JPH0216239B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for imparting a desired pattern to the surface of inorganic or organic materials or molded products thereof, and its purpose is to add value to the materials or molded products. The goal is to obtain products with improved appearance and superior appearance.

In recent years, in addition to improving the so-called hard aspects of materials, that is, the physical properties of materials, there has been a remarkable movement to improve the soft aspects, such as visual sensation, in order to further increase commercial value.

However, painting (patterning) an already formed product or material to give it a satisfactory appearance
technology has not necessarily been discovered.

For example, as a method for printing molded products made of arbitrary materials with arbitrary shapes, a desired pattern is floated on the surface of the water, and in order to attach the pattern, the molded product is pushed from above the water surface through the pattern and below the water surface. Another known method is to add a pattern to a molded product and then dry it to create the same effect as printing.

Although ingenious, this method has problems with productivity and the appearance of the resulting product is unsatisfactory, so to speak.

Furthermore, in recent years, as building materials have become more sophisticated, many attempts have been made to add patterns to hydration-hardened molded products such as cement and plaster to increase their added value.

For example, as seen in Japanese Patent Application Laid-Open No. 52-52965, a sheet is printed using water-soluble ink, the sheet is molded into a desired mold, and then a hydration-curing slurry is injected and cured. Another method is to apply a pattern to a molded article by dissolving a water-soluble ink and transferring the printed pattern to a hydration-cured layer.

Although this method is advantageous, there are significant deficiencies in existing methods.

This defect is because the method described in the above-mentioned JP-A-Sho uses water-soluble ink, so the pattern itself is not water resistant, and the pattern may disappear when immersed in water. Its uses must be limited, and it is not suitable as a building material that requires water resistance.

The present inventors previously reported in Japanese Patent Application No. 56-152172 that after coating a photocurable resin on a material, a film with a pattern printed on it was laid down so that the printed surface was in contact with the resin, and even when irradiated with ultraviolet rays, When the pattern is black or dark colored, the resin under the pattern of these colors cannot be cured or is insufficiently cured, resulting in a disadvantage that good transfer of that portion cannot be carried out.

The inventors of the present invention have been studying a method of freely adding patterns to any material or molded products made of any material, regardless of whether it is black, dark color, or light color, and solved the problem using the following method. We were able to complete the present invention by discovering what could be done.

That is, the present invention involves coating the surface of a material or a molded article with a photocurable resin containing a photopolymerization initiator and an organic peroxide (hereinafter simply referred to as photocurable resin), and then When in a liquid or sticky gel state, a film printed with a pattern using a printing ink that is compatible with the resin is placed so that the printed surface is in contact with the resin, and irradiated with light. At the same time as the resin is cured, the printed pattern on the film surface is transferred to the resin surface, and after the film is removed, a transparent or semi-transparent paint is applied to the transferred surface to create a pattern on the material or molded product. This relates to a method for attaching.

That is, the present invention is applicable to materials or molded products (see Figure 1a).
Photo-curing resin (B in Figure 1 a) is applied to the surface of A).
A film (Fig. 1) on which a pattern (D in Fig. 1 b) is printed using a printing ink that is compatible with the resin when the resin is in a liquid or sticky gel state before it hardens. C) in b) was placed so that the printed surface was in contact with the resin, and at the same time as the resin was cured, the printed pattern D on the film surface was transferred to the resin layer (Fig. 1c), and the film was removed. After that, the transfer surface is further coated with resin (E in Fig. 1d).

According to the present invention, a pattern is provided between the resin layer whose surface layer is transparent or semitransparent and the cured resin layer, and the pattern can be printed on a base material or adhered to printed paper. Unlike conventional molded products, it is possible to obtain molded products with a remarkable depth of flavor and excellent appearance.

When transferring a printed pattern, if the photocurable resin contains only a photopolymerization initiator, the resin under the dark or black pattern will not harden even if it is irradiated with light. Furthermore, even if an organic peroxide is used in combination with a curing accelerator, it will take several tens of minutes to cure at room temperature, and printing ink tends to bleed, resulting in blurred patterns and color separation. be. Furthermore, in the case of high-temperature curing, which usually does not contain a curing accelerator, even if the ambient temperature is high, it still takes several minutes to cure due to the heating of the material, and the plastic film stretches and deforms at high temperatures. This makes it impossible to form a smooth transfer surface.

