Hydraulic transfer method, coating agent for hydraulic transfer film and hydraulic transfer product

Abstract

To provide a stable textured feel by fine irregularities formed on a surface of a decorative layer by a special component added to a coating agent, the coating agent being composed of an energy ray-curable resin composition that is cured by light or heat energy rays, when the coating agent is applied to a printing pattern of a hydraulic transfer film and permeated into the printing pattern to hydraulically transfer the printing pattern.SOLUTION: The coating agent, whose main component is an energy ray-curable resin composition, contains a microfiber filler such as cellulose fiber in an amount of 2 to 19 wt.% based on a weight of components of the coating agent excluding volatile components, and a shape of the microfiber filler imparts fine irregularities to a decorative layer of a hydraulic transfer product.SELECTED DRAWING: Figure 3

Description

Technical Field

[0001] The present invention relates to a hydrographic transfer method for transferring a printed pattern on a dry hydrographic transfer film to an article after reproducing (restoring) the adhesion of the printed pattern of the hydrographic transfer film to be hydrographically transferred to the surface of the article to be decorated, a coating agent for a hydrographic transfer film used in this method, and an improvement in a hydrographic transfer product formed by this method.

Background Art

[0002] In order to decorate the surface of an article having a complex three-dimensional surface, a hydrographic transfer method is used. In this method, a hydrographic transfer film having a water-insoluble printed pattern printed on a water-soluble film (carrier film) is floated on the water surface in a transfer tank. After wetting the water-soluble film of this hydrographic transfer film with water, the article (object to be transferred) is pushed into the water in the transfer layer while contacting the printed pattern of this hydrographic transfer film, and the printed pattern of the hydrographic transfer film is transferred to the surface of the article by utilizing the water pressure generated on the surface of the article at this time, thereby manufacturing a hydrographic transfer product in which a decorative layer (decoration layer) is formed.

[0003] In recent years, it has been required to impart fine irregularities to the surface of a hydrographic transfer product manufactured in this way to impart a texture touch feeling.

[0004] In order to meet this requirement, in one prior art, without applying a top coat on the decorative layer, in order to chemically and physically protect the surface of the decorative layer, a coating agent composed of an energy ray curable resin composition that cures when irradiated with an energy ray such as light or heat is applied to the dry printed pattern of the hydrographic transfer film, and the printed pattern is dissolved by an active component in the curable resin composition to restore its adhesion and perform hydrographic transfer. In this method, an attempt has been made to provide a hydrographic transfer product having a texture touch feeling in which a fine irregularity due to resin beads is imparted to the surface of the hydrographic transfer product and a soft feeling and a wet feeling are combined by using a coating agent containing specific resin beads in a specific ratio in a photocurable resin (see Patent Document 1).

[0005] However, in this prior art, since the resin beads for imparting unevenness are granular, the stress applied in the thickness direction of the decorative layer is received at points. Therefore, when stress is applied in the thickness direction and the surface direction as in the abrasion test, the resin beads are likely to be degranulated from the decorative layer, and a stable texture touch cannot be maintained.

[0006] In addition, a technique of adding unevenness to a decorative layer by mixing wood powder into a coating agent in the form of a solvent that is not cured by light or thermal energy by which the coating agent is integrated with a printing pattern is also disclosed (see Patent Document 2). In this prior art, in order to protect the surface chemically and physically, it is necessary to apply a top coat. In addition, the wood powder is also in an irregular granular shape, and like the previous prior art, it is likely to be degranulated and cannot maintain a stable texture touch.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] The first problem to be solved by the present invention is to penetrate a coating agent mainly composed of an energy ray curable resin component that is cured by irradiation with energy rays that are light or a combination of light and heat into the entire printing pattern of a transfer film and cure it with light or a combination of light and heat of the energy rays of the printing pattern, thereby imparting a chemical and mechanical surface protection function to the decorative layer itself, and to provide a hydraulic transfer method capable of stably imparting a texture touch due to fine unevenness to the surface of the decorative layer.

[0009] The second problem to be solved by the present invention is a coating agent mainly composed of an energy ray curable resin composition that cures by irradiation with energy rays that are light or a combination of light and heat, which penetrates the entire printed pattern of the transfer film and imparts a chemical and mechanical surface protection function to the decorative layer itself by curing of the printed pattern by irradiation with energy rays of light or a combination of light and heat, and stably imparts a texture touch feeling due to fine irregularities to the surface of the decorative layer. An object of the present invention is to provide a coating agent for a hydrostatic transfer film that can achieve this.

[0010] The third problem to be solved by the present invention is to penetrate a coating agent mainly composed of an energy ray curable resin composition that cures by irradiation with energy rays that are light or a combination of light and heat into the entire printed pattern of the hydrostatic transfer film, and by curing of the printed pattern by irradiation with energy rays of light or a combination of light and heat, while imparting a chemical and mechanical surface protection function, to obtain a hydrostatic transfer product in which a decorative layer having a texture touch feeling due to fine irregularities is stably imparted to the surface of the decorative layer.

