JPH0132790B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a decorative sheet, and in particular, when printing a pattern showing metallic brilliance or pearl brilliance on a synthetic resin sheet, it is necessary to effectively express the brilliance pattern. First, it concerns how to fully utilize the skills.

BACKGROUND ART Conventionally, in flooring materials, wallpapers, etc. using synthetic resin sheets, designs that exhibit bright color effects such as so-called metallic or pearl tones have been required, depending on the design preference. In such cases, painting has been done using methods such as regular gravure printing, screen printing, or barley printing in the same way as regular colored inks, but it is difficult to achieve the desired glittering effect and the inks are considerably weakened. The reality is that people have managed to cope with the situation by either putting up with the situation or supplementing it quantitatively by using inks with extremely high concentrations of bright pigments. In particular, the latter method requires a large amount of expensive glitter pigments, resulting in a large cost burden.Also, due to the nature of glitter pigments, the adhesion between the ink layers is poor, and depending on the application, there is a risk of causing delamination. However, this could also lead to complaints.

In particular, when applying a vinyl chloride resin layer on top of a printed layer as a surface layer to provide wear resistance, such as cushion flooring made of vinyl chloride resin, if this is done by laminating a ready-made transparent vinyl chloride film. However, if a transparent vinyl chloride sol coat is applied on the printing layer and the sol coat is cured to form a film at the same time as the base material is heated and foamed, the solvent content in the vinyl chloride sol and the foamed base material of the lower layer may be removed. The foaming decomposition gas and by-products that boil up cause bubbles to occur in the PVC Dull Coat, reducing transparency, while not only disturbing the glitter pattern layer, but also acting on the metallic or pearl pigment components. This results in a decrease in brightness. Further, when a normal colored ink layer is adjacent to a colored ink layer having a foaming suppressing effect, it fuses with the bright ink, which also causes a decrease in brightness.

Furthermore, the above-mentioned foaming process usually creates a surface with a three-dimensional effect by imparting an uneven effect, but in this case as well, the surface area increases, the glitter ink layer expands, the pigment concentration decreases, and the glitter becomes less bright. This results in weakening. Moreover, in these conventional decorative sheets, the bright ink is directly printed on top of the normal colored ink, so they lack depth and three-dimensionality, and are not satisfactory in terms of design.

As a result of intensive research by the present inventors to solve the problems of the above-mentioned prior art, they discovered that the above-mentioned problems could be solved by providing a transparent or semi-transparent barrier coat layer, and based on this knowledge, The present invention has now been completed.

That is, the method for manufacturing a decorative sheet of the present invention includes:
When printing a pattern using bright ink on a synthetic resin sheet, print a pattern using colored ink or bright ink on the synthetic resin layer, with or without a transparent or translucent first barrier coat layer. The present invention is characterized in that a transparent or translucent second barrier coat layer is applied thereon, and a printed pattern is formed using bright ink on the second barrier coat layer.

As the synthetic resin sheet, both a foamable synthetic resin sheet and a non-foamable synthetic resin sheet can be used. Further, a backing material may be provided on the lower surface of this synthetic resin sheet to strengthen it.

A first barrier coat layer is formed on this synthetic resin sheet, and a pattern is printed on the synthetic resin sheet with colored ink or bright ink, or directly on the synthetic resin sheet without forming the first barrier coat layer. If a first barrier coat layer is provided, it can sandwich a colored ink or bright ink layer together with the second barrier coat layer in a sandwich pattern to further protect this ink layer. In addition, when printing directly without providing the first barrier coat layer, a type of ink that suppresses or promotes foaming of the foamable synthetic resin is used as the colored ink to obtain a decorative sheet with so-called chemical embossing. You can also do it.

Patterns using colored ink or bright ink (first
The pattern) can be printed using ordinary printing equipment, but it is particularly preferable to use gravure printing or screen printing.

A second barrier coat layer is provided over this first pattern.

The barrier coat layers (first and second) are coated with a liquid composition before reaction curing using an appropriate coating device, and are reaction cured by an appropriate curing means such as air drying, heating, and ultraviolet irradiation (semi-curing is also included). It can be formed by pressing.

