JP3399700B2 - Hydraulic transfer method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is mainly applied to metal products,
The present invention relates to a hydraulic transfer method that is preferably used when painting various molded articles such as plastic molded articles and ceramic molded articles, and can paint on an extremely wide range of molded articles. In particular, the present invention relates to a hydraulic transfer method capable of forming a printed pattern layer having excellent adhesion even on the surface of a polyolefin molded body, which has been difficult to paint by this method.

[0002]

2. Description of the Related Art In particular, there is a hydraulic transfer method as a method suitable for painting with a printing layer on various molded products having a three-dimensional surface (three-dimensional surface) or a curved surface due to unevenness. The hydraulic transfer method is a primer that can dissolve or swell the printed pattern layer into a fluid state on the printed pattern layer of a hydraulic transfer sheet comprising a water-soluble or water-swellable film having a printed pattern layer on the surface ( (Sometimes called an activator), and then float this hydraulic transfer sheet on water with the printed pattern layer side facing up, and at the stage when the fluidized printed pattern layer extends onto the water surface. This is a method in which a molded article, which is a transfer target, is pushed in from the upper surface thereof, and the printed pattern layer in a fluidized state and extended is transferred to the surface of the molded article by hydraulic pressure. 58798, Japanese Patent Publication No. 2
It is already known from the publication of -32160.

The primer used in the above-mentioned hydraulic transfer method is an organic solvent capable of dissolving (or swelling) the printed pattern layer formed on the hydraulic transfer sheet, and a viscosity for efficiently proceeding the transfer step. A binder resin that can satisfactorily adhere the printed pattern layer after adjustment and transfer to the surface of the transfer target is an essential component, and if necessary, the printed pattern layer fluidized by applying a primer spreads on the water surface. In general, a plasticizer for improving the above-mentioned problem, an extender pigment for preventing coating film cracking of the printed pattern layer which occurs in a drying step after transfer, and the like are blended.

[0004]

By the way, in the above-mentioned conventional hydraulic transfer method, the primer used is a non-polyolefin plastic such as ABS resin, polycarbonate resin or In the case of vinyl resin, acrylic resin, etc., it is possible to form a practically satisfactory adhesive printed pattern layer on the surface of the molded product, but when the material of the molded product is a polyolefin resin such as polyethylene or polypropylene. However, there was a problem that the transferred printed pattern layer had extremely low adhesion and could not be put to practical use.

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have a problem in the above-mentioned conventional hydraulic transfer method, that is, it is difficult to form a printed pattern having excellent adhesiveness on the surface of a polyolefin resin molded article. As a result of further studies to eliminate this problem, when chlorinated polyolefin, which is said to exhibit good adhesion to polyolefin-based plastics, is used as the binder resin for the above-mentioned primer, the adhesion of the printed pattern layer is greatly increased. I found that it can be improved.

However, since chlorinated polyolefin is generally hydrophobic, it is difficult to dissolve it in a hydrophilic organic solvent. Therefore, the solvent composition of a primer using a chlorinated polyolefin resin as a binder resin is inevitable. Therefore, it is inevitable to use a hydrophobic organic solvent. A primer constituted by using such a hydrophobic organic solvent has a drawback that when the hydraulic transfer sheet is floated on the water surface, the printed pattern layer formed on the transfer sheet is difficult to spread uniformly and satisfactorily on the water surface. As a result, it has been found that there is a new problem that only an unclear transfer pattern in which the print pattern layer is broken is obtained. The present invention has been made in view of the above circumstances, and it is possible to form a clear printed pattern with excellent adhesiveness even for a polyolefin resin molded product which was difficult to paint by a conventional hydraulic transfer method. The purpose of the present invention is to provide a hydraulic transfer method.

[0007]