Means for Solving the Problems

[0011] The means for solving the first problem of the present invention is to apply a coating agent mainly composed of an energy ray curable resin composition that cures by irradiating at least an energy ray containing light to a water pressure transfer film having a dried printed pattern of a water-soluble film, and to restore the adhesiveness of the printed pattern by an activating component in the energy ray curable resin composition, transfer the printed pattern to the surface of an article by water pressure to form a pattern transfer layer impregnated with the coating agent on the surface of the article, irradiate at least an energy ray containing light to the pattern transfer layer to cure the pattern transfer layer to form a decorative layer, and wash and remove the water-soluble film of the transfer film remaining on the surface of the decorative layer. In the water pressure transfer method, the coating agent contains a microfiber filler at a ratio of 2 to 19% by weight based on the weight of the components excluding the volatile components in the coating agent, and provides fine irregularities on the surface of the decorative layer by the microfiber filler. A water pressure transfer method is provided. The main body of the coating agent is non-volatile and non-solvent type, but is diluted with a solvent for dilution purposes, and the "volatile components in the coating agent" include such solvents for dilution.

[0012] In the means for solving the first problem of the present invention, the microfiber filler preferably has a fiber diameter that is 1.5 to 5.0 times the film thickness of the decorative layer and a fiber length that is 1.5 to 10.0 times the fiber diameter, and more preferably, the fiber length is 1.5 to 6.5 times the fiber diameter.

[0013] In the means for solving the first problem of the present invention, the microfiber filler is preferably an inorganic fiber such as cellulose fiber and / or glass fiber, carbon fiber, and cellulose fiber is most preferred.

[0014] In the means for solving the first problem of the present invention, the energy ray curable resin composition of the coating agent can be a photo (ultraviolet ray) curable resin or a combination of a photo curable resin and a thermosetting resin.

[0015] In the means for solving the first problem of the present invention, the coating agent preferably further contains a matting agent.

[0016] In the first problem-solving means of the present invention, the coating agent can contain an additional resin component that imparts chemical resistance and / or physical resistance.

[0017] The means for solving the second problem of the present invention is to apply a coating agent mainly composed of an energy ray-curable resin composition that is cured by irradiation with energy rays containing at least light to a water transfer film having a printed pattern dried on a water-soluble film, and the adhesion of the printed pattern is restored by an activating component in the curable resin composition. Then, the printed pattern is water transfer-printed onto the surface of an article to form a pattern transfer layer impregnated with the coating agent on the surface of the article. At least energy rays containing light are irradiated onto the pattern transfer layer to cure the pattern transfer layer and form a decorative layer. The water-soluble film of the water transfer film remaining on the surface of the decorative layer is washed and removed. A coating agent for a water transfer film used in a water transfer method, wherein the coating agent further contains a microfiber filler in a proportion of 2 to 19% by weight based on the weight of the components excluding the volatile components of the coating agent in order to impart fine irregularities to the surface of the decorative layer.

[0018] In the second problem-solving means of the present invention, the microfiber filler preferably has a fiber diameter of 1 to 1000 μm and a fiber length of 1.5 to 10.0 times the fiber diameter.

[0019] In the second problem-solving means of the present invention, the microfiber filler is preferably an inorganic fiber such as a cellulose fiber, a glass fiber, or a carbon fiber, and the cellulose fiber is most preferred.

[0020] In the second problem-solving means of the present invention, the energy ray-curable resin composition of the coating agent can be a photocurable resin or a combination of a photocurable resin and a thermosetting resin.

[0021] In the second problem-solving means of the present invention, the coating agent preferably further contains a matting agent.

[0022] In the second problem-solving means of the present invention, the coating agent can contain an additional resin component that imparts chemical resistance and / or physical resistance.

[0023] The means for solving the third problem of the present invention is to provide a hydrographic transfer product having a decorative layer with a fine uneven surface formed by the first problem-solving means.

[0024] In the third problem-solving means of the present invention, the microfiber filler preferably has a fiber diameter that is 1.5 to 5.0 times the film thickness of the decorative layer and a fiber length that is 1.5 to 10.0 times the fiber diameter. Further, the microfiber filler is preferably any one of cellulose fiber, glass fiber, or carbon fiber, with cellulose fiber being most preferred. Furthermore, the energy ray curable resin composition of the coating agent used for the hydrographic transfer can be a photocurable resin or a combination of a photocurable resin and a thermosetting resin. The coating agent further contains a matting agent, and the coating agent can contain an additional resin component that imparts chemical resistance and / or physical resistance.

[0025] In the third problem-solving means of the present invention, the height of the convex portions of the fine uneven surface of the decorative layer is preferably 10 to 1000 μm.

Effects of the Invention

[0026] According to the present invention, since the coating agent for restoring the adhesiveness by applying it to the printing pattern of the transfer film contains an appropriate weight% of microfiber filler, it is possible to impart fine unevenness in the form of vertically long fibrous shapes. Compared with the granular unevenness of the prior art, the pressure receiving area is dispersed in the longitudinal direction with respect to the stress in the film thickness direction, so that the filler for imparting unevenness does not fall off from the decorative layer, the abrasion resistance is improved, and a texture touch that can be stably maintained for a long time can be obtained.