However, when the present inventors irradiated light in the coexistence of a photopolymerization initiator and an organic peroxide, surprisingly, the organic peroxide was activated even at a temperature (room temperature) under light irradiation conditions that was lower than the operating temperature of the organic peroxide. The material contributes satisfactorily to the curing of the resin, and the resin under the dark or black pattern is cured in seconds at the same time as the transparent part, and troubles caused by keeping the printing film in contact with the resin for a long time can be avoided. They discovered that all of these problems can be solved and completed the present invention.

The difference between the effects of the present invention and other methods is that the present invention has a pattern between the resin and the paint, similar to a sandwich ham, which results in light refraction and transmission.
The repeated reflections from the material or molded product add depth to the appearance. This difference in effectiveness cannot be overemphasized when compared to the difference in appearance.

Furthermore, according to the method of the present invention, the properties of the upper and lower resin layers, for example, the refractive index can be changed, or the resin layer in contact with the material has a higher refractive index than the surface layer paint, or a transparent bead-shaped filler is used. By incorporating various methods such as mixing in materials, it is possible to directly print onto the material with conventional printing ink and freely impart a feeling that cannot be achieved with painted materials.

In particular, the features of the present invention are best exhibited in hydration-cured molded products.

In the past, there have been attempts to improve the commercial value of hydration-cured molded products by adding patterns to them, but these have sometimes been fatal when used as construction materials due to their water resistance and weather resistance. The shortcomings could not be resolved.

Further, it is difficult to implement conventional methods such as thermal transfer, sublimation transfer, and direct printing because the adhesion of printing ink to these hydration-cured molded products is poor.

Furthermore, no improvement in appearance is expected.

However, with the implementation of the present invention, for the first time, any type of hydration-hardened molded product, such as cement products or plaster products, can be painted with water resistance and weather resistance at will, and has a deep appearance. It is possible to obtain beautiful molded products that cannot be seen with conventional hydration-cured molded products.

Organic and inorganic materials to which the present invention is applied,
Alternatively, any molded product falls within the scope of the present invention, as long as it can be painted and a printed film can be applied.

Examples of these are as follows: (i) Natural organic materials include leather, wood, and their processed products, such as plywood, chipboard, hardboard, and particulate board.

(ii) Natural inorganic materials include metals, stones,
There is natural slate.

(iii) Man-made organic materials include paper, synthetic paper, nonwoven fabric, fabric, synthetic leather, and various plastics, such as polycarbonate, polymethyl methacrylate, polystyrene, polyvinyl chloride,
Polypropylene, resin concrete, ABS,
A typical example is FRP (fiber-reinforced plastics).

(iv) Man-made inorganic materials such as cement products,
Examples include hardened gypsum, hardened mixtures of gypsum and cement, magnesia cement products, calcium silicate products, slate or magnesium carbonate products, unglazed earthenware, and bricks.

Of course, these materials include those whose surfaces are coated with a sealing coating as desired. Among the above materials or molded products, (i), (iii), and (iv) are particularly preferred in the present invention.

Of the above (i) to (iv), in the case of (iii) and (iv), aggregate, reinforcing materials such as glass fiber, asbestos fiber, rock wool, organic Of course, fibers, colorants, etc. can be used in combination.

Various types of photocurable resins can be used in the present invention. Examples of these are:
These include unsaturated polyester resins, vinyl ester resins (epoxy-acrylate resins), various unsaturated acrylate resins, and the like.

Of course, these resins can be used in combination. The unsaturated polyester resin contains an α-β unsaturated polybasic acid as one component, and an unsaturated alkyd obtained by esterifying it with a polyhydric alcohol using any polybasic acid in combination with a polymerizable monomer ( monomer). For use in the present invention, there are no particular compositional limitations, and the vinyl ester resin can be prepared by reacting an epoxy resin containing more than one epoxy group with acrylic acid or methacrylic acid to obtain an acryloyl group or It is a prepolymer containing one or more methacryloyl groups, usually dissolved in monomer.