In order to solve the above-mentioned problems, the hydraulic transfer method of the present invention comprises the above-mentioned printing of a transfer sheet formed by forming a printed pattern layer on a substrate made of a water-soluble or water-swellable film. On the pattern layer, a step of applying a primer that dissolves or swells the printed pattern layer, a step of floating the transfer sheet on the water surface so that the printed pattern layer is the upper surface, and a step of applying the primer and floating on the water surface Pressing the transfer target from above the transferred sheet and adhering the print pattern layer to the surface of the transfer target by hydraulic pressure; and removing the base material after adhering the print pattern layer to the transfer target. In the hydraulic transfer method including the step of: wherein the primer is 5 to 50% by weight of alkoxy. (Poly) alkylene glycol mono (meth) acrylate, Graft copolymer of 5 to 50 wt% pyrene resin and the polymerizable unsaturated group-containing vinyl compounds 0-90% by weight and is characterized in that comprising a binder resin. Examples of the alkoxy / (poly) alkylene glycol / mono (meth) acrylate include alkoxy / polyethylene glycol /
Monomethacrylate is preferred. The chlorinated polypropylene preferably has a chlorination rate of 15 to 50%. As the polymerizable unsaturated group-containing vinyl compound,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, (meth) acrylic acid-tert
-Butyl, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid-n
-At least one selected from the group consisting of lauryl, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate is particularly preferably used. The printed pattern layer may be composed of an underprinted print layer formed on the base material and a printed layer having a pattern formed on the underprinted print layer. Further, a top coat layer may be formed on the printed pattern layer of the transfer target having the printed pattern layer transferred to the surface thereof.

[0008]

In the hydraulic transfer method of the present invention having the above-mentioned structure,
As a binder resin, chlorinated polypropylene resin,
A major feature is that it is composed of a copolymer obtained by graft-polymerizing alkoxy / (poly) alkylene glycol / mono (meth) acrylate. Since the alkoxy (poly) alkylene glycol mono (meth) acrylate used here is hydrophilic, the chlorinated polypropylene resin can be rendered hydrophilic by grafting. Therefore, even when the organic solvent composition of the primer is a hydrophobic organic solvent, the printed pattern layer can be uniformly and sufficiently spread on the water surface, and excellent adhesion to the polyolefin resin molded product can be obtained.

[0009]

The present invention will be described in detail below. The base material of the transfer sheet used in the present invention absorbs water by floating on the water surface to swell or dissolve, and when an object is pushed in from above the film floating on the water surface,
A water-soluble film or a water-swellable film is used which has the property of being easily spread and deformed along the shape of an object and which can be subjected to a normal printing process. In particular,
Including polyvinyl alcohol resin, dextrin, gelatin, glue, casein, shellac, gum arabic,
Starch, protein, polyacrylic acid amide, sodium polyacrylate, polyvinyl methyl ether, copolymer of methyl vinyl ether and maleic anhydride, copolymer of vinyl acetate and itaconic acid, polyvinylpyrrolidone, or cellulose, acetyl cellulose, acetyl butyl Cellulose, carboxymethyl cellulose, methyl cellulose,
Cellulose derivatives such as hydroxyethyl cellulose,
A water-swellable or water-soluble film having a thickness of about 10 to 100 μm, such as a single resin or a mixed resin such as sodium alginate, or a film, a nonwoven fabric, a cloth,
Coating on a substrate sheet having the property of absorbing or absorbing liquid, particularly water, such as various porous films, or
Alternatively, a laminated sheet in which the water-swellable or water-soluble film is laminated on the base sheet is used.

The polyvinyl alcohol resin film has various mechanical strengths required for printing and moisture resistance during handling by changing various conditions such as the degree of polymerization, the degree of saponification, and the addition of additives such as starch. It is possible to control the speed of softening due to water absorption after floating on water, the time required for spreading or diffusing, the ease of deformation during transfer, and the like. For example, a more preferable film containing a polyvinyl alcohol (PVA) resin as a main component has a composition of PVA 80%, polymeric water-soluble resin 15%, and starch 5%, and has an equilibrium water content of about 3%.

For forming the printed pattern layer in the present invention, a printing ink containing the following binder resin as a binder component is preferably used. Examples of the binder resin used in the printed pattern layer include thermoplastic urethane resins such as polyester urethane, acrylic urethane, and polycarbonate urethane, or a mixture of two or more resins, polymethylmethacrylate, polyethylmethacrylate, and polyethylmethacrylate. Acrylic resins such as butyl methacrylate are used alone or as a mixture of two or more kinds, or the above-mentioned thermoplastic urethane resins and acrylic resins are the main components, and cellulose derivatives such as nitrocellulose and cellulose acetate, polyester A mixed resin in which a binder for addition such as resin, vinyl chloride, vinyl acetate copolymer resin is mixed is used.

A printing ink containing the binder resin but no colorant, or a hydrocarbon resin such as polyethylene wax or paraffin, a fatty acid amide, a fatty acid, a fatty alcohol and its ester is added. A transparent underprinting layer can be obtained by forming the printed pattern layer using the existing printing ink or the like.

