JPS5933313B2 - Transfer sheet and method for producing decorative materials using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a transfer sheet for producing an inorganic decorative laminate and a method for producing an inorganic decorative laminate using the same.

In recent years, there has been a growing demand for buildings to be non-combustible or flame-retardant.
In order to meet the demands for decorative building materials, there is an increasing demand for non-combustible or flame-retardant decorative laminates. Painted tiles are a traditional product that meets these demands. However, since these painted tiles are obtained by painting and glazing unglazed tiles and firing them at a high temperature of around 1050°C, the colorants that can be used are limited to specific inorganic pigments, and they also require energy consumption. The disadvantage is that the amount of consumption is large. Therefore, traditional painted tiles are not economical enough to be used as general decorative building materials. Painted inorganic-organic composite materials have been developed or proposed to overcome these drawbacks of painted tiles and provide relatively inexpensive non-combustible or flame-retardant decorative laminates.

The methods used for painting include the kneading method, direct printing method, and transfer method. However, the kneading method utilizes the design effect of the colored pattern created by mixing at least the coloring agent inhomogeneously in the process of kneading the inorganic material and the organic polymer material, and has the disadvantage that the finish is unpredictable. There is. The direct printing method, the immediate printing method, and the transfer method involve painting on an inorganic board by direct printing or transfer, and then finishing the surface by overcoating with resin paint, but these methods are not always satisfactory. It wasn't something. In other words, in the case of direct printing, it is extremely difficult to print on an inorganic board. For example, if you are trying to express the appearance of natural stone, even if you can paint it, you will not be able to achieve the delicate depth that natural stones have. I can't get it.

In the case of the single force and transfer force methods, it can be said that the force method is more suitable in terms of expressing the appearance of minute natural objects, but this force method also does not provide a composite body that is satisfactory as a building material. This is because the resin coating formed on the transferred pattern layer has insufficient adhesion to the porous inorganic plate and tends to peel off alone or together with the pattern layer. The present invention
An improved transfer sheet and a decorative board using the same are provided to improve the above-mentioned drawbacks of the transfer force type, that is, to provide a composite decorative board with excellent integrity of the pattern layer, top coat resin film, and porous Z-based inorganic board. The purpose is to provide a manufacturing method.

According to the research of the present inventors, the drawbacks of the conventional transfer method are:
It has been found that this is due to the fact that the pattern layer transferred onto the porous inorganic board prevents the top resin paint from permeating into the inorganic board. In other words, in the case of the transfer method, the general method is to overlay a transfer sheet, which is made by sequentially forming a pattern layer and a sealant layer on a base sheet, on an inorganic board, perform the transfer, and then apply a resin liquid to the surface. However, since the binder resin and sealant resin films that make up the pattern layer block the top coat resin liquid and prevent it from penetrating into the porous inorganic board, the adhesion between the paint film and the inorganic board is improved. This is because there is a lack of unity and peeling is more likely to occur. - It was found that As a result of further research by the present inventors, it has been revealed that such drawbacks can be overcome by reducing the film-forming properties of the pattern layer and selecting a sealant resin. The transfer sheet for producing porous inorganic decorative laminates of the present invention is
This is based on the knowledge mentioned above, and in more detail,
A pattern layer and a heat-sealing layer are provided in this order on one surface of the base sheet, and the pattern layer contains a bonding uniformity of 1 to 20 parts by weight of a colorant selected from 1k organic pigments and inorganic pigments and a binder. It is characterized in that it contains an extender pigment in the weight part, and that the heat seal layer is made of a resin that is soluble in the curable resin liquid.

In addition, the method for producing a porous inorganic decorative board of the present invention includes stacking the transfer sheet on a porous inorganic board so that the heat sealing layer thereof is in contact with the porous inorganic board; and thermally transferring the pattern layer of the transfer sheet to the porous inorganic board together with the heat sealing layer. ; Applying a curable resin liquid to the porous inorganic board from above the transferred pattern layer; Permeating the curable resin liquid into the porous inorganic board through the pattern layer; Curing the curable resin liquid. It is something to do.

The present invention will be explained in more detail below. In the following description, "%" and "parts" are based on weight unless otherwise specified. The base sheet constituting the transfer sheet of the present invention may be a known one, such as various papers and processed papers, synthetic resin films or sheets, metal foils such as aluminum foil, or laminates of two or more of these. 11・
Film etc. can be used.