There are several types of unsaturated acrylate resins.

Although the aforementioned vinyl ester resin is also a type of unsaturated acrylate resin, it is customarily treated as an independent resin.

Examples of unsaturated acrylate resins include (i) polyester (alkyd for coatings), (ii) polyurethane, (iii) spiroacetal, (iv) having more than one acryloyl group or methacryloyl group in the molecule.
)
Typical examples are melamine resin and (v) polyether.
These are utilized with or without monomers.

The photopolymerization initiator used in the present invention may be a conventional photopolymerization initiator, and typical examples include benzoin and its ethers, benzophenone and its nuclear substituted products, thioxanthones, and dibenzyl ketals.

The organic peroxide used in the present invention may be any conventional organic peroxide, and representative examples include ketone peroxides, acyl peroxides, and hydroperoxides.

The printing film used in the present invention is suitably made of plastic, but polypropylene, polyethylene, polyethylene terephthalate, etc. are easily used in terms of cost and ease of handling. Also usable are cellophane and acetal-modified polyvinyl alcohol films (eg, Vinylon (trade name, manufactured by Kuraray Co., Ltd.)). Of course, other films can also be used as long as they adhere to and peel off the cured resin and do not dissolve or swell significantly when they come into contact with the cured resin. It may also be surface-treated to improve adhesion to printing ink.

The printing ink used in the present invention need only have greater affinity for the photocurable resin than for the film, that is, the adhesiveness between the photocurable resin and the ink should be greater than the adhesiveness between the ink and the film. The type is not particularly limited.

In fact, the purpose of the present invention can be fully achieved with general oil-based ink used in gravure printing, offset printing, etc.

Vehicle polymers or oligomers used in printing inks can be of any type that is soluble in organic solvents.

Examples of these include the following types:

Styrene-maleic acid copolymer, polymer or oligomer with a third component added, polyamide resin, polybutene, xylene resin, chlorinated rubber, petroleum resin, 100% alkylphenol resin, oil-soluble phenolic resin, ketone resin, ester gum , lime-cured rosins, rosin-maleic resins, rosin-modified phenolic resins, oil-modified alkyd resins, dry natural and polymerized oils, epoxy resins, cellulose derivatives. In addition to the above, there are polymer latexes that are aqueous dispersions but whose dry film shows lipophilic properties, or polymers that are both water-soluble and soluble in organic solvents, such as methylcellulose, hydroxyethylcellulose, methylhydroxypropylcellulose, and polyvinyl. It is also possible to use pyrrolidone, polyvinyl methyl ether, etc.

In particular, inks made by adding colorants to organic solvent-soluble polymers, which are not commonly used in printing inks, can be used either by printing or by hand-painting.

Furthermore, photocurable vehicles, which have been increasingly used in recent years, can also be used. They mainly consist of unsaturated acrylate resins, namely polyester acrylates, vinyl ester resins, urethane acrylates, and spiroacetal acrylates, with the necessary amount of polyacrylate polyhydric alcohol added thereto and a photosensitizer added. is the main thing.

Polymers that are only soluble in water and insoluble in organic solvents are
Not suitable as a vehicle. This is not only because it is difficult to print on ordinary film, but also because what is printed on hydrophilic film generally does not adhere to the cured surface of lipophilic resin.

Of course, an ink using a water-soluble resin as a vehicle can be used if a hydrophilic curable resin is selected, but there are no particular advantages in terms of performance. Printing inks using vehicles that are both lipophilic and hydrophilic, such as polyvinylpyrrolidone, can also be used in some cases.

Printing in the present invention means drawing a pattern on a desired film by machine or manually.

The paints used when applying a topcoat after curing are classified into hardening type and thermoplastic type. In addition to the types mentioned above, curable paints include epoxy resin, urethane resin, phenolic resin,
Air-curing alkyds, polybutadiene resins, curable melamine-alkyd resins, and the like may also be added. The thermoplastic resin must be soluble in a solvent, have good coating film forming properties, and have practical physical properties of the coating film, including hardness. Examples include styrene homopolymers or copolymers, polymethyl methacrylate homopolymers or copolymers, polyvinyl chloride and vinyl acetate copolymers, and their copolymers with maleic anhydride. Examples include cellulose esters, cellulose esters, etc. These are suitably used in the form of organic solvent solutions or aqueous emulsions.