The primer used in the present invention contains, as a binder resin, 5 to 50% by weight of alkoxy. (Poly) alkylene glycol mono (meth) acrylate, 5 to 50% by weight of chlorinated polyolefin resin, and a polymerizable unsaturated group-containing group. It contains a graft polymer composed of 0 to 90% by weight of a vinyl compound. Specific examples of the alkoxy (poly) alkylene glycol mono (meth) acrylate that can be used in the present invention include 2-methoxyethyl methacrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, methoxydiethylene glycol acrylate, methoxytriacrylate. Ethylene glycol acrylate, methoxytetraethylene glycol acrylate, methoxydipropylene glycol acrylate, ethoxydiethylene glycol acrylate, etc., and NOF CORPORATION's trade name Bremmer PME-100, PME-200 or PME-200.
-400 and the like can be used, and these can be used alone or in combination of two or more.

Among the above-mentioned alkoxy. (Poly) alkylene glycol.mono (meth) acrylates, alkoxy. (Poly) ethylene glycol monomethacrylate is derived from the hydrophilicity / hydrophobicity of the side chain group on the water surface of the printed pattern layer. Since it is excellent in both the spreadability and the stability of the primer itself due to the compatibility with chlorinated polypropylene, in the present invention, alkoxy polyethylene glycol monomethacrylate, specifically, methoxydiethylene glycol acrylate, It is particularly preferable to use methoxytriethylene glycol acrylate, methoxytetraethylene glycol acrylate, ethoxydiethylene glycol acrylate, etc., and Bremmer PME-200 under the trade name of NOF CORPORATION.

The chlorinated polyolefin resin that can be used in the present invention is not particularly limited and can be appropriately selected from those having various chlorination rates and used. However, when the chlorination rate of the chlorinated polyolefin resin is lower than 15%, the solubility in an organic solvent and the storage stability when used as a primer are lowered, and when the chlorination rate is higher than 50%, a polyolefin-based resin is used. In the present invention, it is preferable to use a chlorinated polyolefin resin having a chlorination ratio in the range of 15 to 50% because the adhesion to the substrate tends to decrease.

The polymerizable unsaturated group-containing vinyl compound that can be used in the present invention is not particularly limited, and any compound having a polymerizable unsaturated bond can be used. Specific examples include styrene, α-methylstyrene, vinyltoluene, (meth) acrylic acid, hydroxyethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, amyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid Examples thereof include isobornyl, vinyl chloride, vinyl acetate, dimethyl fumarate, diethyl fumarate, vinyl propionate, dimethyl itaconate and diethyl itaconate, and these can be used alone or in combination of two or more. Among these vinyl compounds, methyl (meth) acrylate, ethyl (meth) acrylate,
(Meth) acrylic acid-n-butyl, (meth) acrylic acid-iso-butyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid hexyl, (meth) acrylic acid-2-ethylhexyl, (meth) Acrylic acid-n-lauryl, cyclohexyl (meth) acrylate, (meth)
Preference is given to using isobornyl acrylate.

In the graft copolymer contained in the binder resin constituting the primer, the alkoxy polyalkylene glycol mono (meth) acrylate is 5
When it is less than 50% by weight, the hydrophilicity of the binder resin to be obtained is deteriorated, so that the spreadability of the printed pattern layer on the water surface is impaired. The adhesion to the substrate is impaired and the storage stability when used as a primer is deteriorated. Further, if the amount of chlorinated polypropylene resin is less than 5% by weight, the adhesion to the polyolefin-based substrate will be reduced, and if it is more than 50% by weight, the hydrophobicity of the binder resin will be strengthened, so that the spreadability of the printed pattern layer on the water surface will increase. It will be damaged. When the amount of the polymerizable unsaturated group-containing vinyl compound is more than 90% by weight, both the adhesiveness to the polyolefin-based substrate and the spreadability of the printed pattern layer on the water surface are impaired.

The above-mentioned graft copolymer is generally prepared by adding a predetermined amount of an alkoxy polyalkylene glycol mono (meth) acrylate and a polymerizable unsaturated group-containing vinyl compound to a chlorinated polypropylene resin in an organic solvent solution. In addition, it can be produced by a known polymerization method in the presence of an appropriate polymerization initiator. As an example, 70 to 10
It is preferable to carry out solution polymerization at 0 ° C. In this case, as a polymerization solvent, an aromatic hydrocarbon such as toluene or xylene is mainly used, and if necessary, cyclohexane, methylcyclohexane, methyl isobutyl ketone, butyl acetate or the like is used in combination. You can Further, as the polymerization initiator used at that time, benzoyl peroxide, organic oxide such as t-butyloxy-2-ethylhexanoate, azobisisobutyronitrile, dimethyl-2,2 ′
Examples include azo compounds such as azobisisobutyrate.

