JP3098533B2 - Transfer sheet by hydraulic transfer - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer sheet used in a step of transferring a printing layer using hydraulic pressure to the surface of various molded articles.

[Prior Art] As a means for applying a printing layer to a surface of a molded article having a complicated surface shape such as a three-dimensional surface (three-dimensional shape) or a curved surface due to unevenness, a liquid having a printing layer formed on the surface is used. After the transfer sheet by pressure is floated on the water surface (liquid surface) with the print layer surface of the transfer sheet facing upward,
There is known a method of transferring a print layer of a transfer sheet onto the surface of a molded article by pressing a predetermined molded article (transferred object) for transferring a print layer from above (Japanese Patent Publication No. Sho 52).
-41682, JP-B-60-58718), transfer by liquid pressure comprising a water-soluble or water-swellable support, and a printing layer using a water-insoluble resin formed on the support as a vehicle. Sheets are used.

In a conventional transfer method using a transfer sheet by hydraulic pressure, following a step of transferring a print layer of the transfer sheet to a transfer target, a top coat is applied on the print layer transferred to the transfer target. Thereby, the abrasion resistance of the transferred printing layer is improved.

[Problems to be Solved by the Invention] However, in the case where a step of applying a top coat to the transfer surface of the print layer is provided after the above-mentioned conventional hydraulic transfer step, there is a trouble in performing the top coat.

On the other hand, the present invention is a transfer sheet capable of forming a surface protection layer for protecting the surface of the transferred printing layer on the transfer printing layer simultaneously with the transfer of the printing layer by hydraulic pressure. In addition, the transfer layer formed on the water-soluble or water-swellable support has excellent flexibility and flexibility, and can be sufficiently stretched and deformed. Provided is a transfer sheet that has good adhesion between a transfer sheet and a transfer target in a transfer step by pressure and has good throwing power to a transfer surface.

[Means for Solving the Problems] The liquid pressure transfer sheet of the first invention comprises a water-soluble or water-swellable support, and a transparent to semi-conductive material formed of a water-insoluble resin formed on the support. A transparent surface protective layer, comprising a printing layer using a water-insoluble resin formed on the surface of the surface protective layer as a vehicle, and a film-forming component of the transparent to translucent surface protective layer, The vehicle of the printing layer using the water-insoluble resin as a vehicle is a butyl methacrylate polymer, an ethyl methacrylate polymer and a butyl methacrylate / ethyl methacrylate copolymer comprising at least one polymer selected from the group consisting of: is there.

The transfer sheet by liquid pressure of the second invention is the same as the transfer sheet of the first invention, except that the transparent to translucent surface protective layer made of a water-insoluble resin, that is, the film-forming component is a butyl methacrylate polymer And a surface protective layer comprising at least one polymer selected from the group consisting of an ethyl methacrylate polymer and a butyl methacrylate / ethyl methacrylate copolymer.

The liquid pressure transfer sheet according to the third aspect of the present invention is the liquid pressure transfer sheet according to the first or second aspect, wherein the printing layer on the surface of the surface protective layer, that is, the vehicle is butyl methacrylate. The printing layer comprising at least one polymer selected from a polymer, an ethyl methacrylate polymer and a butyl methacrylate / ethyl methacrylate copolymer contains a polyethylene wax having a molecular weight of 2,000 to 4,000.

In the transfer sheet by liquid pressure of the present invention having the above structure, the water-soluble or water-swellable support for forming the transfer layer composed of the surface protective layer and the print layer includes a water-soluble or water-swellable support. Films such as polyvinyl alcohol resin, dextrin, gelatin, glue, casein, shellac, gum arabic, starch, protein, polyacrylamide, sodium polyacrylate, polyvinyl methyl ether, copolymer of methyl vinyl ether and maleic anhydride, A film having a thickness of about 10 to 100 μm made of a copolymer of vinyl acetate and itaconic acid, polyvinylpyrrolidone, acetylcellulose, acetylbutylcellulose, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, sodium alginate or the like is used.