Next, examples will be shown below to help understand the present invention.

Example 1 100 parts by weight of α-type hemihydrate gypsum (hereinafter referred to as "parts"), 35 parts of water, and 1/4 into a mold of 600 x 600 x 15 mm ³ on which synthetic paper "YUPO" manufactured by Oji Yuka Co., Ltd. was laid as release paper. ″Glass fiber 1 part, hydroxyethyl cellulose
Inject 0.1 part of the kneading slurry and harden.

After demolding, 1 part of benzoyl peroxide was added and dissolved in 100 parts of Spirac U-3155 manufactured by Showa Kobunshi Co., Ltd. (containing benzophenone as a photopolymerization initiator) as a photocurable resin, and this was mixed to a thickness of 0.2 mm. After coating with a flow coater, it was gelled by passing it through a 20 cm path under an ultraviolet irradiation machine at room temperature with an output of 30 kW at a rate of 15 m/min (residence time under light irradiation of approximately 4 seconds). The surface was sticky like jelly. The length of the lamp part of the irradiation device is approximately 1 m. The same applies to everything below.

A polyethylene terephthalate film, on which a brown Casimir onyx pattern was printed using an oil-based ink containing a styrene-maleic acid copolymer resin and a ketone resin by screen printing, was uniformly adhered to the film while being pressed with a roller.

Next, using the same device again, the resin is passed through at a speed of 5 m/min (residence time under light irradiation of about 12 seconds) to once harden the resin.

When the film is removed, the onyx pattern is completely transferred to the coating surface.

Furthermore, after coating the same resin with a flow coater to a thickness of 0.2 mm, the output was 50 kW (the length of the lamp part was approximately 1.6 m, the same applies hereafter), and the area 20 cm below the ultraviolet irradiation device was coated at 5 m/min (approx. 19 seconds).

A Kashmir onyx-like artificial marble with a surface hardness of 5H, stain resistance, and a deep pattern was obtained.

Comparative Example 1 When the same operation was performed except that U-3155 was used alone as a photopolymerization initiator without using benzoyl peroxide, when the film was peeled off, the brown onyx dark brown stripes (second Figure F) was not photocured, and that portion was not transferred. Therefore,
As a product, it was completely worthless.

Comparative Example 2 Does not contain benzophenone as a photopolymerization initiator,
A spiroacetal resin containing only benzoyl peroxide in the same amount as in Example 1 is designated as U-3155N.

When the same work as in Example 1 was carried out using U-3155N, the resin layer did not harden over the entire surface even after applying the printing film and passing through the irradiation machine, making it impossible to transfer the molded product. I couldn't get it.

Comparative Example 3 Using the same α-type hemihydrate gypsum used in Example 1, and using a gypsum board that had been injected and hardened into the same mold,
Instead of Spirac, apply vinyl roll #92 made by Showa Kobunshi Co., Ltd., which is a thermoplastic methyl methacrylate copolymer resin solution, to a thickness of 0.2 mm and let it cool at room temperature.
After being left for 10 minutes, when the adhesiveness reached the level of adhesive tape, a polyethylene terephthalate film printed in the same brown Casimir Onyx pattern as used in Example 1 was pressed with a roller and left to stand. The situation when the film was peeled off after being left for 1 day, 3 days, and 7 days was as follows: After 1 day: Adhesive, most of the pattern remained on the film, and part of it was transferred to the material. Moreover, the transferred pattern was blurred.

3 days later: Same as above 7 days later: The pattern had been transferred to such an extent that part of it remained on the film, but the pattern had collapsed and was no longer clear.

Example 2 Using the same mold as in Example 1, 85 parts of white Boltland cement, 15 parts of white anhydrite, 100 parts of white silica sand, and 1 part of Melment (trade name, manufactured by Showa Denko, melamine resin cement water reducing agent) A mixed slurry of , 60 parts of water, and 3 parts of alkali-resistant glass fiber was injected, allowed to stand for 3 hours, steam-cured at 70 to 75°C for 3 hours, and then allowed to stand at room temperature.