The binder resin thus obtained can be used as a primer for hydraulic transfer by mixing it with an appropriate organic solvent. Any organic solvent can be used as long as it can dissolve the graft copolymer and can also dissolve (or swell) the printed pattern layer formed on the transfer sheet. But good. Specific examples of the organic solvent that can be used, pentane, hexane, heptane, octane, mineral spirits, toluene, xylene, cyclohexane, ethylbenzene, tetralin,
Decalin, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, benzyl alcohol, diacetone alcohol, ethylene glycol, propylene glycol, glycerin,
Methyl acetate, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, ethyl ether, isopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Diethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl Ether, propylene glycol monomethyl ether acetate, and Idemitsu Kosan Co., Ltd. super sol series (trade name) and the like, which may be used by mixing one or two or more kinds.

The organic solvent must be kept at a viscosity suitable for transfer at least until the print pattern layer on the transfer sheet is in a fluidized state and transferred to the transfer step, and the print pattern after transfer is maintained. In the step of drying the layer, it is desirable that the organic solvent to be used is well covered with a solvent and easily dried. Therefore, the boiling point range of the organic solvent used is preferably 50 to 300 ° C. 30% by weight preferably contains a high boiling solvent of 200 to 300 ° C.

There is no particular limitation in producing a primer for hydraulic transfer using such a binder resin. Generally, the above graft copolymer and an organic solvent are used in an amount of 5 to 50% by weight of the graft copolymer and 50 to 95 of an organic solvent.
It is obtained by mixing in the range of% by weight. The primer obtained by the above composition can be used as it is as a primer for dissolving the printed pattern layer on the transfer sheet, but it is preferable to further add an inorganic fiber and a plasticizer to the primer, if necessary. The inorganic fibers are useful for preventing the occurrence of coating film cracks when the printed pattern transferred to the surface of the molded article is dried, and the plasticizer has the effect of improving the spreadability of the printed pattern layer on the water surface.

The inorganic fiber used in the primer is 5 to 30 parts by weight based on 100 parts by weight of the binder resin.
It is preferable to use it in the range of 20 parts by weight and the plasticizer in the range of 20 to 100 parts by weight. The inorganic fiber that can be used is not particularly limited, and generally has a fiber diameter of 0.5 to 1.0 μm and a fiber length of 10 to 30.
It is preferably about μm, and specific examples thereof include Arbolex YS series and M series manufactured by Shikoku Chemicals Co., Ltd. In addition, specific examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, dioctyl adipate, dioctyl sebacate, epoxy plasticizers, trimellitic acid plasticizers, polyester plasticizers and the like.

Further, for the primer, a resin (for example, an organic solvent-soluble thermosetting acrylic resin or a thermoplastic acrylic resin) other than the above graft copolymer, a pigment (for example, talc, mica, calcium carbonate) is used. , Clay, barite, etc.) and various other additives known in paint applications (eg, dispersants, defoamers,
It is acceptable to add a surfactant or the like) within a range that does not impair the characteristics of the primer.

In the present invention, the water used for floating the transfer sheet is adjusted to an appropriate temperature depending on the properties of the water-soluble or water-swellable film which is the base material in the transfer sheet. For example, if a starch film (trade name: Oblate) is used as the water-soluble film, the water temperature is 3
It is desirable that the temperature is 0 to 40 ° C., and in order to accelerate the dissolution at the time of removing the film, an amylase or the like is added to 2 to 40 ° C.
It is preferable to add about 4%.

Various molded products can be used as the transferred material in the present invention. The resin molded article may be made of a non-polyolefin resin or a polyolefin resin, for example, ABS resin, polystyrene resin, polycarbonate resin, AES.
Resin (ABS resin with improved weather resistance), polypropylene resin, polyethylene resin, polyphenylene oxide resin,
Injection molding and extrusion molding of synthetic resins, melamine resins, phenol resins, formalin resins, urea resins, fibrous resins, etc., consisting of homopolymers or copolymers of polyvinyl chloride resins, etc. or mixtures selected from these. Various synthetic resin molded products such as hollow molded products and vacuum molded products can be used. Also, metal products,
It is also possible to use a ceramic molded product or the like. Furthermore, those having concave or convex portions, those having flat surfaces, those having a two-dimensional or three-dimensional curved surface, those having through holes, those having a lattice shape, and the like of most shapes can be used.
It is also possible to use a material having a fine embossing for producing a texture such as wood, stone, or a building on the surface.