The pattern layer provided on the base sheet contains a binder, a coloring agent selected from organic pigments and inorganic pigments, and an extender pigment.

The binder is preferably one that is not easily dissolved by the curable resin liquid described below.

Otherwise, it will be dissolved by the curable resin liquid that is overcoated after the transfer and the image will become unclear. However, since the resin liquid preferentially penetrates into the porous inorganic plate, it is okay for the binder to be dissolved to some extent by the resin liquid.
In addition, when aiming for a blurring effect, it is also possible to use a relatively highly soluble binder. Preferred binders include, for example, vinyl chloride resin, polyvinyl alcohol, polyvinyl acetal, cellulone derivatives, polycarbonate, polyamide, polyester, and polybutyral. One kind or a mixture of two or more kinds of resins such as the following can be used. Examples of inorganic pigments that can be used as the colorant include titanium white, carbon black, yellow lead, cadmium yellow, cadmium red, ultramarine blue, iron oxide, and alumina white. Further, as the organic pigment, Lake Red, Benjishin Yellow, Phthalocyanine Blow, Sinclair Red, etc. can be used. In any case, as the coloring agent, any organic or inorganic pigments other than those mentioned above can be suitably used depending on the desired color tone. In addition, extender pigments used as penetration enhancers include calcium carbonate, tare, talc, barium sulfate, calcium sulfate,
Silica or the like can be used.

In the present invention, the extender pigment constituting the pattern layer reduces the film-forming properties of the pattern layer and acts as a penetration enhancer that allows the topcoat resin liquid after transfer to penetrate into the porous inorganic plate.

Therefore, the content of these components in the pattern layer has an important meaning, and the extender pigment should be in the range of 1 to 20 parts based on the binder part. Particularly preferred is 5 to 10 parts. If it is less than 1 part, the penetration promoting effect will be poor, and if it exceeds 20 parts, the strength of the pattern layer will be insufficient and the suitability for coating will be insufficient.

Further, the extender pigment preferably has an average particle size of 10 μm or less in order to harmonize the effect as a penetration enhancer with the denseness of the pattern layer and suitability for coating. Each component constituting the above-mentioned pattern layer is used in an amount of 5 to 50 parts of methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, methyl acetate, butyl acetate, methanol,
The ink composition is kneaded with a solvent such as ethanol, cyclohexanone, and cellosolve, and if necessary, a plasticizer and other various known additives to form an ink composition of about 200 to 600 cps. Then, a pattern layer with an arbitrary pattern is formed by printing in a single color or in multiple colors on the base sheet.

Coating amount of this pattern layer (on dry basis, the same applies hereinafter)
is preferably in the range of 1 to 109/Trl. Next, a heat-sealing layer is formed on the pattern layer, but the resin constituting the heat-sealing layer needs to be soluble in the curable resin liquid described below. This is because after transfer, the heat-seal layer is located between the pattern layer and the porous inorganic board, so the heat-seal layer is dissolved by the hardening resin liquid that has passed through the design layer, and the heat-sealing layer is melted into the porous inorganic board along with the hardening resin liquid. It is necessary for it to penetrate. Preferably, a linear saturated polyester resin, a butyral resin, a vinyl chloride resin, or the like is used as the resin constituting the heat seal layer. These resins are kneaded together with a solvent and other known additives including a plasticizer as an optional component to form an ink composition.
1-59/ on the pattern layer by gravure printing or other conventional methods.
A heat-sealing layer is formed by applying the following amount. Next, the transfer sheet thus formed is stacked on a porous inorganic plate so that its heat-sealing layer is in contact with the transfer sheet, and heated to a surface temperature of 100, for example, using a hot plate or a hot roll.
The pattern layer is transferred to the inorganic plate via the heat-sealing layer by heat-pressing at ~250°C for 1-2 seconds and peeling off the base sheet.

Porous inorganic boards treated in this way include, for example, unglazed tile boards, gypsum boards, magnesium carbonate boards,
Calcium carbonate boards, asbestos perlite boards, asbestos cement boards, etc. can be used.