As an unsaturated polyester resin, 100 parts of Rigorakku #2004 manufactured by Showa Kobunshi Co., Ltd., 2 parts of methyl ethyl ketone peroxide, 0.03 part of accelerator E, and 1 part of benzoin isopropyl ether as a photopolymerization initiator were added, and sprayed with 0.3 to 0.4 parts of benzoin isopropyl ether. mm thick, and a printed film made by printing two fashion models using an oil-modified alkyd printing ink was attached to a polyethylene terephthalate film, and immediately passed between rubber defoaming rolls to remove the film. Made bubbles.

Next, the sample was passed through an ultraviolet irradiation device with an output of 30 kW over a distance of 20 cm at room temperature at a speed of 2 m/min. When the film was peeled off after curing, the pattern was completely transferred to the resin surface.

Next, a mixed resin of 100 parts of Rigorac #2025C, an unsaturated polyester resin manufactured by the same company, 1.5 parts of methyl ethyl ketone peroxide, and 0.5 parts of cobalt naphthenate, was sprayed to a thickness of 0.2 to 0.3 mm and cured at room temperature. .

After hardening, it was wet sanded with #600 sandpaper and buffed. A beautiful decorative board on which the two fashion models stand out was obtained.

At this time, if only benzoin isopropyl ether is used without using organic peroxide and accelerator,
The black part of the hair was not cured and the transfer was incomplete.

Example 3 A mold similar to Example 1 was made with a thickness of 2 as a first step.
The following blended slurry was injected so that the amount was 1 mm.

White cement 100 parts Silica fine powder 100 parts Expanding agent (Exban manufactured by Onoda Cement Co., Ltd.) 8 parts Melment 1 part Black pigment (SS BLACK-C manufactured by Sanyo Shiki Co., Ltd.) 10 parts Water 60 parts Hydroxyethyl cellulose 0.2 parts The whole becomes uniform after 45 minutes When it became jelly-like, the remaining 13 mm was lined and injected with the following formulation.

Portland cement 100 parts Mountain sand 150 parts Expansion agent (trade name "Exban" manufactured by Onoda Cement Co., Ltd.) 10 parts Melment 1 part 1/4" glass fiber 3 parts Ethylene-vinyl acetate emulsion containing 5 mol% ethylene 10 parts Overnight After being left to stand, steam curing was performed at 75°C for 3 hours.
After leaving it in a drying room at 30°C overnight, 100 parts of Lipoxy R-802 manufactured by Showa Kobunshi Co., Ltd. containing 10% glass beads as a vinyl ester resin was added to harden the organic peroxide-based vinyl ester resin manufactured by Kayaku Nouri Co., Ltd. 3 parts of agent 382,
0.5 part of cobalt naphthenate and 1 part of Irgakiure #651 (dibenzyl ketal type) manufactured by Ciba Co., Ltd. as a photopolymerization initiator were added, and the mixture was painted with a brush to a thickness of 0.4 to 0.5 mm. Once gelatinized at room temperature, it is further coated with the same blended resin to a thickness of 0.2 to 0.3 mm, and immediately coated with aluminum lacquer, which is a mixture of nitrocellulose lacquer and silver mud (aluminum paste), on the polyethylene terephthalate film. , a landscape painting was attached and hardened.

Curing was carried out under an ultraviolet irradiation device with an output of 50kW.
cm at a speed of 2 m/min.

When the film was removed after curing, the silver mud landscape painting was completely transferred to the black background.

Next, the photocurable Spirac U-3155 used in Example 1 was coated with a flow coater to a thickness of 0.2 mm, and then passed through a 20 cm path under an ultraviolet lamp with an output of 50 kW at a speed of 5 m/min at room temperature. Ta.

The coating film hardness of the obtained molded product was 4 to 5 days, and it looked like a silver mud landscape painting floating on a black base, and was extremely beautiful and could be used as a decorative material.

Comparative Example 4 Among the methods described in Example 3, when only Irgakiyua #651 was used, the resin part under the silver-colored landscape painting only gelled into an agar-like state, and the pattern in that part could not be transferred. It was impossible.