A transparent to translucent surface protective layer made of a water-insoluble resin formed on a water-soluble or water-swellable support, the film-forming component of the surface protective layer is a butyl methacrylate polymer,
It is composed of at least one polymer selected from an ethyl methacrylate polymer and a butyl methacrylate / ethyl methacrylate copolymer, and is provided on a surface of a water-soluble or water-swellable support by gravure printing, roll coating, It is formed to a thickness of about 1 to 20 μ by spray coating, various printing methods, and the like.

In the surface protective layer, lubricants, for example, waxes and waxes such as polyethylene wax, paraffin wax and montan wax, fluorine resins such as polyvinylidene fluoride and polytetrafluoroethylene, and silicone resins such as polysiloxane, When a lubricant such as talc is added to the surface protective layer, the releasing property of the lubricant is imparted to the surface protective layer, so that the surface protective layer can release external force when subjected to friction or scratching. Is played. Therefore, by providing a surface protective layer to which a lubricant is added, an effect of reducing the intrusion of external force into the transfer layer is exerted, so that the surface protective layer has abrasion resistance and scratch resistance.

The lubricant added to the surface protective layer does not impair the transparency or translucency of the surface protective layer with the lubricant, and furthermore, the compatibility with the solvent used when forming the surface protective layer and From the viewpoint of coating performance and the like, polyethylene wax is preferred, and the best results are obtained particularly when polyethylene wax having a molecular weight of 2,000 to 4,000 is added at a ratio of 2 to 15% by weight. When a polyethylene wax having a molecular weight of 5000 or more is used, the transparency of the surface protective layer is reduced.

The printing layer on the surface of the surface protective layer is a vehicle made of at least one polymer selected from a butyl methacrylate polymer, an ethyl methacrylate polymer and a butyl methacrylate / ethyl methacrylate copolymer, and coloring with a dye or pigment. Agents and other optional components such as plasticizers, stabilizers, waxes and greases,
A desiccant, an auxiliary desiccant, a curing agent, a thickener, a dispersant, a filler and the like are kneaded sufficiently with a solvent and a diluent, using an ink or a paint, for example, an intaglio printing method, a lithographic printing method, By means of letterpress printing, screen printing, brush coating, spatula coating, spray coating, etc.
It is formed into characters, symbols, etc.

[Effects of the Invention] The hydraulic transfer sheet of the present invention is used in the same manner as a conventional transfer sheet used for forming a transfer printing layer by hydraulic pressure, and includes a transfer object. After the printing layer and the transparent to translucent surface protection layer covering the printing layer are transferred to the transfer surface, the printing layer for decoration can be seen through the surface protection layer. .

That is, the transfer method using the transfer sheet by liquid pressure of the present invention floats the transfer sheet on the liquid surface, and activates the printing layer and the surface protection layer in the transfer sheet with an activator, Further, for example, an object to be transferred, such as a plastic molded product, a metal molded product, a wood molded product, glass, an inorganic molded product, or the like, is pressed onto the transfer sheet from above the liquid surface, so that the print layer and the surface of the transfer sheet are The activator for activating the print layer and the surface protective layer is used to transfer the protective layer to the transfer object, even after the transfer sheet is floated on the liquid surface, or the transfer sheet. Before floating on the liquid surface.

The activator for activating the print layer and the surface protective layer in the transfer sheet has a property of swelling or partially dissolving the vehicle used for the print layer and the film forming component used for the surface protective layer. A slow-drying solvent that has and does not dry until the transfer step with the transfer sheet is completed, such as cellosolve, cellosolve acetate, carbitol, carbitol acetate, butyl cellosolve, butyl carbitol, butyl cellosolve acetate Boiling point of butyl carbitol acetate, 100
A single or mixed solvent of a polyhydric alcohol solvent having a temperature of not less than ° C is used.