[0027] Also, if the microfiber filler for imparting unevenness contained in the coating agent is cellulose fiber, the environmental load during hydrostatic transfer can be reduced, which is environmentally beneficial. On the other hand, if the microfiber filler is carbon fiber or glass fiber, the mechanical strength of the decorative layer can be improved.

Brief Description of the Drawings

[0028]

Figure 1

Figure 2

Figure 3

Figure 4

Modes for Carrying Out the Invention

[0029] While referring to the drawings, embodiments of the present invention will be described in detail. FIG. 1 systematically shows the steps of the hydrographic transfer method to which the present invention is applied. As shown in FIG. 2, this hydrographic transfer method includes a step 100 of preparing a hydrographic transfer film 10 having a printed pattern 14 printed and dried on a water-soluble film (carrier film) 12, a step 200 of preparing a coating agent mainly composed of a curable resin composition that cures when irradiated with energy rays of light or a combination of light and heat on the printed pattern 14 of the hydrographic transfer film 10, a step 300 of applying this coating agent to the printed pattern 14 of the hydrographic transfer film 10 to restore the adhesiveness of the printed pattern 14 by the activating component in the curable resin composition, a step (transfer step) 400 of hydrographically transferring the printed pattern 14 of the hydrographic transfer film 10 onto the surface of an article 20 to form a pattern transfer layer 16 (layer before curing of the decorative layer 22) (see FIG. 4) in which the coating agent penetrates the surface of the article 20, a step (curing step) 500 of irradiating the pattern transfer layer 16 with energy rays of light or a combination of light and heat to cure the pattern transfer layer 16 and form the decorative layer 22 shown in FIG. 3, and a step (washing and removing step) 600 of washing and removing the water-soluble film 12 of the transfer film 10 remaining on the surface of the decorative layer 22.

[0030] Details of these steps 100 to 600 will be sequentially described below.

[0031] (Hydrographic Transfer Film) The water-soluble film 12 of the hydrographic transfer film 10 is made of a water-soluble material mainly composed of, for example, polyvinyl alcohol that absorbs water and becomes wet and softens. This water-soluble film 12 touches the water in the transfer tank during hydrographic transfer, softens, and wraps around the article to be decorated so that hydrographic transfer can be performed. In the case of general hydrographic transfer, the printed pattern 14 is previously applied on the water-soluble film 12 by gravure printing or the like, and is in a dry and solidified state in which the adhesiveness is completely lost before hydrographic transfer in order to store the hydrographic transfer film 10 in a rolled state or the like. Note that this printed pattern 14 includes not only a pattern in the strict sense but also a plain (patternless) printed layer.

[0032] (Main component of the coating agent) The coating agent (also called an activator) used in the present invention is mainly composed of a curable resin composition that is cured by energy rays containing at least light (specifically, ultraviolet rays). The non-solvent activator can activate the dried printed pattern 14 of the water transfer film 10 by the activating component in this resin composition to restore the adhesiveness. When this coating agent is applied to the printed pattern 14 of the water transfer film 10, in addition to the function of restoring the adhesiveness of the above-mentioned printed pattern 14, the energy ray curable resin composition, which is the main component of the coating agent, penetrates the entire printed pattern 14 (total area, total thickness) and has the function of mixing the energy ray curable resin composition with the printed pattern 14 to integrate with the printed pattern 14. As described later, the printed pattern 14 in which the energy ray curable resin composition is mixed is transferred to an article to form a pattern transfer layer 16, and this pattern transfer layer 16 is cured by energy rays containing light to form a decorative layer 22 (see FIGS. 3 and 4). The energy ray curable resin composition needs to contain at least a photocurable resin composition that can rapidly progress the curing in the presence of water-swelled water-soluble film 12 and moisture in the curing process of the pattern transfer layer 16. However, this energy ray curable resin composition may also contain a thermosetting resin composition in addition to the photocurable resin composition. In this case, as a dual-cure type resin composition by light and heat, it is cured by irradiation with energy rays of light and heat.

[0033] (Examples of components of the coating agent) When the energy ray curable resin component of the coating agent is a photoenergy ray curable resin composition, this photoenergy ray curable resin component contains a photopolymerizable monomer and a photoinitiator. From the viewpoint of the photopolymerizable monomer penetrating into the printing pattern 14 and being activated to a transferable state, it is preferably a bifunctional monomer. This bifunctional monomer can be 1,6 - hexanediol diacrylate, cyclohexyl acrylate, dipropylene glycol diacrylate. However, considering the penetrability into the ink of the printing pattern 14, the dissolving power, and a more suitable SP value, 1,6 - hexanediol diacrylate and dipropylene glycol diacrylate are preferred. The photopolymerizable monomer can be a combination with a polyfunctional monomer such as a bifunctional monomer and a tetrafunctional monomer, and may further contain a photopolymerizable oligomer for the purpose of improving the film strength of the decorative layer 22 after curing of the pattern transfer layer 16 and the adhesion to the transfer body. As the photopolymerizable oligomer, a polyfunctional oligomer and a bifunctional oligomer can be used alone or in combination according to the performance such as film strength. A specific compounding example of the photopolymerizable oligomer, the photopolymerizable monomer, and the photoinitiator is preferably such that the photopolymerizable oligomer is 25 to 56% by weight, the photopolymerizable monomer is 33 to 65% by weight, and the photoinitiator is 5 to 10% by weight based on the total amount of the photocurable resin composition.