Example 4 On a 15 mm thick, 300 x 300 white calcium silicate plate manufactured by Onoda Cement Co., Ltd., 100 parts of Lipoxy VR-77 manufactured by Showa Kobunshi Co., Ltd. was added as a photocurable vinyl ester resin containing no monomer, and Ciba was added as a photopolymerization initiator. Add 1 part of Irgakiure #651 from the company, and 1 part of lauroyl peroxide, and spray paint a resin solution uniformly dissolved in 50 parts of ethyl acetate to a thickness of about 0.3 mm, and air dry it indoors for about 3 hours. A coating film with surface tack is obtained. This was then screen-printed with a Sergino Marble-like pattern on polypropylene film using an oil-based ink using a vehicle mainly composed of rosin-maleic acid resin, which was then crimped through an adhesive roll using an ultraviolet irradiator with a 30kW output. It passed through the lower 20 cm at 3 m/min and was cured.

When the film was peeled off, a board with the Sergino marble pattern completely transferred onto the calcium silicate board was obtained.

This was then spray-painted with Kansai Paint Co., Ltd.'s hardening polyurethane paint Acryk 2026GL Clear to a thickness of approximately 70μ, and after curing was given a buff finish.

A decorative calcium silicate board with a deep pattern was obtained.

In this case, if lauroyl peroxide is not used in combination, the dark gray part of Cergino Marble will be incompletely cured, and when the film is peeled off, no pattern will remain on the resin layer, and it will remain on the film layer, resulting in a product with commercial value. I can't get it.

Example 5 Outer plate for a hardened cement cylinder with an outer diameter of 45 cm, a thickness of 3 cm, and a length of 100 cm (100 parts of white cement, 100 parts of white silica powder, 120 parts of water, 2 parts of Melment, 3 parts of 1/4" glass fiber, (obtained from 20 parts of ethylene-vinyl acetate resin emulsion and 10 parts of swelling agent), 100 parts of Showa Kobunshi Co., Ltd. Rigorak 150HR as an unsaturated polyester resin, 10 parts of styrene, 2 parts of methyl ethyl ketone peroxide, and cobalt naphthenate. 0.03 parts, 1 part of benzoin isobutyl ether,
A uniformly dissolved resin is coated to a thickness of 0.4 to 0.5 mm, and immediately an Italian marble "brown travertine" pattern is printed on a propylene film using oil-modified alkyd printing ink combined with ketone resin, which is then printed by pressure bonding. The light was passed through a 20 cm distance below the lamp in a 30 kW ultraviolet irradiation device at a speed of 5 m/min at room temperature.

After curing, the film is removed to obtain a cylinder shell with a completely transferred brown travertine pattern.

This is finished by spray painting methyl methacrylate copolymer resin solution vinyl roll #92 manufactured by Showa Kobunshi Co., Ltd. as a thermoplastic acrylic clear lacquer.

A cylindrical shaped article with a surface hardness of H, gloss, and a feeling of natural marble with an embossed pattern was obtained.

In this case, if only benzoin isobutyl ether, which is a photopolymerization initiator, is used, the travertine pattern is dark yellowish brown, so the curing of the resin is generally poor, the coating film becomes crumbly, and the transferability is affected. , surface uniformity cannot be expected.

Example 6 Waterproof plywood with a thickness of 9 mm was cut into 300 x 300 mm ^{2 pieces} , and this was coated with unsaturated polyester resin (Rigorak #2245 manufactured by Showa Kobunshi Co., Ltd.) 100 parts talc 100 parts calcium carbonate 50 parts methyl ethyl ketone peroxide 1 part naphthene A putty mixed with 0.5 parts of cobalt acid is applied, once hardened, and then polished to form a smooth surface. After applying a mixed resin of 100 parts methyl ethyl ketone peroxide 1 part cobalt naphthenate 0.03 parts benzoin isopropyl ether 1 part to a thickness of 0.5 to 0.6 mm with a brush, , a black-purple rosewood pattern printed with an oil-based ink mainly composed of lime-cured rosin and rosin-maleic acid resin was adhered to a polypropylene film.

It is completely cured by passing it through a 20cm length at room temperature at a speed of 5m/min under an ultraviolet irradiation device with an output of 30kW.

