JPH0737196B2 - Manufacturing method for painted products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a method for mainly painting various molded products such as metal products, plastic molded products, and ceramic molded products by a transfer method. In particular, the present invention provides a method for obtaining a painted molded article having excellent water resistance, wet heat resistance, and hot water resistance.

[Conventional technology]

In particular, a water-soluble film having an activated printed pattern layer on the surface is used as a means for painting with the printed pattern layer on the complex structure surface of various molded articles having a three-dimensional surface (three-dimensional shape) or a curved surface due to unevenness. A method for transferring the printed pattern layer onto the surface of the molded product by using water pressure by floating the transfer film described above on the water surface with the printed pattern layer surface of the film as the upper surface and pressing the molded product to be painted from the upper surface. Are known (Japanese Examined Patent Publication No. 52-41683 and Japanese Patent Laid-Open No. 5)
4-33115).

[Problems to be solved by the invention]

By the way, the printed pattern layer in the obtained molded product obtained by the above-mentioned transfer method is such that the printed pattern layer in the transfer film is simply transferred and fixed to the surface of the molded product to be painted. The molded pattern has poor water resistance, moist heat resistance, warm water resistance, etc., and thus has the drawback that it is not possible to obtain a painted molded article having high robustness.

On the other hand, the present invention solves the drawbacks of the conventional hydraulic transfer method, and particularly easily and reliably obtains a painted molded article having excellent properties in water resistance, wet heat resistance, and hot water resistance. Could provide a method.

[Means for solving problems]

According to the method for producing a decorative molded article of the present invention, the surface of the decorative molded article to be painted is a curable resin layer surface which is dry but has not yet been completely cured. That is used, and after transferring the printed pattern layer on the transfer film, forms a curable resin layer so as to cover the transferred printed pattern layer on the surface of the curable resin layer of the above-mentioned molded article base material. Then, the curable resin layers existing on both upper and lower sides of the printed pattern layer are completely cured.

That is, in the method for producing a decorative molded article of the present invention, a transfer film composed of a water-soluble or water-swellable film having a print pattern layer is prepared so that the print pattern layer surface of the transfer film is the upper surface. After floating on top, an activator containing a solvent that dissolves the print pattern layer in the transfer film is applied to the print pattern layer of the transfer film, or the activator is added to the print pattern layer of the transfer film. After coating, the first step of floating the transfer film on the water surface so that the print pattern layer surface of the film is the upper surface, and painting from the upper surface of the transfer film floating on the water surface. The surface to be coated is a curable resin layer surface which is dry but has not yet been completely cured. The second step of spreading and adhering to the outer peripheral surface by hydraulic pressure, and removing the water-soluble or water-swellable film in the transfer film to cure the printed pattern layer in the transfer film on the decorative molded article substrate. A third step of transferring to the resin layer surface, a fourth step of forming a curable resin layer so as to cover the transferred printed pattern layer on the curable resin layer surface of the decorative molded article substrate, and the printed pattern The fifth step is to completely cure the curable resin layers existing on both upper and lower sides of the layer.

The configuration of the present invention will be described below with reference to the drawings.

As shown in FIG. 1, the first step of the method for producing a decorative molded article of the present invention is to transfer a transfer film 3 comprising a water-soluble or water-lubricating film 2 having a printed pattern layer 1 to the transfer film 3. After the printed pattern layer 1 of the film 3 is floated on the water surface 5 of the water tank 4 with its upper surface facing upward, an activator 6 containing a solvent that dissolves the printed pattern layer 2 of the transfer film 3 is applied to the printed pattern layer 1 Or the activator 6 is applied to the print pattern layer 2 of the transfer film 3 and then the transfer film 3 is applied so that the print pattern layer 1 side of the film 3 is the upper surface. 5, the printed pattern layer 1 of the transfer film 3 is in a state of being covered with the activator 6, and the transfer film 3 is in a state of floating on the water surface 5. .