[0034] (Photoinitiator of the energy ray curable resin composition) The photoinitiator is for initiating the photopolymerization reaction of the photopolymerizable oligomer and the photopolymerizable monomer. In the coating agent used in the present invention, in order to dissolve and penetrate the ink of the printing pattern 14 in which the photoenergy ray (ultraviolet ray) curable resin composition is dried and solidified, it is preferable that the photoinitiator contains both a surface - curing type photoinitiator and an internal - curing type photoinitiator. As the surface - curing type photoinitiator, for example, a hydroxyketone - based one can be used, and as the internal - curing type photoinitiator, for example, an acylphosphine oxide - based one can be used.

[0035] (Essential additional components of the coating agent) The coating agent used in the present invention further contains microfiber fillers such as plant fibers or inorganic fibers in an amount of 2 to 19% by weight based on the weight of the components excluding the volatile components of the coating agent, in addition to the above main components. This microfiber filler has a function of imparting fine irregularities excellent in abrasion resistance to the surface of the decorative layer 22. When the content of the microfiber filler is less than 2% by weight, the irregularities become sparse and the effect of imparting irregularities becomes insufficient. On the other hand, when the content exceeds 19% by weight, the amount of the energy ray-curable resin composition, which is the main component of the coating agent, relatively decreases. As a result, the mechanical strength of the decorative layer 22 formed after curing decreases, and the microfiber filler is likely to be exposed on the surface of the decorative layer, significantly reducing the abrasion resistance of the decorative layer 22. In the present invention, the "microfiber" means a fiber having a fiber diameter of 1 to 1000 μm.

[0036] (Preferred form of microfiber filler) The microfiber filler used in the present invention has a fiber diameter that is 1.5 to 5.0 times, preferably 1.7 to 3.5 times, the film thickness of the decorative layer 22 (the layer after curing of the pattern transfer layer) formed by hydrostatic transfer, and has a fiber length that is 1.5 to 10.0 times, preferably 1.5 to 6.5 times, the fiber diameter. The reason will be described in detail later with reference to the description of specific examples. Although the microfiber filler may include those outside the above ranges of fiber length and fiber diameter, it is preferable that the microfiber filler having the above fiber diameter and fiber length accounts for 50% by weight or more, more preferably 80% by weight or more, and most preferably 90% by weight or more of the total weight of the microfiber filler.

[0037] (Preferred components of microfiber filler) The preferred microfiber filler used in the present invention is a cellulose fiber such as a plant fiber, an inorganic fiber such as a glass fiber or a carbon fiber. Particularly, from the viewpoints of abrasion resistance and low environmental load, cellulose fiber is most preferable.

[0038] (Other additive components of coating agent) The coating agent used in the present invention preferably further contains a matting agent in addition to the above energy ray curable resin composition and microfiber filler in order to impart a matting effect to the decorative layer. As long as this matting agent does not inhibit the abrasion resistance of the decorative layer and the formation of fine irregularities, those conventionally used in the coating agent for water pressure transfer can be used. 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 organic fillers or resin beads selected from acrylic resin, urethane resin, nylon resin, polypropylene resin, or urea-based resin, and any of them can be used alone or in combination. It is desirable that the volume average particle diameter of the matting agent is smaller than the fiber diameter of the microfiber filler. Specifically, depending on the fiber diameter of the microfiber filler, preferably, those having a diameter smaller than the fiber diameter in the range of 0.5 to 50 μm, more preferably 1 to 15 μm, and most preferably 5 to 10 μm can be used. The reason for making the particle size of the matting agent smaller than the microfiber diameter is that if the particles Diameter of the matting agent are larger than the fiber diameter of the microfiber filler, it becomes easy to degranulate as in the prior art and the abrasion resistance of the decorative layer decreases.

[0039] (Additional resin component for imparting chemical resistance and / or physical resistance) The coating agent used in the present invention may further contain an additional resin component for imparting chemical resistance and / or physical resistance. Specifically, a high molecular weight additional resin component that has compatibility with the main component energy ray curable resin composition and does not inhibit curing can be used. When the energy ray curable resin composition is an acrylic resin composition, this additional resin component is preferably a non-reactive acrylic resin. The preferred molecular weight (weight average molecular weight measured by gel permeation chromatography) of this non-reactive acrylic resin is 50,000 to 100,000, and the particularly preferred molecular weight is 60,000 to 80,000. Further, when blending this non-reactive acrylic resin, a diluting solvent in an amount that does not inhibit the effects of the present invention may be blended for viscosity adjustment.