In the activator, a solvent having a boiling point of less than 100 ° C., such as ketones, is mixed with the above-mentioned slow-drying solvent to dissolve the film-forming components of the vehicle of the printing layer and the surface protective layer. By adding a resin of the same system as the vehicle of the printing layer in the transfer sheet, the transfer performance of the transfer sheet to the transfer object can be further improved.

Furthermore, by adding a plasticizer such as DOP or DBP to the activator, the penetration of the activator into the printing layer or surface protective layer of the transfer sheet can be increased, and by adding an extender, The coatability of the activator can be improved.

In addition, the transfer sheet by hydraulic pressure of each of the present invention is a film-forming component of a transparent to translucent surface protective layer made of the above-described water-insoluble resin, and a vehicle of a print layer formed on the surface protective layer. Since both are made of at least one polymer selected from butyl methacrylate polymer, ethyl methacrylate polymer and butyl methacrylate / ethyl methacrylate copolymer, the transfer layer transferred by hydraulic transfer is used. A certain surface protective layer and a printing layer have excellent flexibility and flexibility, and can cope with sufficient elongation and deformation.

For this reason, the transfer sheet by hydraulic pressure of the present invention is
The adhesiveness between the transfer sheet and the object to be transferred during the transfer step by liquid pressure is good, and the throwing power to the surface to be transferred is also good.

EXAMPLES Hereinafter, the specific structure of the hydraulic transfer sheet of the present invention will be described with reference to manufacturing examples, and a hydraulic transfer printing method using the transfer sheet will be described.

Example 1 Preparation of Transfer Sheet The surface of a polyvinyl alcohol resin film having a thickness of 40 μm was subjected to a gravure printing method using a printing ink having the following ink composition [1A] by 0.7 g (solid content) / m ^2.
After forming a solid surface protective layer on the entire surface of the present invention, a printing layer having an abstract pattern is formed on the surface of the surface protective layer by a gravure printing method using the following ink composition [1B]. An example transfer sheet [1] by liquid pressure was obtained.

Ink composition [1A] Butyl methacrylate / ethyl methacrylate copolymer ‥‥ 26 parts by weight polyethylene wax (molecular weight: 3000) ‥‥ 10 parts by weight methyl ethyl ketone ‥‥ 64 parts by weight Ink composition [1B] butyl methacrylate / ethyl methacrylate copolymer ‥ ‥ 10 to 20 parts by weight Face ‥‥ 10 to 60 parts by weight [Titanium oxide (white), carbon (black), isoindoline (yellow), quinacridone (red), cyanine (blue)] Methyl ethyl ketone ‥‥ 20 to 80 parts by weight Part Preparation of activator An activator having the following mixture composition [1C] was prepared.

Mixed composition [1C] (1) butyl cellosolve acetate ‥‥ 26 parts by weight (2) butyl carbitol acetate ‥‥ 26 parts by weight (3) butyl methacrylate polymer ‥‥ 8 parts by weight (4) dioctyl phthalate ‥‥ 20 parts by weight ( 5) Sedimentable barium sulfate ‥‥ 20 parts by weight Transfer printing by liquid pressure The activator of the mixed composition [1C] was applied to the printing layer surface side of the transfer sheet [1] by liquid pressure at 12 g / m ² . Then, the transfer sheet was floated on a water surface at a water temperature of 30 ° C. so that the printing layer surface on which the activator was applied was on the upper surface, and after one minute, the polystyrene resin molded body for the outer frame of the air conditioner was lifted up. Then, a transfer sheet was spread and adhered to the surface of the molded body.

Then, the polystyrene resin molded body with the transfer sheet extended and adhered to the surface is pulled out of the water, showered with warm water of 40 ° C. for 30 minutes, and further showered with clear water to remove the polyvinyl alcohol resin film of the transfer sheet. Then, the resultant was subjected to drying to obtain an outer frame of an air conditioner made of a polystyrene resin molded body to which a print layer of the transfer sheet and a surface protective layer covering the print layer were transferred.