Further, composite materials such as wood wool cement boards, pulp cement boards, glass fiber reinforced cement boards, etc., which are made by mixing pulp, synthetic fibers, glass fibers, carbon fibers, etc. into the above-mentioned materials for reinforcement, can be used. At this time, unglazed tiles with residual heat immediately after firing, cement products immediately after steam curing,
By utilizing the heat generated during the manufacturing process of inorganic plates such as hardened gypsum during exothermic reaction due to hydration, thermal transfer can be performed by stacking transfer sheets and pressing them together without special heating. Next, a curable resin liquid is overcoated by any method on the pattern layer formed on the inorganic board at a ratio of 5 to 500 f1/i, for example, and passed through the pattern layer to dissolve the sealant layer and form a porous resin. The resin is cured when it penetrates to a depth of 1 to 2000 μm below the surface of the inorganic plate. The reason why a curable resin liquid is used is that it can provide a decorative surface with excellent hardness and heat resistance.

As the curable resin, a thermosetting resin can be used, but preferably a radiation curable resin that is cured by irradiation with ultraviolet rays or electron beams can cure physical properties such as surface hardness and even the porous inorganic layer. Alternatively, it is used for reasons such as being able to shorten the process. As the ultraviolet curable resin or electron beam curable resin used in the present invention, known resins can be used as they are.

Examples of UV-curable resins include acryloyl groups,
A resin having a radically polymerizable unsaturated group such as a methacryloyl group, an allyl group, a vinyl ether group, or an acrylamide group is used. Among these, those having an acryloyl group are preferred, and for example, epoxy acrylate, polyester acrylate, polyurethane acrylate, etc. are used alone or in combination. In the present invention, an ethylenically unsaturated monomer can be added in an amount of 80% or less of the total amount in order to adjust the viscosity of the ultraviolet curable resin as described above when applying the top coat. Ethylenically unsaturated monomers used for this purpose include styrene monomers such as styrene and α-methylstyrene; methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, and acrylic acid. Acrylic acid esters such as butyl acrylate, methoxybutyl acrylate, and phenyl acrylate; methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, and lauryl methacrylate Acid esters; unsaturated carboxylic acid amides such as acrylamide and methacrylamide; 2-(N,N-dimethylamino)ethyl acrylate, methacrylic acid 2-(N,N-
of unsaturated acids such as dimethylamino)ethyl, 2-(N,N-dibenzylamino)ethyl acrylate, (N,N-dimethylamino)methyl methacrylate, and 2-(N,N-diethylamino)propyl acrylate. Substituted amino alcohol esters; ethylene glycol diacrylate,
Propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate,
Examples include polyfunctional compounds such as triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, and diethylene glycol dimethacrylate.
3. Photosensitizers added to impart UV curability to the composition include, for example, benzoin, benzoin ether, benzophenone, acetophenone, benzyl,
Xanthone, thioxanthone, or derivatives thereof are used. 4.The ultraviolet curing resin liquid is
For example, 100 parts of the above-mentioned ultraviolet curable resin is kneaded with 20 to 80 parts of ethylenically unsaturated monomer, 0.1 to 5 parts of photosensitizer, and optional additives such as plasticizer added as needed. By doing so, it is used as a resin liquid with a viscosity of about 500 to 1000 cps. Further, as the electron beam curable resin liquid, the above-mentioned ultraviolet ray curable resin liquid may be used as it is or without the photosensitizer.

The curable resin liquid that has passed through the pattern layer and penetrated into the porous inorganic board as described above is heated. It is cured by conventional methods such as ultraviolet irradiation or electron beam irradiation.

Curing with ultraviolet rays is performed by irradiating for about 10 to 30 seconds using, for example, three to five 400 W/CfL high-pressure mercury lamps. Further, curing with an electron beam is performed using a linear filament type electron beam accelerator such as Electrocurtain manufactured by Energy Science.
This is carried out by irradiating a dose of about 1 to 10 megarads (based on the weight of the resin liquid) with an electron beam having an energy in the range of 0 to 1000 KeV, preferably 100 to 300 Ke. As described above, according to the present invention, when a pattern layer is thermally transferred to a porous inorganic board such as an unglazed tile via a heat-sealing layer, and a curable resin layer is further coated to obtain an inorganic decorative board, the pattern layer is By reducing the film-forming properties of the porous inorganic board and allowing the top coat resin liquid to penetrate the porous inorganic board through the pattern layer and harden it, an inorganic decorative board with excellent integrity between the base inorganic board and the surface decorative layer can be obtained.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 A pattern layer was formed on the polypropylene surface of paper/polypropylene composite processed paper (0.6 m 1 thickness) using three color inks (a) with the following composition by gravure printing with a total coating amount of 2f1/Rrl for the three colors. Then, apply a heat sealing agent with the following composition (
b) was applied to the entire surface by gravure printing at a ratio of 19/A to obtain a transfer sheet.