[0040] (Hydrostatic transfer product) When a coating agent containing a microfiber filler is applied to the printing pattern of a hydrostatic transfer film and penetrates to hydrostatically transfer onto the surface of an article, as shown in FIGS. 3 and 4, a hydrostatic transfer product 24 having a decorative layer 22 is formed. As already described, the coating agent contains a microfiber filler 30 having a fiber diameter 1.5 to 5.0 times the film thickness of the decorative layer 22 and a fiber length 1.5 to 10.0 times the fiber diameter. Therefore, the microfiber filler 30 in the coating agent that has penetrated into the printing pattern 14 of the hydrostatic transfer film is mixed into the decorative layer 22, and a longitudinally elongated surface 24S with fine unevenness is formed by this microfiber filler 30. The height of the convex portion of the unevenness of this surface with fine unevenness is preferably a value of 10 μm or more, expressed as the Rz value (maximum height roughness) conforming to JIS B0601:2001, and more preferably 10 to 1000 μm. The height of this convex portion is obtained based on the fiber diameter of the microfiber filler contained in the coating agent. When the height of this convex portion is 10 μm or more, a stable texture touch can be obtained. However, when the height of this convex portion is less than 10 μm, the unevenness effect is insufficient and a good texture touch cannot be obtained.

[0041] (Uneven surface of the decorative layer of the hydrostatic transfer product) The thickness of the decorative layer 22 is adjusted by the thickness of the printing pattern of the hydrostatic transfer film and the coating amount of the coating agent. Here, the thickness of the decorative layer 22 is represented by the vertical dimension from the bottom of the concave portion of the uneven surface 24S to the interface where the decorative layer 22 contacts the article (transfer object) 20. In addition, the portion where the ratio of the fiber diameter of the microfiber filler to the film thickness of the decorative layer is in the range of 1.5 to 5.0 (the microfiber filler occupied area = hereinafter simply referred to as the filler effective occupied area) is most preferably the entire surface of the decorative layer. The filler effective occupied area with respect to the area of the region where the decorative layer 22 of the article (transfer object) 20 is formed is at least 60%, but more preferably 80% or more. The portion deviating from the filler effective occupied area is caused by the variation in the coating thickness of the coating agent and the distribution of the fiber diameter of the microfiber filler. Therefore, the coating agent preferably has as little variation as possible when being applied.

[0042] (Specific Example) Next, specific examples of the present invention will be described in detail below.

[0043] (Example 1) 2 parts by weight of cellulose fibers (ARBOCEL BE600-30 manufactured by Rettenmaier Japan Co., Ltd.: average fiber diameter 18 μm, average fiber length 30 μm) as a microfiber filler was added to 100 parts by weight of a photocurable resin composition obtained by mixing 20 parts by weight of an acrylic UV-curable activator (Uvicure S Clear HE manufactured by Daicel Chemical Industries, Ltd.), 80 parts by weight of an acrylic UV-curable activator containing a matting agent (Uvicure S Matting Clear HE manufactured by Daicel Chemical Industries, Ltd.), and 16.3 parts by weight of a non-reactive acrylic resin (Uvicure S Polymer manufactured by Daicel Chemical Industries, Ltd.). After mixing and stirring, a coating agent for a hydrostatic transfer film of Example 1 was prepared.

[0044] (Examples 2 to 7, 13, 14) Coating agents for hydrostatic transfer films of Examples 2 to 7 and Example 13 were prepared by mixing components in the same manner as in Example 1, except that the blending amount of the cellulose fibers in Example 1 was changed as shown in Tables 1 to 3.

[0045] (Example 8) Instead of the microfiber filler of Example 1, another cellulose fiber (ARBOCEL (registered trademark) BE800 manufactured by Rettenmaier Japan Co., Ltd.: average fiber diameter 20 μm, average fiber length 130 μm) was used, and the components were blended in the same manner as in Example 1 except that the blending amount was 4 parts by weight to prepare a coating agent for a hydrostatic transfer film of Example 8.

[0046] (Example 9) Instead of the microfiber filler of Example 1, carbon fiber (XN150-10 manufactured by Nippon Graphite Co., Ltd.: average fiber diameter 20 μm, average fiber length 130 μm) was used, and the components were blended in the same manner as in Example 1 except that the blending amount was 4 parts by weight to prepare a coating agent for a hydrostatic transfer film of Example 9.

[0047] (Example 10) Instead of the microfiber filler of Example 1, cellulose fiber (ARBOCEL (registered trademark) BE800 manufactured by Rettenmaier Japan Co., Ltd.: average fiber diameter 20 μm, average fiber length 130 μm) was classified by a dry classification device to have an average fiber diameter of 20 μm and an average fiber length of 200 μm, and the components were blended in the same manner as in Example 1 except that the blending amount was changed to 16 parts by weight to prepare a coating agent for a hydrostatic transfer film of Example 10.

[0048] (Example 11) Instead of the microfiber filler of Example 1, cellulose fiber (ARBOCEL (registered trademark) BE600-30 manufactured by Rettenmaier Japan Co., Ltd.: average fiber diameter 18 μm, average fiber length 30 μm) was classified by a dry classification device to have an average fiber diameter of 20 μm and an average fiber length of 25 μm, and the components were blended in the same manner as in Example 1 except that the blending amount was changed to 16 parts by weight to prepare a coating agent for a hydrostatic transfer film of Example 11.

[0049] (Example 12) Instead of the microfiber filler of Example 1, cellulose fibers (ARBOCEL® BE800 manufactured by Rettenmaier Japan Co., Ltd.: average fiber diameter 20 μm, average fiber length 130 μm) were classified by a dry classification device to obtain cellulose fibers with an average fiber diameter of 20 μm and an average fiber length of 250 μm. The components were blended in the same manner as in Example 1 except that the blending amount was changed to 16 parts by weight, and a coating agent for a hydrostatic transfer film of Example 12 was prepared.