The transfer film 3 used in this step may be a film having a water-soluble or water-swellable film 2 and a printed pattern layer 1 formed on one surface of the film 2 as essential constituent elements. . Preferable specific examples of the water-soluble or water-swellable film 2 include polyvinyl alcohol resin, textulin, gelatin, glue, casein, serratum, gum arabic, starch, protein, polyacrylic acid amide, sodium polyacrylate, polyvinyl. Methyl ether, copolymers of methyl vinyl ether and maleic anhydride, copolymers of vinyl acetate and itaconic acid, polyvinylpyrrolidone, or cellulose derivatives such as cellulose, acetyl cellulose, acetyl butyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, alginic acid. A film having a thickness of about 10 to 100 μm, such as a soda resin or a mixed resin, can be used. The polyvinyl alcohol resin film has various mechanical conditions such as degree of polymerization, saponification, and addition of additives such as starch, mechanical strength required for printing, moisture resistance during handling, and water resistance. It is possible to control the speed of softening due to water absorption after being floated, the time required for spreading or diffusing, the ease of deformation during transfer, and the like. An example of a more preferable film containing a polyvinyl alcohol (PVA) resin as a main component is a composition of 80% PVA resin, 15% polymeric water-soluble resin and 5% starch, and an equilibrium water content of about 3%.

The water used for floating the transfer film 3 is adjusted to an appropriate temperature depending on the properties of the water-soluble or water-swellable film 2 constituting the film 3. For example, when a starch-based film (trade name: Oblate) is used as the water-soluble film, the water temperature is preferably about 40 to 50 ° C,
Further, it is preferable to add amylase or the like in an amount of about 2 to 4% in order to accelerate the dissolution at the time of removing the film.

As the ink composition for forming the printed pattern layer 1 on the surface of the water-soluble or water-swellable film 2, known ones can be used, and examples thereof include linseed oil, soybean oil and synthetic drying oil. Various fats and oils, ethyl cellulose,
Cellulose derivatives such as ethyl hydroxyethyl cellulose, cellulose acetate propionate, nitrocellulose, and cellulose acetate, polystyrene, styrene resins such as poly α-methylstyrene and styrene copolymer resins, polymethyl methacrylate, polyethyl methacrylate, polyacrylic acid. A homopolymer or copolymer resin of acrylic or methacrylic resin such as ethyl or polybutyl acrylate,
Rosin, rosin-modified maleic acid resin, rosin-modified phenolic resin, rosin ester resin such as polymerized rosin, polyvinyl acetate resin, coumarone resin, vinyltoluene resin,
Vinyl chloride resin, polyester resin, butyral resin,
Vehicle containing at least one selected from polyamide resin, vinyl chloride-vinyl acetate copolymer resin, polyvinylidene chloride, melamine resin, silicone resin, chlorinated rubber, rubber derivative of cyclized rubber, glue, casein, dextrin, zein, etc. Can be used. The ink composition is usually colored with a dye or a pigment, but in some cases, it may be colorless without coloring. or,
It may contain a pearl pigment, a metal powder, or the like for the purpose of producing a special effect. In order to form the printed pattern layer 1 as a combination of dots independent of each other, it is preferable to use gravure printing, gravure offset printing, screen printing, or the like. A printing plate prepared according to the shape of each point described above. Should be done using. Further, when forming the print pattern layer 1, the ink constituting each point flows in an undried state and the points do not connect to each other, so that the viscosity is higher than that in normal printing and the drying speed is higher. It is better to use fast ink. Further, in order to make the print pattern layer 1 have a desired thickness, it is preferable to use a plate having a large amount of ink transfer, but if the amount of ink transfer is excessive, dots may still be connected. Taking these points into consideration, taking the gravure printing method as an example, a gravure printing plate with a plate depth of about 20 μm to 50 μm and a cell width / bank width of about 5/2 and Zahn Cup No. 4 were used. Time required for outflow is 9 to 15
It is preferable to form the printed pattern layer 1 using an ink composition for about 2 seconds.