As organic pigments, Sinclair Red was used for the red ink, Phthalocyanine Blue was used for the blue ink, and Benzidine Yellow was used for the yellow ink.

(b) Heat sealant composition Linear saturated polyester resin 30 parts Solvent (methyl ethyl ketone: ethyl acetate little ene=
1:1:1) 70 copies of the transfer sheet obtained above
It was pressed between stacking rolls onto a 30 cwL square unglazed tile with residual heat of 00 to 200°C, and the base processed paper was peeled off.

On the pattern layer of the decorative tile obtained above, an acrylic ultraviolet curable paint (c) having the composition below was applied at a rate of about 300 g/m'' by a flow coating method and left for 20 seconds. The paint was cured by irradiating it with ultraviolet light for 20 seconds using three high-pressure mercury lamps.

(c) UV-curable paint Polyester acrylate 100 parts Methyl acrylate 50 parts Benzoyl 2 parts The decorative material thus produced had high adhesion as the organic polymer compound penetrated into the porous interior.

Example 2 A transfer sheet was obtained in the same manner as in Example 1, except that a 0.2 mm thick polyester film was used as the base sheet instead of the composite processed paper.

Next, 1 piece of plaster was placed in a formwork of 60 (V7l x 60cm).
After pouring a hydration hardening material having a blending ratio of 0.00 parts, 43 parts of water, 0.5 parts of glass fiber, and 3 parts of urea resin, and leaving it at room temperature for 1 hour, the above transfer sheet was superimposed on the cured material and pressed with a roll. I let it happen.

When the base sheet was peeled off, the pattern layer was transferred to the cured product due to the reaction heat of the plaster curing process. The pattern layer of this decorative plaster is coated with an acrylic electron beam curable paint (d) having the composition shown below at a rate of about 300 g/m'' by a flow coating method,
The coating was left to stand for 20 seconds, and then irradiated with an electron beam for 1 second at an acceleration voltage of 250 KV, a dose of 5 megarads (based on the weight of the coating), and an oxygen concentration of 250 ppm to cure the coating. (d) Electron beam curable paint polyester acrylate 100 parts acrylic acid 2 −
(N,N-dimethylamino)ethyl 50 parts The cosmetic material thus produced had high adhesion as the organic polymer compound penetrated into the inside of the inorganic porous material.

Claims (1)

[Scope of Claims] 1. A pattern layer and a heat-sealing layer are provided in this order on one surface of a base sheet, and the pattern layer contains a binder, a coloring agent selected from organic pigments and inorganic pigments, and 1 weight of the binder. 1 to 20 parts by weight of an extender pigment, and the heat-sealing layer is made of a resin soluble in a curable resin liquid. 2 A pattern layer and a heat-sealing layer are provided in this order on one side of the base sheet, and the pattern layer contains a binder, a coloring agent selected from organic pigments and inorganic pigments, and 1 to 20 parts by weight of the binder. Prepare a transfer sheet containing a weight part of extender pigment and in which the heat-sealing layer is made of a resin soluble in a curable resin liquid; Overlaying the transfer sheet on a porous inorganic plate so that the heat-sealing layer is in contact with the transfer sheet; Transfer sheet The pattern layer is thermally transferred to the porous inorganic board together with the heat-sealing layer; a curable resin liquid is applied to the porous inorganic board from above the transferred pattern layer; the curable resin liquid is passed through the pattern layer and onto the porous inorganic board. A method for producing a porous inorganic decorative board, characterized by infiltrating and curing the curable resin liquid. 3. The method according to item 2 above, wherein the pattern layer is thermally transferred using residual heat during manufacturing of the porous inorganic board. 4. The method according to item 2 or 3 above, wherein the curable resin liquid is a radiation curable resin liquid, and after coating and permeating the porous inorganic plate, the curable resin liquid is cured by irradiating with radiation.