The material for the barrier coat layer may be any material that can be quickly cured by air drying, heating, ultraviolet irradiation, etc., and can form a strong film. Specific examples of these materials include acrylic urethane resins formed from isocyanate-containing bodies and active hydrogen (-OH, -COOH, -NH2 _, etc.) containing bodies that react with isocyanate-containing substances at appropriate temperatures to form molecular crosslinked structures. , polyester urethane resins, polyether urethane resins, epoxy urethane resins, mixtures or copolymer resins of these, or unsaturated polyesters and polyesters containing ultraviolet sensitizers. -Acrylate-based, epoxy-acrylate-based,
Monomers such as polyether-acrylate,
Ultraviolet curable paints (UV paints) consisting of oligomers and prepolymers, and electron beam curable paints (EB paints) that form a dry coating film by electron beam irradiation with similar chemical components. Reaction-curing resins such as various alkyd resin paints, unsaturated polyester resin paints, and epoxy resin paints, which cause molecular crosslinking reactions when present, are preferred.

Furthermore, a printed pattern (second pattern) using bright ink is formed on the second barrier coat layer.

Further, a third barrier coat layer may be further formed on the second pattern to further ensure the adhesion of the bright ink layer.

After forming the first pattern and the second pattern as described above, a transparent synthetic resin layer may be further formed thereon as a surface layer. This improves strength and abrasion resistance, and makes it possible to obtain a decorative sheet that is more durable and more desirable. Further, in cases where strength and abrasion resistance are not so required, such as wallpaper, it is not necessary to provide the above-mentioned synthetic resin layer, and a backing agent alone is sufficient.

Moreover, when a foamable synthetic resin is used as the synthetic resin sheet, this is foamed to obtain a foamed decorative sheet.

FIGS. 1 to 3 are schematic sectional views showing structural examples of the decorative sheet of the present invention.

In FIG. 1, a foam layer 13 is placed on the backing material 11.
are formed, and colored ink layer 15, colored ink layer 15', and colored ink layer 1 containing a foaming inhibitor are formed thereon.
7-piece colored ink pattern (first pattern)
is formed, and a second barrier coat layer 19 is formed thereon.
A bright ink layer 21 is further formed thereon to print a second pattern, and a transparent synthetic resin layer is formed as a surface layer 23.

FIG. 2 is a sectional view showing a case in which a third barrier coat layer 22 is provided on the bright ink layer 21 (second pattern), and FIG. 3 is a sectional view showing a type in which a surface layer 23 is not provided. It is.

In the above description, a first barrier coat layer (which may be omitted), a colored ink layer, or a bright ink layer (first
Although the description has focused on the case of forming a second barrier coat layer (a pattern), a bright ink layer (a second pattern), the order in which each layer is formed is not particularly limited in the present invention. For example, as shown in FIG. 4, on the release layer 27 on the base paper 25, a bright ink layer 21 (second pattern), a second barrier coat layer 19, a colored ink layer 15, a colored ink containing a foaming inhibitor, etc. Ink layer 17 (first
A decorative sheet may be manufactured by previously manufacturing a transfer paper on which a pattern of 1) is formed and performing transfer printing using this transfer paper. FIG. 5 similarly shows the layer structure of the transfer paper; in this case, the bright ink layer 21 is formed between the third barrier coat layer 22 and the second barrier coat layer 19.
It is sandwiched between the two in the shape of a sandwich. Alternatively, a surface layer 23 may be formed as an upper layer of the release layer 27, and each of the above layers may be laminated on this surface layer 23 to form a transfer paper.

In addition, as shown in FIG. 6, a bright ink layer 21, a second barrier coat layer 19, a colored ink layer 15, and a foam-suppressing colored ink layer 17 are applied to one side (back side) of a transparent or translucent synthetic resin film. A decorative sheet may be manufactured by preparing a formed back print film in advance and pasting this film. FIG. 7 shows the bright ink layer 21
A type of backpunto film sandwiched between two barrier coat layers is shown.

In the present invention, a tough barrier coat layer is formed between the bright ink layer and other ink layers. The barrier coat layer is strongly bonded to each ink layer by reaction curing, and since this layer itself is a tough transparent or semitransparent layer, it protects the ink layer from foam decomposition products and adverse effects caused by heating. It is possible to prevent fusion of bright ink and normal colored ink, reduction in brightness of bright ink, and disturbance of patterns.