When the polypropylene film is peeled off after curing, a cured coating film with perfectly transferred rosewood grains is obtained.

Furthermore, by painting the same blended resin to a thickness of 0.5 to 0.6 mm, curing at room temperature, and polishing and buffing to give a surface finish, a beautiful decorative board that looked just like natural rosewood was obtained.

In this case, if only benzoin isopropyl ether was used, the curing of the coating film would be poor, probably due to the dark color of the rosewood, and the transfer would not be complete.
Residue on the film is particularly noticeable in dark colored areas. The coating film is also soft and only looks like hard agar.

Example 7 On a transparent polycarbonate plate of 300 x 300 x 5 mm ³ ,
As a photocurable resin, Spiroacetal type unsaturated acrylate resin Spirac U- manufactured by Showa Kobunshi Co., Ltd.
3163 (containing a benzophenone derivative photopolymerization initiator) was added with 1 part of tert-butyl perbenzoate, and coated with this to a thickness of 0.2 mm, a pansy flower pattern was applied to the polyethylene terephthalate film using an oil-modified alkyd film. The paper was screen-printed using oil-based ink, and then passed through a 30-cm tube under an ultraviolet irradiation device with an output of 30 kW at room temperature at a rate of 5 m/min to cure.

When the film was removed, a polycarbonate plate with a completely transferred floral pattern was obtained.

Furthermore, the same type of photocurable resin from the same company, Spirac U-3155, was applied to a thickness of 0.2 mm.
Curing was carried out using the same irradiation equipment at a speed of 3 m/min.

The surface hardness of the obtained polycarbonate plate is 5H,
The result is a beautiful molded board with a flower pattern that stands out.

In this case, when only U-3163 was used, the deep blackish-purple part of the pansy flower remained in a soft gelled state, and transfer could not be expected at all.

Furthermore, when only tert-butyl perbenzoate is used in combination with the base resin of U-3163 (which does not contain a photoinitiator), the uncolored transparent part will not harden under the same light irradiation conditions as in this example. Ta.

Example 8 After polishing the surface of a 500 x 500 x 15 mm ³ FRP honeycomb sander board with #320 abrasive paper, Lipoxy R manufactured by Showa Kobunshi Co., Ltd. was used as a vinyl ester resin.
To 100 parts of -840, 1.5 parts of methyl ethyl ketone peroxide, 0.2 parts of cobalt naphthenate, and 1 part of dibenzyl photopolymerization initiator were added, coated to a thickness of 0.1 to 0.2 mm, and allowed to gel at room temperature. This gel state is maintained for approximately one day.

A polypropylene film with a dark brown mottled pattern called "Botechino", an Italian marble, printed using an oil-based ink made from a styrene-maleic acid copolymer was adhered to the gel, and an output of 30 kW was produced. 20cm below the UV irradiation device
was passed at a speed of 5 m/min at room temperature.

When the film was peeled off, a honeycomb plate with the Botechino pattern completely transferred to the resin layer was obtained.

Furthermore, 50% of Kansai Paint Co., Ltd.'s Acryk 2026GL Clear was used as a hardening polyurethane clear paint.
I spray painted it to ~70μ and finished it by buffing.

We were able to obtain an FRP sandwich board that has the same feel as natural marble.

In addition, when dibenzyl is used alone, the dark brown part of the Perlino pattern becomes incompletely hardened.
The transferability cannot be expected. However, when dibenzyl is used alone, the printed film is not adhered in a gel state, but is adhered to a liquid resin.

Example 9 On a 0.2 mm thick polyethylene terephthalate sheet cut to 600 x 600 mm ² , a non-woven fabric of Panelon #2502 manufactured by Dainik Co., Ltd. (polyester-nylon-rayon material) cut to the same size was placed, and a photocurable non-woven fabric was placed. A polyhydroxyl polyester with a hydroxyl value of 54 and an acid value of 1.9 synthesized from adipic acid and ethylene glycol as a saturated acrylic urethane, 1,6-hexamethylene diisocyanate, 2
Urethane acrylate reacted with -hydroxyethyl acrylate and represented by the following formula: C=C-R ₁ -R-R ₁ -C=C (wherein -C=C is a 2-hydroxyethyl acrylate residue, _R1 is a 1,6-hexamethylene diisocyanate residue, R is a polyhydroxyl polyester residue) 100 parts, 30 parts of ethyl acrylate, 20 parts of trimethylolpropane triacrylate, 50 parts of 1,6-hexanediol diacrylate, light As a polymerization initiator, 2 parts of Irgakiure #651 manufactured by Ciba was added,
Furthermore, it was impregnated with a photocurable urethane acrylate resin to which 1 part of benzoyl peroxide was added.