The hydraulic transfer method of the present invention will be described below. FIG. 1 is an explanatory view showing an embodiment of the hydraulic transfer method of the present invention. First, the print pattern layer 2 is formed on the base material 1 by an appropriate printing method such as a gravure printing method to form the transfer sheet 3. Here, the printed pattern layer 2 may directly form the printed pattern layer 2 having a pattern on the substrate 1 by using a printing ink containing a colorant, or a printing ink containing no colorant, or After forming a transparent underprinting layer using a printing ink that contains a hydrocarbon resin such as polyethylene wax, paraffin, fatty acid amides, fatty acids, fatty alcohols and their esters, etc., this underprinting is performed. A printed pattern layer having a pattern may be formed on the printed layer by using a printing ink containing a colorant.

Next, on the printed pattern layer 2 of the transfer sheet 3,
The primer 4 is applied by a known coating method such as brush coating, spray coating, roll coating, curtain flow coating, and gravure coating so that the wet coating film thickness is about 10 to 30 μm. Then, when the printed pattern 2 layer is in a fluid state, the transfer sheet 3 is floated on the water surface so that the printed pattern layer 2 is the upper surface as shown in FIG. In the present invention, in order to float the transfer sheet 3 on the surface of the water, it is possible to float the sheet-shaped ones one by one, or it is possible to continuously float the roll-shaped one while flowing water in one direction. . In this step, the base material 1 of the transfer sheet 3 is floated downwards, that is, the printed pattern layer 2 is on the upper surface, and is floated on the water surface. At this time, air bubbles are generated between the transfer sheet 3 and the water surface. It is necessary to prevent the transfer sheet 3 from entering and to prevent the transfer sheet 3 itself from wrinkling.

After that, when the printed pattern layer 2 is spread on the water surface, the molded article 5 as the transfer target is pushed into the water from above. At this time, it is necessary to prevent bubbles from entering between the transfer sheet 3 and the molded product 5. A part or all of the molded product 5 is settled in water, and the transfer sheet 3 extends along the surface shape of the molded product 5. And
When the transfer sheet 3 is brought into close contact with the surface of the molded product 5 by the water pressure, the printed pattern layer 2 on the upper surface is bonded to the surface of the molded product 5. Here, in the step of pushing the molded product 5 into water, before the printed pattern layer 2 which is brought into a fluid state by the primer and is spread on the water surface is inactivated by drying, that is, the printed pattern layer 2 is wet. Of course, it is carried out before losing the sex.

Thus, after the printed pattern layer 2 is transferred to the surface of the molded product 5, the molded product 5 is taken out of water, and the substrate 1 remaining on the printed pattern layer 2, that is, the water-soluble or water-swellable film remains. Remove things. In order to remove the base material 1, shower cleaning of the molded product 5 with water is the most efficient and preferable method. As a result, the base material 1 attached to the molded product 5 is completely removed, and the stains generated during transfer are also washed. The water temperature at this time varies depending on the material of the substrate 1 used, etc., but is generally 15-60.
C. is suitable, and a cleaning time of about 1 to 10 minutes is sufficient.

Then, by drying and removing water droplets adhering to the molded product 5, a molded product whose surface is decorated with the printed pattern layer 2 as shown in FIG. 2 is obtained. Further, if necessary, a drying top coat layer for protection may be preferably formed on the surface of the printed pattern layer 2 transferred to the molded article 5 after the water droplets are dried and removed. The top coat layer can be formed, for example, by an ordinary coating means using a thermosetting urethane resin or acrylic resin as a coating film component.

In the above embodiment, the transfer sheet 3 was floated on the water surface after the primer 4 was applied on the transfer sheet 3, but in the method of the present invention, these steps may be reversed. There is no such thing. That is, after the transfer sheet 3 is floated on the water surface so that the printed pattern layer 2 is the upper surface,
A primer may be applied on the printed pattern layer 2.

Hereinafter, manufacturing examples and examples according to the present invention will be described. The copolymerization ratio or mixing ratio of each component is shown in parts by weight unless otherwise specified. [Production Example of Binder Resin Constituting Primer] A 1-liter four-necked flask equipped with a stirrer, a cooler and a monomer dropping device was charged with each component of the composition (A) shown in Table 1 below and stirred, The inner temperature was raised to 90 ° C, and the temperature was further held at 90 ° C for 20 minutes. Then the monomer mixture of composition (B) was added dropwise over 1 and a half hours
After the dropping was completed, the component of the composition (C) was added, and the mixture was kept at 90 ° C. for 3 hours to complete the polymerization. Next, the copolymer solution is diluted with toluene as a diluent, and the binder resin solutions V1 to
V5, W1 and W2 were obtained.