[0050] (Example 15) Instead of the microfiber filler of Example 1, cellulose fibers (ARBOCEL® BE600-30 manufactured by Rettenmaier Japan Co., Ltd.: average fiber diameter 18 μm, average fiber length 30 μm) were classified by a dry classification device to obtain cellulose fibers with an average fiber diameter of 25 μm and an average fiber length of 30 μm. The components were blended in the same manner as in Example 1 except that the blending amount was changed to 16 parts by weight, and a coating agent for a hydrostatic transfer film of Example 15 was prepared.

[0051] (Comparative Example 1) As shown in Table 4, a coating agent for a hydrostatic transfer film of Comparative Example 1 was prepared by blending the resin components in the same manner as in Example 1 without blending any filler.

[0052] (Comparative Example 2) A coating agent for a hydrostatic transfer film of Comparative Example 2 was prepared by blending the components in the same manner as in Example 1 except that the blending amount of the cellulose fibers of Example 1 was changed as shown in Table 4.

[0053] (Comparative Example 3) A coating agent for a hydrostatic transfer film of Comparative Example 3 was prepared in the same manner as in Example 1, except that 16 parts by weight of spherical acrylic particles with an average particle diameter of 20 μm were blended instead of the microfiber filler of Example 1. The spherical acrylic particles were prepared by the following method. 20 parts by weight of divinylbenzene (DVB), 10 parts by weight of ethylene glycol dimethacrylate, and 0.1 part by weight of Peroyl (registered trademark) L (polymerization initiator, NOF Corporation) were mixed to prepare an oil phase. Next, 100 parts by weight of ion-exchanged water and 0.005 part by weight of sodium lauryl sulfate were mixed to prepare an aqueous phase. The above oil phase was added to this aqueous phase, and a suspension was prepared using an ultrasonic homogenizer. This suspension was purged with nitrogen and heated at 80 °C for 4 hours to carry out polymerization to obtain a slurry in which spherical acrylic particles were formed. The spherical acrylic particles recovered by filtering this slurry were dried and then classified using a dry classification device.

[0054] (Comparative Examples 4 and 5) Coating agents for hydrostatic transfer films of Comparative Example 4 and Comparative Example 5 were prepared in the same manner as in Comparative Example 3, except that the average particle diameter of the spherical acrylic particles in Comparative Example 3 was changed to 30 μm (Comparative Example 4) and 50 μm (Comparative Example 5), respectively. Each spherical acrylic particle was prepared by the same production method as the spherical acrylic particle in Comparative Example 3, and those classified into the respective particle diameters as described above were used.

[0055] Hydrostatic transfer was performed by the following method using the coating agents of Examples 1 to 15 and Comparative Examples 1 to 5. (i) Hydrostatic transfer film As the hydrostatic transfer film, a film having a printing pattern of a sawn pattern, which is sold by the licensee of the hydrostatic transfer technology of the applicant, Taika Co., Ltd., under the name of "Art Hose", was used. (ii) Coating of the coating agent The coating agent was applied to the hydrostatic transfer film of (i) with a kiss roll reverse coater equipped with a coating roll at the coating thicknesses described in Tables 1 to 4 corresponding to each Example and Comparative Example. (iii) Object to be transferred (article) The object to be transferred was a flat plate made of ABS resin (manufactured by Technos UMG Co., Ltd.) with dimensions of 100 mm × 200 mm × 3 mm. (iV) Hydrographic transfer The hydrographic transfer film 12 with the coating agent of each example and comparative example applied to the printing pattern side was floated on water, and the hydrographic transfer film 12 was stretched to a stretch ratio of 150%. Then, the object to be transferred 20 was pressed against it for hydrographic transfer. Ultraviolet rays were irradiated onto the pattern transfer layer 16 formed by transferring the printing pattern 14 onto the object to be transferred 20 to cure it and form the decorative layer 22. After that, the water-soluble film 12 of the hydrographic transfer film 10 was removed through a washing and removing process and a drying process, and hydrographically transferred products of Examples 1 to 15 and Comparative Examples 1 to 5 were obtained. The curing of the pattern transfer layer 16 by ultraviolet irradiation was performed using an A-type metal halide lamp (manufactured by GS Yuasa Power Supply Co., Ltd., MAN800NL) under the conditions of peak intensity Ip = 250 mW / cm 2 , integrated light quantity E = 2600 mJ / cm 2 by irradiating under these conditions. The film thickness of the decorative layer 22 was observed with a microscope equipped with a length measuring function (Keyence VHX7000) for the cross-sectional cut surface in the thickness direction. An arbitrary measurement point P0 in the region where unevenness was formed was selected, and the shortest distance from the bottom of the unevenness to the surface of the object to be transferred was measured for the thickness. Further, based on the measurement point P0, the thicknesses at three positions each moved 0.75 mm and 1.5 mm in the horizontal direction of the cross-section were measured in the same manner, and the measured values of the thicknesses at these three points were obtained by arithmetic mean.