The activator 6 contains a solvent having a property of dissolving the printed pattern layer 1 in the transfer film 3, and an operation for transferring the printed pattern layer 1 of the transfer film 3 to the surface of the decorative molded article substrate 7. Does not evaporate until it is completed on the water surface 5, does not corrode the molded article base material 7, and is formed on the surface of the molded article base material 7 to be painted. It is preferable that the curable resin layer 8 contains a solvent having properties such that it does not dissolve rapidly. Specific examples of such a solvent include pentane, hexane, heptane, octane, and the like, or a mixed liquid of gasoline, petroleum, benzine, mineral spirits,
Aliphatic hydrocarbons such as petroleum naphtha, aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexane and ethylbenzene, halogenated hydrocarbons such as trichloroethylene, perchlorethylene, chloroform and carbon tetrachloride, methyl alcohol, Monohydric alcohols such as ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, benzylchol, diacetone alcohol, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl Ketones such as cyclohexanone and isophorone, ethyl ether, isopropyl ether, ethylene glycol mono-methyl ether, ethylene glycol mono-ethyl ether , Ethers such as diethylene glycol mono-methyl ether, diethylene glycol mono-ethyl ether, diethylene glycol mono-butyl ether, diethylene glycol di-butyl ether, ethylene glycol mono-methyl ether acetate, ethylene glycol mono-ethyl ether acetate , Diethylene glycol mono
Acetates such as methyl acetate, diethylene glycol / mono / ethyl ether / acetate, diethylene glycol / mono / butyl ether / acetate, esters such as butyrate, nitro hydrocarbons, nitriles, amines, other acetals, acids, furan Etc. are used alone or as a mixed solvent. As the activator, a resin soluble in the solvent in the activator, for example, a vinyl halide monomer such as vinyl chloride and vinylidene chloride, styrene and its derivatives, a vinyl ester monomer such as vinyl acetate, and allyl alcohol. And allyl esters, acrylic acid, methacrylic acid, itaconic acid,
Unsaturated carboxylic acids such as crotonic acid, maleic acid or fumaric acid, ester derivatives of the above unsaturated carbonic acids, nitrile derivatives or acid amide derivatives thereof, N-methylol derivatives of acid amide derivatives of the above unsaturated carboxylic acids and The same N-alkyl methylol ether derivative, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl isocyanate, allyl isocyanate, 2-hydroxyethyl-acrylate or -methacrylate, 2-hydroxypropyl-acrylate or -methacrylate, ethylene glycol-monoacrylate. Or-monomethacrylate, ethylene glycol-diacrylate or-dimethacrylate, maleic anhydride, itaconic anhydride, methyl vinyl ketone, butane Ene ethylene, propylene,
Thermoplastic resins such as homopolymers or copolymers of monomers such as dimethylaminoethyl methacrylate, vinyl pyridine, tert-butylaminoethyl methacrylate, monoallyl ethers of polyhydric alcohols, polyamide resins, polyester resins , Phenolic resins, melamine resins, urea resins, epoxy resins, diallyl phthalate resins, silicon resins, polyurethane resins and the like, or thermosetting resins or modified resins or initial condensation products thereof, natural resins, rosin and When an activator consisting of a swelling liquid to which a resin such as a derivative thereof, a cellulose derivative, a natural or synthetic rubber, or a petroleum resin is added in an amount of about 5 to 60% by weight of a solvent, the viscosity of the activator is used. The adjustment is easy, the coating means is not limited, and the printing pattern layer of the transfer film is not affected. Since the ink holding time is long, there is an advantage that the transfer process can take a long time. The activator may be applied by gravure coating, offset gravure coating, roll coating, bar coating, spray coating, ultrasonic coating, or the like, and the activator coating amount is about 1 to 50 g / m ² .

In order to float the transfer film 3 on the water surface, it is possible to float the sheet-shaped films one by one, or the roll-shaped film can be continuously floated on the water surface while flowing water in one direction. In this step, the print pattern layer 1 on the transfer film 3 is floated on the water surface so that
At this time, it is necessary to prevent bubbles from entering between the water-soluble or water-swellable film 2 of the transfer film 3 and the water surface 5 and to prevent the transfer film 3 from wrinkling.