[0033]

[Table 1]

[Preparation Example of Primer] Using each of the binder resin solutions (V1 to V5, W1 and W2) obtained above, the components were uniformly mixed with the compositions shown in Table 2 below to prepare a primer.

[Example 1] Polyvinyl alcohol film (Hiselon C-300 manufactured by Nigo Film Co., Ltd.)
A gravure printing ink containing a mixed resin of 40 parts by weight of polybutyl methacrylate resin, 50 parts by weight of polyethyl methacrylate resin, and 10 parts by weight of nitrocellulose as a binder component on a base material made of The print pattern layer thus formed was formed by a gravure printing method to obtain a transfer sheet. On the printed pattern layer of the obtained transfer sheet,
The primer (Example No. 1) shown in Table 2 below was applied by a gravure coating method so as to have a wet film thickness of 15 μm. Before the printed pattern layer, which has been wet by the action of the primer, dries, transfer the sheet to a water temperature of 30 ° C.
The printed pattern layer was floated on the water surface of. Here, the spread state of the printed pattern layer when the transfer sheet was floated on the water surface was visually observed and evaluated according to the following evaluation criteria.
The results are shown in Table 2 below (spreadability). ○: The pattern is not distorted and spreads in a highly uniform state. ◇: The pattern is slightly distorted, but it is not a problem in practical use. △: The dispersibility is insufficient, and part of the pattern is also recognized.

Subsequently, after the base material swells, a polypropylene resin three-dimensional molded article is pushed in from above the transfer sheet to bring the transfer sheet into close contact with the molded article, and the printed pattern layer is adhered to the surface of the molded article by water pressure. It was Then, the molded product was pulled out from water, and a shower having a water temperature of 30 ° C. was sprayed on the molded product to remove the base material remaining on the surface. Furthermore, with a blower at 80 ° C for 20 minutes,
Water droplets adhering to the surface were removed and the printed pattern layer was dried to obtain a molded product having the printed pattern layer transferred to the surface.

The appearance of the printed pattern layer formed on the surface of the obtained molded product was visually observed and evaluated according to the following evaluation criteria. The results are shown in Table 2 below (transferability). ○: There is no pattern break and a clear printed pattern is formed. ◇: A range where pattern breaks occur very slightly but are not a practical problem. △: Pattern breaks occur and a uniform pattern appearance cannot be obtained. Regarding the adhesion of the pattern layer, JIS-K-540
0, an adhesion test (clearance interval 1 mm, number of squares 100) was carried out by the "8.5.1 cross cut method", and the evaluation was made according to the following evaluation criteria. The results are shown in Table 2 (Adhesiveness) below. ◯: No trace of peeling was observed, and the adhesion was extremely good (10
0/100) ◇; Adhesion is good with slight cracks in the coating along the cut surface (100/100) △: Slight peeling is observed, but practical use range (90
Or more / 100) x: Peeling is recognized (less than 90/100)

[Examples 2 to 6] In the above Example 1,
A molded article having a printed pattern layer transferred to the surface was obtained in the same manner except that the primer (Example Nos. 2 to 6) shown in Table 2 below was used as the primer. The spreadability, transferability, and adhesion of the printed pattern layer were also evaluated in the same manner as in Example 1. The results are summarized in Table 2 below.

[Comparative Examples 1 and 2] In the above Example 1,
A molded article having a printed pattern layer transferred to the surface was obtained in the same manner except that the primer (Comparative Example Nos. 1 and 2) shown in Table 2 below was used as the primer. The spreadability, transferability, and adhesion of the printed pattern layer were also evaluated in the same manner as in Example 1. The results are summarized in Table 2 below.

[0040]

[Table 2]

From the results shown in Table 2, according to the hydraulic transfer method of the present invention, even if the organic solvent composition of the primer is composed of a hydrophobic solvent, the spreadability of the printed pattern on the water surface is good and the pattern collapses. A clear transfer pattern can be formed without
In particular, it was found that a printed pattern layer having excellent adhesiveness can be formed even on a polyolefin-based resin molded product that is not surface-treated to increase the adhesiveness.