[0056]

Table 1

[0057]

Table 2

[0058]

Table 3

[0059]

Table 4

[0060] Each item of the evaluation in Table 1-4 was set as follows. (1) Initial touch feeling Using a small surface roughness measuring instrument (SURFTEST SJ-210 manufactured by Mitutoyo Corporation), the Rz value (maximum height roughness) was measured in accordance with JIS B0601:2001 on the surface of the decorative layer of the hydrostatic transfer product. When the Rz value was 15 or more, it was judged as excellent (◎), when the Rz value was 10 or more and less than 15, it was judged as good (○), when the Rz value was 5 or more and less than 10, it was judged as acceptable (△), and when the Rz value was less than 5, it was judged as poor (×). (2) Touch feeling after wear resistance test Using a wear and friction tester (Academic Promotion Type Friction Fastness Tester AB-301 manufactured by Tester Sangyo Co., Ltd.), the surface of the decorative layer of the hydrostatic transfer product was friction processed 5000 times under the conditions of a load of 1 kg and a speed of 40 mm / second with H1 felt as the abrading agent. Using a handy gloss meter (HG268 manufactured by Suga Test Instruments Co., Ltd.), the gloss value before the test (G0) and the gloss value after the test (G T ) were measured. When there was no peeling of the transfer pattern of the decorative layer and no decrease in gloss (G T / G0>95%), it was judged as excellent (◎). When there was no peeling of the transfer pattern of the decorative layer and a slight decrease in gloss occurred (95>G T / G0≧90%), it was judged as good (○). When there was no peeling of the transfer pattern of the decorative layer and an obvious decrease in gloss occurred (G T / G0<90%), it was judged as acceptable (△). When peeling of the transfer pattern of the decorative layer occurred, it was judged as poor (×).

[0061] Next, the evaluation will be described as follows while comparing between the examples of the present invention and between the examples and the comparative examples in relation to various elements of the filler that contribute to the fine uneven surface of the decorative layer.

[0062] (Shape of filler) In Comparative Examples 3 to 5, the filler is not fibrous but granular. Therefore, as in Comparative Examples 2 and 3, even if there is an initial tactile sensation, there is no abrasion resistance. Thus, it can be understood that, different from all the examples of the present invention using fibrous fillers, the texture tactile sensation cannot be maintained over a long period of time.

[0063] (Filler blending amount = parts by weight) Comparative Example 1 does not contain any filler, so there is no unevenness imparted to the surface of the decorative layer. Also, in Comparative Example 2, although a fibrous filler is used, its content deviates beyond the upper limit of "2 to 19% by weight" required in the present invention, which is 30% by weight based on the weight of the components excluding the volatile components of the coating agent. Therefore, unevenness is imparted to the surface of the decorative layer, but the abrasion resistance decreases, and it can be understood that the tactile sensation cannot be maintained over a long period (refer to "×" for the tactile sensation after the abrasion resistance test in Comparative Example 2). In addition, it can be understood that in Examples 1 and 2, the content of the microfiber filler is close to the lower limit at 2.2 and 4.3% by weight respectively, and the initial tactile sensation is slightly inferior.

[0064] (Filler material) Examples other than Example 9 use a microfiber filler of cellulose, and Example 9 uses a microfiber filler of carbon fiber. However, in all cases, the initial tactile sensation is "〇" or more, and the tactile sensation after the abrasion resistance test is "△ (acceptable)" in Examples 11, 12, and 15, and it can be understood that it can withstand use. However, considering the environmental load, cellulose is more preferable.

[0065] (Filler dimensions) In Examples 11, 12, and 15, the magnification (L / D) of the fiber length with respect to the fiber diameter of the microfiber filler used is outside the upper limit (Example 12) and the lower limit (Examples 11, 15) of the preferable range of 1.5 to 10, and also outside the lower limit (Example 13) and the upper limit (Example 15) of the fiber diameter (D / T) with respect to the thickness of the decorative layer of the microfiber filler used in Examples 12 and 15. Therefore, it can be understood that the tactile sensation after the abrasion resistance test of the decorative layers of these Examples 11, 12, and 15 is slightly degraded to "Δ (Good)". In addition, in Example 11, the initial tactile sensation is also slightly degraded, which is because the L / D is close to the lower limit.

[0066] (Most Preferred Embodiment) Examples with high evaluations for both the initial tactile sensation and the tactile sensation after the abrasion resistance test are Examples 3, 4, 7 to 9, which are the result of appropriately selecting both the content and dimensions of the microfiber filler. In particular, it can be understood that it is preferable that the L / D of the filler is in the range of 1.5 to 6.5 and the D / T is in the range of 1.7 to 3.3.

[0067] (Others) Note that Examples 1 to 15 contain a matting agent and a non-reactive polymer in the coating agent, and in any case, it can be understood that these additional components do not inhibit the evaluation of the tactile sensation.

Industrial Applicability

[0068] The coating agent of the present invention mainly comprises an energy ray curable resin composition, which is applied to the printing pattern of a transfer film to activate it and penetrate the entire printing pattern to impart chemical and physical surface protection functions to the resulting decorative layer. In addition to the energy ray curable resin composition, a microfiber filler is added to impart fine irregularities to the surface of the decorative layer, so that a stable texture feeling can be maintained over a long period of time, and it has high industrial applicability.