In the second step of the method of the present invention, the surface to which the painting is applied in the direction of the arrow from above the transfer film 3 on the water surface in the first step has been dried but has not yet been completely cured. The curable resin layer 8 surface, which is not the curable resin layer 8, is lowered, and a part or all of the curable resin base material 7 is allowed to settle in water to form air bubbles between the transfer film 3 and the decorative molded article base material 7. The transfer film 3 is extended along the surface shape of the molded article base material 7 so as not to enter, and is brought into close contact with the curable resin layer 8 of the molded article base material 7 by hydraulic pressure.

The molded article base material 7 used in this step is, for example, ABS resin, polystyrene resin, polycarbonate resin, AES resin (ABS resin improved weather resistance), polypropylene resin,
Polyethylene resins, polyphenylene oxide resins, polyvinyl chloride resins and other homopolymers or copolymers, as well as synthetic resins consisting of mixtures selected from these, melamine resins, phenol resins, formalin resins, urea resins, fibrin Injection molded products such as resin
Various synthetic resin molded products such as extrusion molded products, hollow molded products, vacuum molded products, metal products, ceramic molded products, etc. can be used, but those with concave or convex parts or flat products Almost any shape such as one having a two-dimensional or three-dimensional curved surface, one having a through hole, one having a lattice shape can be applied, and further, for producing a texture of wood, stone, fabric, etc. on the surface. It is also possible to use those provided with minute embosses. The curable resin layer 8 in the molded article substrate 7 is a thermosetting resin such as a thermosetting acrylic resin, a polyurethane resin, an epoxy resin, a melamine resin, or a polyester resin, or a prepolymer having an ethylenically unsaturated bond in the molecule. Alternatively, it is formed by an ionizing radiation-curable composition comprising an oligomer, a monomer having an ethylenically unsaturated bond in the molecule, or a composition containing a mixture thereof as a main component. Examples of the prepolymer or oligomer having an ethylenically unsaturated bond in the molecule used in the above-mentioned ionizing radiation-curable composition include unsaturated polyesters, polyester acrylates, epoxy acrylates, urethane acrylates, polyol acrylates, Various acrylates such as melamine acrylate, polyester methacrylate, epoxy methacrylate, urethane methacrylate, polyol methacrylate, polyol methacrylate, various methacrylates such as melamine methacrylate, and the like. Examples of the monomer having an ethylenically unsaturated bond in the molecule include: Styrene-based monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate Acrylic esters such as butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, phenyl acrylate, etc., Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, etc., Unsaturation of acrylamide, methacrylamide, etc. Carboxylic acid amide, acrylic acid 2- (N, N-
Substituted amino alcohol esters of unsaturated acids such as dibenzylamino) ethyl, (N, N-dimethylamino) methyl methacrylate, 2- (N, N-diethylamino) propyl acrylate, ethylene glycol diacrylate, propylene glycol di Acrylate, neopentyl glycol diacrylate, 1,6-hexanediol di-acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, etc. Functional compounds and / or polythiol compounds having two or more thiol groups in the molecule, eg trimethylolpropane trithioglycolate , Trimethylolpropane lithiopropionate, pentaerythritol tetrathioglycolate and so on.

The curable resin layer 8 may be formed to have a thickness of about 2 to 100 μm, and is formed by means of spraying, depping, brush coating, or the like. In addition, the curable resin layer 8
It is necessary to satisfy the requirement that it is dried but has not yet been completely cured, and accordingly, it is in a semi-cured state or an uncured state.

After the printed pattern layer 1 is sufficiently fixed on the surface of the curable resin layer 7 of the decorative molded article substrate 7 in the second step, in the third step, the water-soluble or water-swellable film in the transfer film 3 is used. The step of removing 2 is carried out. In order to remove the water-soluble or water-swellable film 2 in the transfer film 3, it is the most efficient and preferable method to wash the transferred material with a shower so that the adhered film 2 can be completely removed. Is removed by
Dirt generated during transfer is also cleaned. At this time, the water temperature varies depending on the material of the water-soluble film used, but generally 15 to 60 ° C is suitable, and the cleaning time is 1 to 10 ° C.
Minutes are enough.