In other words, when the synthetic resin sheet is a foamable synthetic resin sheet, after all printing is completed on the foamable synthetic resin sheet, it is heated to a temperature higher than the decomposition temperature of the foaming agent to cause it to foam. When ink and bright ink are printed directly on top of each other, they are heated to the same temperature, so
Fusing with each other or dispersion of bright ink occurs,
This causes a decrease in brightness. In contrast, in the present invention, by providing a barrier coat layer between each ink layer, it is possible to prevent the inks from fusing with each other. Further, the barrier coat layer can firmly fix the bright ink, prevent the bright ink from dispersing, and prevent a decrease in brightness.

In order to further ensure the adhesion of the bright ink by the barrier coat layer, one preferred embodiment is to sandwich the bright ink layer between the barrier coat layers in the form of a sandwich. In addition, in transfer printing using transfer paper, a barrier coat layer is applied after printing with bright ink is formed on the release layer, so as the barrier coat layer reacts and hardens, the bright ink layer can be firmly fixed.
The same applies to the case of pasting with back print film. In addition, when performing bright ink printing on the barrier coat layer, by printing the bright ink layer immediately after applying the barrier coat and before the barrier coat layer is completely cured, the bright ink layer can be printed. It has a good grip and is preferred.

Furthermore, this barrier coat layer prevents the decomposition products, by-products, plasticizer vapor, etc. that accompany the foaming of the foamable synthetic resin from scattering, and can effectively prevent a decrease in brightness.

On the other hand, even when the synthetic resin sheet is a non-foaming synthetic resin sheet, a film is laminated on the surface using heat and pressure to protect the patterns printed on it and to increase the abrasion resistance of the surface. Or, after applying a sol, it is often heated and cured. Such problems during heating can also be solved in the same way as in the case of the foamable synthetic resin sheet described above.

By providing a barrier coat layer in this way, it is possible to eliminate various causes that cause a decrease in the brightness of bright ink, and the original brightness effect of bright ink can be maintained, so if the minimum necessary brightness ink is used, Well, you can save on expensive glitter ink.

In addition, this transparent reaction-curing barrier layer partially fuses with the glitter ink or colored ink and has excellent adhesive properties, so it fixes the glitter pigment ink layer, which has coarse particles that are particularly susceptible to cohesive failure, and creates strong interlayer and Intralayer strength can be obtained. Therefore, it is possible to effectively prevent peeling within the ink layer and between the ink layers, which tends to occur when bright ink and colored ink are directly adhered. , a decorative sheet can be obtained that can be used satisfactorily for applications that require resistance to impact and the like.

Furthermore, between the first pattern and the second pattern,
Since the transparent layer formed by the barrier coat layer is present, it is possible to obtain a highly tasteful decorative sheet that has depth (three-dimensional effect) as a whole, and is also preferable in terms of design.

As is clear from the above explanation, the gist of the present invention is to provide a barrier coat layer, and conventionally known materials such as synthetic resin sheets, colored inks, bright inks, backing agents, surface layers, release papers, etc. Both can be used. Although these components are well known in this technical field and do not require explanation, some of them will be explained as follows.

As the bright ink, materials with light reflectivity,
For example, iron powder, copper powder, silver powder, aluminum powder,
Metal pigments such as metal fibers, natural pearlescent pigments collected from fish and shellfish, pearlescent pigments obtained by coating mica with metal oxides such as titanium oxide, pearlescent pigments obtained from heavy metal salt crystals, etc. Other examples include those in which potassium titanate whiskers, glass powder, glass fibers, metal-deposited films, etc. are dispersed in a normal vehicle.

Examples of resins for foamable synthetic resins include polyvinyl chloride, polyvinyl acetate, copolymers thereof, copolymers of these and other resins, olefin resins such as polyethylene and polypropylene, styrene, In addition to aromatic vinyl resins such as α-methylstyrene, thermoplastic resins such as polyester resins, polyamide resins, and polycarbonate resins, synthetic rubbers such as butadiene can be used alone or in combination with desired resins. Can be done. Of course, plasticizers, stabilizers, fillers, and other desired formulation aids can be used in these resins.