Explanation of Signs

[0069] 10 Hydrostatic transfer film 12 Water-soluble film 14 Printing pattern 16 Pattern transfer layer 20 Article to be decorated 22 Decoration layer 24S Surface with unevenness 30 Microfiber filler 100 Preparation process of the hydrostatic transfer film 200 Preparation process of the coating agent 300 Coating process of the coating agent 400 Hydrostatic transfer process 500 Curing process by energy ray irradiation 600 Washing and removing process of the water-soluble film

Claims

1. A water transfer method, which comprises applying a coating agent mainly composed of an energy ray-curable resin to a water transfer film having a printed pattern dried thereon to restore the adhesiveness of the printed pattern by an activating component in the energy ray-curable resin, water-transferring the printed pattern onto the surface of an article to form a pattern transfer layer impregnated with the coating agent on the surface of the article, irradiating at least light energy rays onto the pattern transfer layer to cure the pattern transfer layer to form a decorative layer, and washing and removing the water-soluble film of the water transfer film remaining on the surface of the decorative layer, wherein the coating agent contains a microfiber filler at a ratio of 2 to 19% by weight based on the weight of the components excluding the volatile components of the coating agent, and the microfiber filler imparts fine irregularities to the surface of the decorative layer.

2. The water transfer method according to Claim 1, wherein the microfiber filler has a fiber diameter 1.5 to 5.0 times the film thickness of the decorative layer and a fiber length 1.5 to 10.0 times the fiber diameter.

3. The water transfer method according to Claim 1, wherein the microfiber filler is any one of cellulose fiber, glass fiber or carbon fiber.

4. The water transfer method according to Claim 1, wherein the energy ray-curable resin of the coating agent is a photocurable resin or a combination of a photocurable resin and a thermosetting resin.

5. The water transfer method according to Claim 1, wherein the coating agent further contains a matting agent.

6. The water transfer method according to Claim 1, wherein the coating agent contains an additional resin component for imparting chemical resistance and / or physical resistance.

7. A coating agent mainly composed of an energy ray-curable resin composition that is cured by at least light energy rays is applied to a water pressure transfer film having a printed pattern dried on a water-soluble film, and the adhesion of the printed pattern is restored by an activating component in the energy ray-curable resin composition. The printed pattern is water pressure transferred onto the surface of an article to form a pattern transfer layer impregnated with the coating agent on the surface of the article. At least light energy rays are irradiated onto the pattern transfer layer to cure the pattern transfer layer and form a decorative layer. The water-soluble film of the water pressure transfer film remaining on the surface of the decorative layer is washed and removed. A coating agent for a water pressure transfer film used in a water pressure transfer method, wherein the coating agent contains a microfiber filler in a proportion of 2 to 19% by weight based on the weight of the components excluding the volatile components of the coating agent in order to impart fine unevenness to the surface of the decorative layer. The coating agent for a water pressure transfer film is characterized by this.

8. The coating agent for a water pressure transfer film according to claim 7, wherein the microfiber filler has a fiber diameter of 1 to 1000 μm and a fiber length of 1.5 to 10.0 times the fiber diameter. The coating agent for a water pressure transfer film.

9. The coating agent for a water pressure transfer film according to claim 7, wherein the microfiber filler is any one of cellulose fiber, glass fiber or carbon fiber. The coating agent for a water pressure transfer film.

10. The coating agent for a water pressure transfer film according to claim 7, wherein the energy ray-curable composition of the coating agent is a photocurable resin or a combination of a photocurable resin and a thermosetting resin. The coating agent for a water pressure transfer film.

11. The coating agent for a water pressure transfer film according to claim 7, wherein the coating agent further contains a matting agent. The coating agent for a water pressure transfer film.

12. The coating agent for a water pressure transfer film according to claim 7, wherein the coating agent further contains an additional resin component that imparts chemical resistance and / or physical resistance. The coating agent for a water pressure transfer film.

13. A water pressure transfer product characterized by having a decorative layer with a fine uneven surface formed by the method according to claim 1.

14. The water pressure transfer product according to claim 13, wherein the microfiber filler has a fiber diameter of 1.5 to 5.0 times the film thickness of the decorative layer and a fiber length of 1.5 to 10.0 times the fiber diameter. The water pressure transfer product.

15. A hydrostatic transfer product according to claim 13, wherein the microfiber filler is any one of cellulose fiber, glass fiber or carbon fiber.

16. A hydrostatic transfer product according to claim 13, wherein the energy ray curable resin composition of the coating agent used for the hydrostatic transfer is a photocurable resin or a combination of a photocurable resin and a thermosetting resin.

17. A hydrostatic transfer product according to claim 13, wherein the coating agent further contains a matting agent.

18. A hydrostatic transfer product according to claim 13, wherein the coating agent contains an additional resin component that imparts chemical resistance and / or physical resistance.

19. A hydrostatic transfer product according to claim 13, wherein the height of the convex portions of the fine irregularities of the decorative layer is 10 to 1000 μm.

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