Example 7 A molded product having a printed pattern layer transferred to the surface thereof was obtained in the same manner as in Example 1 except that a polystyrene resin molded product was used as the molded product. An acrylic type coating was applied on the printed pattern layer of the obtained molded product to form a top coat layer. The obtained molded product had excellent surface properties such as moisture resistance, light resistance, and chemical resistance.

Example 8 Polyvinyl alcohol film (Hiselon C-300 manufactured by Nigo Film Co., Ltd.)
On a substrate consisting of, a transparent underprinting layer for solid printing is formed by a gravure printing ink containing a binder component consisting of polymethylmethacrylate resin and polyethylene wax, and then on the underprinting layer. The gravure printing ink containing 40 parts by weight of polybutyl methacrylate resin, 50 parts by weight of polyethyl methacrylate resin, and 10 parts by weight of nitrocellulose as a binder component is used to gravure a printed pattern layer having a pattern. A transfer sheet was formed by a printing method. The printed pattern layer of the obtained transfer sheet was coated with the primer (Example No. 1) shown in Table 2 so as to have a wet film thickness of 15 μm by the gravure coating method. The transfer sheet was floated on the water surface at a water temperature of 30 ° C. so that the printed pattern layer was the upper surface before the printed pattern layer that was wet by the action of the primer was dried. Subsequently, after the base material swelled, a three-dimensional molded product made of ABS resin was pushed in from above the transfer sheet to bring the transfer sheet into close contact with the molded product, and the printed pattern layer was adhered to the surface of the molded product by hydraulic pressure. Then, the molded product was pulled out from water, and a shower having a water temperature of 30 ° C. was sprayed on the molded product to remove the base material remaining on the surface. Further, water drops adhering to the surface were removed and the printed pattern layer was dried by a blower at 80 ° C. for 20 minutes to obtain a molded product having the printed pattern layer transferred to the surface. The molded product thus obtained has a printed pattern layer consisting of a printed layer having a pattern and a transparent underprinting layer thereon, and the printed pattern on the surface of the molded product is clear. Yes, the adhesion of the printed pattern layer was also good

[Example 9] Polyvinyl alcohol film (Hiselon C-300 manufactured by Nigo Film Co., Ltd.)
A transparent solid underprinting layer is formed on a base material made of (1) by a gravure printing ink containing a binder component made of a mixed resin of 70 parts by weight of polyester resin and 30 parts by weight of nitrocellulose and polyethylene wax. Then, a printed pattern layer having a pattern is formed on the underprinted printing layer by a gravure printing method using a gravure printing ink containing a mixed resin of 70 parts by weight of polyester urethane resin and 30 parts by weight of nitrocellulose as a binder component. Formed into a transfer sheet. The printed pattern layer of the obtained transfer sheet was coated with the primer (Example No. 1) shown in Table 2 so as to have a wet film thickness of 15 μm by the gravure coating method. The transfer sheet was floated on the water surface at a water temperature of 30 ° C. so that the printed pattern layer was the upper surface before the printed pattern layer that was wet by the action of the primer was dried. Subsequently, after the base material swelled, a three-dimensional molded product made of ABS resin was pushed in from above the transfer sheet to bring the transfer sheet into close contact with the molded product, and the printed pattern layer was adhered to the surface of the molded product by hydraulic pressure. After this,
The molded product was pulled out from water, and a shower having a water temperature of 30 ° C. was sprayed on the molded product to remove the substrate remaining on the surface. Further, it is dried by a blower at 80 ° C. for 20 minutes to remove water droplets adhering to the surface,
A molded product having a printed pattern layer transferred to the surface was obtained. The molded product thus obtained has a printed pattern layer consisting of a printed layer having a pattern and a transparent underprinting layer thereon, and the printed pattern on the surface of the molded product is clear. Yes,
The adhesion of the printed pattern layer was also good

[Example 10] A two-component urethane type coating was applied on the printed pattern layers of the molded articles obtained in Examples 8 and 9 to form a top coat layer. The obtained molded product had surface properties excellent in moisture resistance, light resistance, and chemical resistance.

[0046]

Industrial Applicability As described above, the hydraulic transfer method of the present invention is characterized in that the transfer pattern sheet is formed by forming a print pattern layer on a base material made of a water-soluble or water-swellable film. A step of applying a primer that dissolves or swells the print pattern layer, a step of floating the transfer sheet on the water surface so that the print pattern layer is the upper surface, and an upper part of the transfer sheet on which the primer is applied and floated on the water surface. And a step of pressing the transfer target body from the substrate and adhering the print pattern layer to the surface of the transfer target body by water pressure, and a step of removing the base material after adhering the print pattern layer to the transfer body. In the transfer method, the primer is 5-50% by weight of alkoxy. (Poly) alkylene glycol.mono (meth) acrylate and 5-50 of chlorinated polypropylene resin. The amount% and a polymerizable unsaturated group-containing vinyl compounds 0-90 graft copolymer of wt% being characterized by containing as a binder resin.