After transferring the printed pattern layer 1 to the surface of the curable resin layer 8 in the third step, the printed pattern layer 1 is transferred onto the transferred surface of the printed pattern layer 1.
The fourth step of forming a curable resin layer so as to cover the is carried out.

The formation of the curable resin layer in the fourth step can be carried out in exactly the same manner as the case of forming the curable resin layer 8 described above.

In the subsequent fifth step, the above-mentioned curable resin layer 8 and the curable resin layer formed in the fourth step are completely cured, and heat curing treatment or ionization of X-rays, γ-rays, electron beams, ultraviolet rays, etc. is performed. The irradiating treatment with sexual radiation is carried out according to the type of resin constituting the curable resin layer.

The decorative molded article indicated by reference numeral 9 in FIG. 2 is obtained by the above steps, and includes the decorative molded article base material 7,
A completely cured resin layer 18 formed on the surface of the molded article substrate 7, the printed pattern layer 1 transferred to the resin layer 18, and the printed pattern layer 18 are formed so as to cover the same. It is composed of a completely cured resin layer 10.

〔Example〕

Hereinafter, a specific configuration of the method of the present invention will be described with reference to examples.

Example 1 Cellophane [manufactured by Nigo Film Co., Ltd .: Hi-Selon C-31]
[0] was gravure printed with a gravure printing ink [KLCF Muki manufactured by Morohoshi Ink Co., Ltd.] on a printed pattern layer having a grain pattern of cedar, dried and wound to obtain a roll-shaped transfer film.

Next, an activator consisting of CF primer [made by Morohoshi Ink Co., Ltd.] was coated on the printed pattern layer surface of the transfer film at a rate of 13 g / m ² by a gravure printing method, and this was applied at a water temperature of 27
Float with the printed pattern layer on the water surface at ℃
After a second, the base material for the painted article to be painted was pressed in, and the transfer film was brought into close contact with the surface of the base material to transfer the printed pattern layer to the surface of the base material. In addition, the above-mentioned base material for decorative molding is
An aluminum plate having a resin layer composed of 20 g / m ² of epoxymelamine-based paint obtained by immersing a 6 μm-thick alumite-treated aluminum plate in epoxymelamine-based paint and drying it at 150 ° C. for 2 minutes is there.

After transferring the print pattern layer to the resin layer surface made of the epoxy melamine-based coating material of the base material, the base material for the painted article is drawn out of water, and a shower having a water temperature of 30 ° C. is sprayed on it.
The cellophane on the surface was removed, and the surface was dried at 40 ° C. for 20 minutes.

Next, an epoxy melamine-based paint is applied to the surface of the printed pattern layer of the above-mentioned molded article base material by a spraying method at a rate of 20 g / m ² , and further dried at 200 ° C. for 20 minutes, and the top and bottom of the printed pattern layer are coated. The epoxy melamine resin layer present on both sides was completely cured.

The printed pattern layer on the aluminum plate, which is the thus obtained decorative molded product, has excellent water resistance, resistance to moist heat and hot water resistance, and the decorative molded product was suitable for interior materials. .

Example 2 Cellophane [manufactured by Nigo Film Co., Ltd .: Hi-Selon C-31]
[0] was subjected to gravure printing with a gravure printing ink [KLCF] manufactured by Morohoshi Ink Co., Ltd., and dried and wound to obtain a transfer film in a roll form.

Then, an activator composed of CF primer (Moroshi Ink Co., Ltd.) was coated on the printed pattern layer surface of the transfer film at a rate of 13 g / m ³ by a gravure printing method, and this was applied at a water temperature of 27
Float with the printed pattern layer on the water surface at ℃, and after 80 seconds, press in the base material for the painted article to be painted, and attach the transfer film to the surface of the base material The printed pattern layer was transferred to. In addition, the above-mentioned base material for the molded article is a urethane resin-based paint (Origiplate Z manufactured by Origin Electric Co., Ltd.) applied to a molded article obtained by injection molding a polycarbonate resin by a spray gun and then dried at 60 ° C. for 20 minutes. It is a polycarbonate resin molded product having a urethane resin layer having a thickness of 20μ as illustrated.