Next, the polyethylene terephthalate film printed with the brown Casimir Onyx used in Example 1 was crimped and cured by passing it through a distance of 20 cm at a speed of 5 m/min under an ultraviolet irradiation device with an output of 30 kW at room temperature. I let it happen.

When the film was removed, the Casimir Onyx pattern was completely transferred onto the surface of the urethane acrylate resin impregnated into the nonwoven fabric and cured.

Furthermore, using the same resin, after painting with a flow coater to a thickness of 0.2 mm, it was coated under the same irradiation equipment for 20 minutes.
cm was passed at a speed of 2 m/min at room temperature. When the polyethylene terephthalate sheet material was peeled off, the translucent nonwoven fabric was visible, and a decorative board with a brown Kashmir onyx-like pattern was created on the surface and was flexible enough to be bent at will.

In this case, if only Irgakiure #651 is used, the same phenomenon as described in Comparative Example 1 occurs, and a perfect transfer product cannot be obtained.

In addition, when using only benzoyl peroxide,
Of course, it does not harden even after passing through the irradiation device, but if you try to force it to harden and stop the conveyor and hold it in that state for about 6 minutes, it will begin to gel, but at the same time large and small bubbles will appear all over the surface. This caused the product to not be uniform, making it extremely impractical.

Example 10 The cured gypsum board used in Example 1 was similarly coated with 100 parts of Spirac U-3155 as a photocurable resin to which 1 part of benzoyl peroxide was added to a thickness of 0.3 to 0.4 mm, and then the following coating was applied. Lay the printed film so that the pattern is in close contact with the resin.

The printing film was prepared using a polyethylene terephthalate film, a photocurable vinyl ester resin SP-1509 manufactured by Showa Kobunshi Co., Ltd., and 3 parts of Irgakiure #651 and 2 parts of benzoyl peroxide as a vehicle, and mixed with the required pigments. Screen print a black serpentine pattern using printing ink,
20cm below the ultraviolet irradiation device with an output of 30kW.
An acetone-insoluble type is used by passing the sample at a speed of m/min.

The sample is passed 20 cm under an ultraviolet irradiation device with an output of 50 kW at a speed of 2 m/min at room temperature.

When the film is peeled off after curing, a cured coating film with the pattern of black noble serpentine transferred thereto is obtained.

In addition, as a curable transparent polyurethane resin,
Spray paint Acrylic 2026GL Clear, manufactured by Kansai Paint Co., to a thickness of approximately 70μ.

After buffing and finishing, the result is a deep black noble serpentine molding that looks even better than the real thing.

In this case, if only U-3155 is used, the black part of the noble serpentinite will not harden quickly and only a molded product with poor transfer will be obtained.

Furthermore, if only U-3155N (U-3155 base resin containing only benzoyl peroxide without adding a photoinitiator) is used, it will not harden over the entire surface.
The coating remained liquid.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of the manufacturing process of the present invention, and FIG. 2 is a diagram showing a transferred pattern. In the figure: A...base material, B...photocurable resin, C...
...Film, D...Printed pattern, E...Paint, F...
...The dark brown streaks of Brown Onyx.

Claims (1)

[Claims] 1. A photocurable resin containing a photopolymerization initiator and an organic peroxide is applied to the surface of a material or molded product, and the resin is in a liquid or sticky gel state before it hardens. A film printed with a pattern using a printing ink that has an affinity for the resin is placed so that the printed surface is in contact with the resin, and at the same time the resin is cured by irradiation with light, the printed pattern on the film surface is A method of adding a pattern to a material or molded product, which involves transferring the pattern onto a resin surface, removing the film, and then painting the transfer surface with transparent or translucent paint.