Example 2 In the manufacturing process of the transfer sheet by the hydraulic pressure of Example 1, except that a polyethylene wax having a molecular weight of 1500 was used in place of the polyethylene wax having a molecular weight of 3,000 in forming the surface protective layer, a process corresponding to that of Example 1 was used. The same steps as those described above were carried out to obtain a transfer sheet [2] by hydraulic pressure which is another example of the present invention.

Example 3 In the step of manufacturing the transfer sheet by hydraulic pressure in Example 1, when forming the surface protective layer, instead of the 0.7 g (solid content) / m ² solid surface protective layer on the entire surface, 1.4 g (solid content) was used. ) / M ²
The same steps as those in Example 1 were carried out except that a solid surface protective layer was formed on the entire surface of Example 1 to obtain a transfer sheet [3] by hydraulic pressure which was another example of the present invention. .

Comparative Example 1 In the manufacturing process of the transfer sheet by hydraulic pressure of Example 1, except that the formation of the surface protective layer was omitted, the same process as the corresponding process of Example 1 was performed. To obtain a transfer sheet [4].

[Experiment] The friction fastness of the surface of a molded article having a transfer printing layer obtained using the transfer sheet by hydraulic pressure of Examples 1 to 3 and Comparative Example 1 was determined by the Gakushin-type friction fastness. A test was conducted using a tester, and the number of reciprocating frictional elements required until the abstract pattern consisting of the gravure printing layer applied to the surface of the molded body completely disappeared was measured. The transfer printing using the hydraulic transfer sheets according to Examples 2 to 3 and Comparative Example 1 was performed in the same manner as the hydraulic transfer printing procedure described in Example 1. The results are shown in Table 1.

The Gakushin-type friction fastness tester used a friction cloth (Kanakin No. 3) on the surface and reciprocated six friction elements with a load of 200 g at a speed of about 30 times / minute. It was done.

[Effects of the Invention] As is clear from the examples and comparative examples, according to the hydraulic transfer sheet of the present invention, the surface is protected on the surface of the print layer transferred simultaneously with the transfer of the print layer by the hydraulic pressure. Since the surface protective layer is formed, a painted molded article having a surface excellent in abrasion resistance can be obtained without complicated work.

Further, in the transfer sheet by hydraulic pressure of the present invention, the film forming component of the surface protective layer and the vehicle of the printing layer are both butyl methacrylate polymer, ethyl methacrylate polymer and butyl methacrylate / ethyl methacrylate copolymer. Since the transfer layer is composed of at least one polymer selected from the group consisting of a surface protective layer and a printing layer, the transfer layer has excellent flexibility and flexibility, and has sufficient elongation and deformation. Can respond to.

For this reason, the transfer sheet by hydraulic pressure of the present invention is
The adhesiveness between the transfer sheet and the object to be transferred during the transfer step by liquid pressure is good, and the throwing power to the surface to be transferred is also good.

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) B44C 1/175

Claims (3)

(57) [Claims] 1. A water-soluble or water-swellable support, a transparent to translucent surface protective layer formed of a water-insoluble resin formed on the support, and a surface formed on the surface of the surface protective layer. It consists of a printing layer using a water-insoluble resin as a vehicle, and the film-forming component of the transparent to translucent surface protective layer, and a vehicle of the printing layer using the water-insoluble resin as a vehicle.
A liquid pressure transfer sheet comprising at least one polymer selected from a butyl methacrylate polymer, an ethyl methacrylate polymer, and a butyl methacrylate / ethyl methacrylate copolymer. 2. The transfer sheet according to claim 1, wherein a lubricant is added to a transparent to translucent surface protective layer made of a water-insoluble resin. 3. The liquid according to claim 1, wherein a polyethylene wax having a molecular weight of 2,000 to 4,000 is added to the print layer formed on the surface of the surface protective layer. Transfer sheet by pressure.