After transferring the printed pattern layer to the urethane resin layer surface consisting of the urethane resin-based paint of the base material, draw out the base material of the painted molded product from water and spray a shower with a water temperature of 30 ° C to remove the cellophane on the surface. And further dried at 40 ° C. for 20 minutes.

Then, a urethane resin-based paint is applied to the printed pattern layer surface of the above-mentioned molded article base material by a spray method to form a urethane resin layer having a film thickness of 20 μ, and then dried at 80 ° C. for 30 minutes to obtain a printed pattern layer. The urethane resin layers on both upper and lower sides were completely cured.

The polycarbonate resin molded article thus obtained, which is a painted molded article, has a printed pattern layer having excellent water resistance, wet heat resistance, and hot water resistance, and is suitable as an automobile interior material.

[Operation and effect of the present invention]

The method for producing a decorative molded article of the present invention comprises the constitution as described above, and the transfer surface of the decorative molded article substrate to which the print pattern layer of the transfer film is transferred is dried. The surface of the curable resin layer is not completely cured, but the printed pattern layer on the transfer film is transferred to the surface of the curable resin layer by the hydraulic transfer method, and the printed pattern layer is further coated to cure. Is a method for producing a decorative molded article, which comprises forming a functional resin layer and finally completely curing the curable resin layers existing on both upper and lower sides of the printed pattern layer.

Therefore, in the manufacturing method of the decorative molded article of the present invention,
Even if the painting surface of the painted article base material to which painting is applied is a complicated surface such as a rotating cone, it can be easily carried out without being restricted by its shape. Since the formation of the print pattern layer transferred and formed on the surface is formed by a usual printing means on the water-soluble or water-swellable film which is the transfer film, the action of producing a fine pattern, It is effective.

Further, in the method for producing a decorative molded article of the present invention, the fixing strength between the printed pattern layer and the decorative surface of the decorative molded article substrate is high, and the entire surface of the printed pattern layer is completely cured. Since a molded article coated with a curable resin layer can be obtained, it is possible to obtain a printed pattern layer having an extremely excellent action particularly on water resistance, wet heat resistance, warm water resistance, etc. It is a thing.

[Brief description of drawings]

FIG. 1 is a model cross-sectional view illustrating an intermediate step in one embodiment of a method for manufacturing a decorative molded product of the present invention, and FIG. 2 is a decorative molded product obtained by the method for manufacturing a decorative molded product of the present invention. Of 1
It is a model cross section which shows an example. 1: Printed pattern layer, 2: Water-soluble or water-swellable film, 3:
Transfer film, 5: water surface, 6: activator, 7: base material for painted article, 8: curable resin layer that is not completely cured, 10, 18:
A completely cured curable resin layer.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-58-53480 (JP, A) JP-A-58-191187 (JP, A)

Claims (2)

[Claims] 1. A transfer film comprising a water-soluble or water-swellable film having a printed pattern layer, which is floated on the water surface with the printed pattern layer surface of the transfer film facing upward, and then transferred. An activator containing a solvent that dissolves the print pattern layer in the film is applied to the print pattern layer of the transfer film, or after the activator is applied to the print pattern layer of the transfer film, the transfer film is transferred. The first step of floating the film on the water surface so that the printed pattern layer surface of the film is the upper surface, and the surface to be painted is not dried from the upper surface of the transfer film floating on the water surface. Of the curable resin layer, which is not yet completely cured, is pressed in, and the transfer film is hydraulically spread and adhered to the outer peripheral surface of the decorative molded article substrate. And a third step of removing the water-soluble or water-swellable film in the transfer film to transfer the printed pattern layer in the transfer film to the curable resin layer surface of the decorative molded article substrate. And a fourth step of forming a curable resin layer so as to cover the printed pattern layer transferred to the curable resin layer surface of the decorative molded article substrate, and on the printed pattern layer,
A fifth step of completely curing the curable resin layers present on both lower sides, and a method for producing a decorative molded article. 2. The method for producing a decorative molded article according to claim 1, wherein the curable resin layer is composed of a thermosetting resin.