example 2>
After forming the first protective layer and before forming the pattern layer, the entire surface of the second protective layer (thickness 3 μm) is solid-printed by gravure printing using the following resin composition containing an ionizing radiation curable resin. A hydraulic transfer film in which a water-soluble film/first protective layer/second protective layer/design layer was laminated was obtained in the same manner as in Example 1 except that the film was formed.
(Resin composition forming second protective layer)
Bifunctional polycarbonate acrylate (weight average molecular weight 10,000, 95 parts by mass), tetrafunctional urethane acrylate (weight average molecular weight 6,000, 5 parts by mass), silica (particle diameter 1.3 μm, 30 parts by mass)

<Example 3>
A water-soluble transfer film was obtained in the same manner as in Example 2 except that the following resin composition containing an acrylic polyol was used as the resin composition forming the second protective layer.
(Resin composition forming second protective layer)
Acrylic polymer polyol (weight average molecular weight 30,000, hydroxyl value 80 mgKOH/g, 80 parts by mass), urethane urea resin (glass transition point 40° C., 20 parts by mass), and silica (10 parts by mass, particle diameter 1.3 μm)

<Comparative Example 1>
A water-soluble transfer film was obtained in the same manner as in Example 1, except that the first protective layer and the second protective layer were not formed and the picture layer was directly formed on the water-soluble film. With respect to the obtained hydraulic transfer film, the design property of the decorative molded product and the transfer processability (following property) were evaluated. The results are shown in Table 1.

<Comparative example 2>
The following resin composition containing an ionizing radiation curable resin and urethane beads, which forms the second protective layer and does not form the first protective layer, is formed on the water-soluble film by gravure printing. A water-soluble transfer film was obtained in the same manner as in Example 2 except that the protective layer (thickness 3 μm) was formed entirely and solidly. With respect to the obtained hydraulic transfer film, the design property of the decorative molded product and the transfer processability (following property) were evaluated. The results are shown in Table 1.
(Resin composition forming second protective layer)
Bifunctional polycarbonate acrylate (weight average molecular weight 10,000, 95 parts by mass), tetrafunctional urethane acrylate (weight average molecular weight 6,000, 5 parts by mass), silica (particle diameter 1.3 μm, 10 parts by mass)

<Manufacture of decorative molded products>
3 g/m ² of the activator composition having the following composition was applied to the pattern layer of each of the hydraulic transfer films obtained above, and the activator composition was made uniform with a smoothing roll, and the activator coating step (b) of the pattern layer was performed. ), the transfer target is pressed against the hydraulic transfer film floating on the water surface, and the pattern layer is brought into close contact with the transfer surface of the transfer target by water pressure (c), and the film removal step by washing (d) , And the curing step (e), a decorative molded product was obtained. In the curing step of the first protective layer, electron beam irradiation (accelerating voltage 165 kV, irradiation dose 50 kGy (5 Mrad)) was applied from the first protective layer side of the water pressure transfer film to cure the first protective layer. .. When the second protective layer contained an ionizing radiation curable resin, it was similarly cured. A cylindrical resin molded body having a diameter of 35 mm and a length of 250 mm was used as the transferred body.

(Composition of activator composition)
Phthalic acid 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

(1) Evaluation of design property The decorative molded product obtained above was visually observed, and its design property was evaluated according to the following criteria. The results are shown in Table 1.
◯: The unevenness corresponding to the uneven shape of the first protective layer was well expressed, the conduit portion was recognized as a recess, and a delicate three-dimensional effect was obtained.
(Triangle|delta): Although the unevenness|corrugation feeling corresponding to the uneven|corrugated shape of a 1st protective layer fell a little, it was fully visible and the delicate three-dimensional effect which does not cause a problem in practical use was obtained.
X: Since the unevenness corresponding to the uneven shape of the first protective layer disappeared, a delicate three-dimensional effect could not be obtained.

By forming the first protective layer with an ionizing radiation curable resin and further forming it into an uneven shape, it is possible to obtain a decorative molded product having a delicate and highly three-dimensional design. I understand.

10 Water-Soluble Film 21 First Protective Layer 22 Second Protective Layer 30 Picture Layer 31 Dark Part 40 Transferee 1 Hydraulic Transfer Film 2 Decorative Molded Product

Claims (6)

A hydraulic transfer film having a water-soluble film, a first protective layer, and a pattern layer in this order,
The first protective layer forms an uneven shape on the surface of the water-soluble film,
The first protective layer contains an ionizing radiation curable resin,
The ionizing radiation curable resin forming the first protective layer contains a polyfunctional polycarbonate (meth)acrylate,
A second protective layer is provided between the first protective layer and the pattern layer,
A hydraulic transfer film, wherein the second protective layer contains an ionizing radiation curable resin that is the same as or different from the ionizing radiation curable resin that forms the first protective layer . The hydraulic transfer film according to claim 1, wherein the ionizing radiation-curable resin forming the second protective layer is different from the ionizing radiation-curable resin forming the first protective layer. The water pressure according to claim 1 or 2 , wherein the uneven shape is formed by a portion having the first protective layer on the surface of the water-soluble film and a portion not having the first protective layer. Transfer film. It said first protective layer comprises a matting agent, hydraulic transfer film according to any one of claims 1-3. The manufacturing method of the hydraulic transfer film which has the following processes (A), (A'), and (B) in order.
Step (A) is a step of laminating a first protective layer containing an ionizing radiation curable resin so as to form an uneven shape on the surface of the water-soluble film , wherein the ionizing radiation curable resin is a polyfunctional resin. Step (A′) containing polycarbonate (meth)acrylate Ionizing radiation curable resin which is the same as or different from the ionizing radiation curable resin which forms the first protective layer on the first protective layer. A step of stacking a second protective layer containing (B) a step of stacking a pattern layer on the second protective layer A method for producing a decorated molded article, which includes the following steps (a) to (e).
Step (a) Floating the water pressure transfer film according to any one of claims 1 to 5 on the water surface so that the water-soluble film side faces the water surface side. Step (b) Activator on the picture layer side of the water pressure transfer film. Activator applying step of applying the composition Step (c) The transferred material is pressed on the water pressure transfer film floating on the water surface through the steps (a) and (b), and the pattern layer is covered by water pressure. Step of adhering to the transfer surface of the transfer member (d) Removal of water-soluble film adhered to the transfer surface of the transfer member Step (e) Irradiation with ionizing radiation from the first protective layer side And then curing the first protective layer.