Example Polyvinyl chloride (emulsion type, =
1400) 60 parts by weight, polyvinyl chloride (suspension type, = 800) 40 parts by weight, DOP 45 parts by weight,
A foamable synthetic resin composition consisting of 5 parts by weight of TXIB, 2 parts by weight of zinc white, 2 parts by weight of ADCA, and 10 parts by weight of calcium carbonate was mixed with a high-speed stirrer to form a foamable sol. This was continuously applied to a long piece of asbestos paper with a thickness of 0.5 m/m and a width of 1900 m/m using a reverse roll coater, and then this was continuously passed through an oven at 160°C. The material was semi-gelled (semi-cured) and made into a sheet-like material suitable for printing.
The thickness of the foamable semi-gel sheet at this time is 0.3m/
It was m. Subsequently, a pattern was first printed on this foamable semi-gel sheet using a foam suppressor ink having the following composition using a first gravure roll.

Vinyl chloride/vinyl acetate copolymer resin 6 parts by weight Titanium oxide pigment 15 Foaming inhibitor 14 Ethyl acetate 10 Methyl ethyl ketone 24 Toluene 24 Xylol 7 Similarly, the following results were obtained using the second and third gravure rolls, respectively. Printing was done with ink of normal composition.

Colored ink No. 2 Vinyl chloride/vinyl acetate copolymer resin 7 parts by weight Quinacridone red pigment 6 Ethyl acetate 7 Methyl ethyl ketone 37 Toluene 37 Butyl acetate 6 Colored ink No. 3 Vinyl chloride/vinyl acetate copolymer resin 7 Parts by weight Isoindolinone yellow pigment 8 Ethyl acetate 5 Methyl ethyl ketone 37 Toluene 37 Ethyl acetate 6 Next, a barrier coat layer composition having the following composition was applied to the entire surface of the printed layer using a fourth gravure roll. Coated and cured.

Vinyl chloride/vinyl acetate copolymer resin 10 parts by weight Acrylate resin 5 Polyisocyanate 5 Ethyl acetate 15 Methyl ethyl ketone 25 Toluene 40 Next, using the fifth gravure roll, print with pearlescent ink with the following composition and finished all printing.

Vinyl chloride/vinyl acetate copolymer resin 8 parts by weight Titanium/mica pearl gold color pigment
15 〃 Ethyl acetate 15 〃 Methyl isobutyl ketone 40 〃 Toluene 40 〃 Dinitropropane 2 〃 Finally, on top of these printing layers, a transparent sol to form a wear-resistant layer mainly composed of polyvinyl chloride is reverse rolled. After coating with a coater, these were heated to 200°C to foam the foamable synthetic resin layer (semi-gel sheet) and gelatinize the transparent sol, and then cooled to obtain the decorative sheet shown in Figure 1. (Total thickness 2.3m/m).

This product has a sufficient glittering effect even with a small amount of pearl pigment, and shows a deep pearlescent luster.Furthermore, the embossing is formed in synchronization with the printing, so it is rich in design, and the back side is made of asbestos paper. It was reinforced with a transparent wear-resistant layer on the surface, making it suitable as a flooring material.

[Brief explanation of drawings]

FIGS. 1 to 3 are cross-sectional views showing examples of the structure of the decorative sheet obtained by the present invention. Figures 4 and 5
The figure is a sectional view showing a transfer paper used in carrying out the present invention. FIGS. 6 and 7 are cross-sectional views of back print films used in the practice of the present invention. 11... Batting backing material, 13... Foaming layer, 15, 15'...
Colored ink layer, 17... Colored ink layer containing foaming inhibitor, 19... Second barrier coat layer, 21... Bright ink layer, 22... Third barrier coat layer, 23... Surface layer, 25... Base paper, 27... Peeling layer.

Claims (1)

[Claims] 1. When printing a pattern using bright ink on a synthetic resin sheet, the pattern using colored ink or bright ink is printed on the synthetic resin layer with or without a transparent or translucent first barrier coat layer. A method for producing a decorative sheet, which comprises printing, applying a transparent or translucent second barrier coat layer thereon, and further forming a printed pattern using bright ink on the second barrier coat layer.