Therefore, it is possible to easily and reliably paint a molded product having a three-dimensional surface (three-dimensionally shaped surface) or a curved surface due to unevenness, and it is possible to cope with mass production. It can also be applied to polyolefin resin molded products that have been difficult to apply the hydraulic transfer method in the past, especially to polyolefin resin molded products that are not subjected to surface treatment to increase adhesion, and transfer in a very wide range. It is possible to form a printed pattern layer having excellent adhesion to the body and having a clear pattern. Further, since the binder resin itself is imparted with hydrophilicity, even if the organic solvent composition of the primer is composed of a hydrophobic solvent, the spreadability of the printed pattern on the water surface is good, and the pattern collapse There is an advantage that a clear transferred pattern can be formed. Moreover,
Since the solvent composition of the primer does not necessarily have to be composed of a hydrophilic solvent, it is possible to reduce the cost of the primer by composing it with a hydrophobic solvent, and it is excellent in practicality.

If the printed pattern layer is composed of an underprinted print layer formed on the base material and a printed layer having a pattern formed on the underprinted print layer, the surface of the transferred material In this, a printed pattern layer having excellent surface physical properties is formed, which is composed of two layers including a printed layer having a pattern and a transparent underprinted printed layer thereon. Further, if a topcoat layer is formed on the printed pattern layer of the transfer target having the printed pattern layer transferred on the surface, desired surface properties can be imparted according to the application.

[Brief description of drawings]

FIG. 1 is an explanatory view showing an embodiment of a hydraulic transfer method of the present invention.

FIG. 2 is a cross-sectional view showing an example of a molded product obtained by the hydraulic transfer method of the present invention.

[Explanation of symbols]

1 ... Substrate, 2 ... Printed pattern layer, 3 ... Transfer sheet, 4
…… Primer, 5 …… Molded product (transferred material).

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masato Yamamori 12-1 Shirawase, Katsura-cho, Toyota-shi, Aichi Trinity Industry Co., Ltd. (56) Reference JP-A-9-76700 (JP, A) JP-A-6-16847 (JP, A) JP-A-63-197685 (JP, A) JP-A-63-60782 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B44C 1/175

Claims (6)

(57) [Claims] 1. A step of applying a primer that dissolves or swells the printed pattern layer on the printed pattern layer of a transfer sheet in which the printed pattern layer is formed on a substrate made of a water-soluble or water-swellable film. And a step of floating the transfer sheet on the water surface so that the printed pattern layer is on the upper surface, and pressing the transfer object from above the transfer sheet coated with the primer and floated on the water surface, the transfer object by hydraulic pressure. A step of adhering the printed pattern layer to the surface of the substrate, and a step of adhering the printed pattern layer to an object to be transferred and then removing the base material, wherein the primer is alkoxy (poly). 5 to 50% by weight of alkylene glycol mono (meth) acrylate,
A hydraulic transfer method comprising a graft copolymer comprising 5 to 50% by weight of a chlorinated polypropylene resin and 0 to 90% by weight of a vinyl compound containing a polymerizable unsaturated group as a binder resin. 2. The alkoxy. (Poly) alkylene glycol mono (meth) acrylate is alkoxy.
The hydraulic transfer method according to claim 1, wherein the hydraulic transfer method is polyethylene glycol monomethacrylate. 3. The hydraulic transfer method according to claim 1, wherein the chlorinated polypropylene has a chlorination rate of 15 to 50%. 4. The vinyl compound containing a polymerizable unsaturated group is methyl (meth) acrylate, ethyl (meth) acrylate, -n-butyl (meth) acrylate, -iso-butyl (meth) acrylate, (Meth) acrylic acid-ter
t-butyl, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid-
2. At least one selected from the group consisting of n-lauryl, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
The described hydraulic transfer method. 5. The printed pattern layer comprises an underprinted print layer formed on the base material, and a print layer having a pattern formed on the underprinted print layer. 1
The described hydraulic transfer method. 6. A hydraulic transfer, comprising forming a topcoat layer on the printed pattern layer of a transfer-receiving body having a printed pattern layer transferred on its surface by the hydraulic transfer method according to claim 1. Method.