JPS6286030A - Manufacturing method for uneven decorative material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] Purpose of the Invention [Industrial Application Field] The present invention is directed to a method for producing a material having excellent surface physical properties such as heat resistance, abrasion resistance, stain resistance, and solvent resistance, which is embossed by a chemical embossing method. The present invention relates to a method of manufacturing a textured decorative material.

[Prior technology] When producing uneven decorative materials, there are some that employ the chemical embossing method and emboss a single foamed resin layer without a top coat, but polyvinyl chloride resin is usually used as the foamed resin. Because of this, the surface properties are poor.

If a urethane-based or acrylic-based ionizing radiation-curable resin is used as a top coat, it will harden immediately if applied before the foamable resin foams, so foaming will be suppressed and preferred embossing will not be obtained.

Furthermore, if the foaming resin is applied after foaming, the resin may not be able to be applied to the recesses, or may go too far into the recesses, causing the embossed feel to be lost.

[Problems to be Solved by the Invention] The purpose of the present invention is to improve the above-mentioned drawbacks, to provide an emboss with high design quality, especially an emboss that matches the pattern if desired, and with excellent surface properties. An object of the present invention is to provide a method for manufacturing an uneven decorative material.

Structure of the Invention [Means for Solving the Problems] The manufacturing method of the present invention will be explained with reference to the drawings.
As shown in the figure, a foamable resin layer 2A containing a foaming agent is provided on the entire surface of the base material 1, and then printed with a printing ink containing a foaming inhibitor, and then cured with uncured ionizing radiation on the entire surface. After providing the synthetic resin layer 5A, as shown in FIG.
At the same time as forming the foamed resin layer 2B by heating and foaming, the portion printed with a printing ink containing a foaming inhibitor is made into a recess 6, and as shown in FIG. 3, by irradiating ionizing radiation 8 to crosslink and harden As shown in FIG. 4, the method is characterized in that an ionizing radiation-cured resin layer 5B is obtained.

As a preferred embodiment of the present invention, as shown in FIGS. 1 to 4, a pattern is printed with a printing ink 4 containing a foaming inhibitor, and printing without a foaming inhibitor is also performed before and/or after. Print the pattern using Ink 3.

As the base material, one can be used that is appropriately selected depending on the intended use of the uneven decorative material obtained by the method of the present invention. For example, if the application is wallpaper, flame-retardant backing paper that has undergone flame-retardant treatment is usually used. For bedding sheets such as cushion floors, asbestos sheets or glass fiber non-woven fabrics are used.

In addition, anything that is normally used as a base material for decorative materials can be used, including various papers, plastic films, wood base materials, gypsum base materials, fiber cement boards, concrete boards, metal foils or sheets or boards. For example, a complex of these may be used.

Commonly used foaming agents, foamable resins, and foaming inhibitors may be used. The foamable resin layer is formed by applying a foamable resin by flow coating, roll coating, gravure coating, or the like.

As the printing ink, any commonly used product may be used, whether or not it contains a foaming inhibitor.

Typical examples of ionizing radiation are electron beams and ultraviolet rays.
The former is emitted from various electron beam accelerators, and is 50 to 100
An electron beam with an energy in the range of 0 KeV, preferably 100 to 300 KeV is used, the latter coming from a high pressure mercury lamp or other ultraviolet source.

The ionizing radiation-curable resin used in the present invention is a thermoplastic resin having a radically polymerizable unsaturated group, and there are the following two types.

(1) A polymer having a glass transition temperature of O to 250'C and having a radically polymerizable unsaturated group.

Specifically, the following methods (i) to (
Those into which radically polymerizable unsaturated groups have been introduced according to (d) can be used.

■ Monomers with hydroxyl groups: N-methylol acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate,
2-Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, etc. Monomers with carboxyl groups Niacrylic acid, methacrylic acid, acryloyloxyethyl monomer Succinate, etc. ■ Monomers with epoxy groups such as nigericidyl methacrylate ■ Monomers with aziridinyl groups: 2-aziridinylethyl methacrylate, allyl 2-aziridinyl propionate, etc. ■ Monomers with amine groups Monomers with sulfone groups: 2-acrylamide-2-methylpropanesulfonic acid, etc. Monomers with isocyanate groups = 2 , an adduct of a diisocyanate and a radically polymerizable monomer having active hydrogen, such as an equimolar adduct of 4-toluene diisocyanate and 2-hydroxyethyl acrylate. In order to control or match the physical properties of the cured film, the above compounds can also be copolymerized with monomers copolymerizable therewith. Such copolymerizable monomers include, for example, methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate,
Isobutyl methacrylate, t-butyl acrylate,
t-butyl methacrylate, isoamyl acrylate,
Examples include isoamyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate.

Next, radically polymerizable unsaturated groups are introduced into the polymer obtained as described above by methods (a) to (d) described below.

(a) In the case of a polymer or copolymer of a monomer having a hydroxyl group, a monomer having a carboxyl group such as acrylic acid or methacrylic acid is subjected to a condensation reaction.

(b) In the case of a polymer or copolymer of monomers having a carboxyl group or a sulfone group, the monomers having the aforementioned hydroxyl group are subjected to a condensation reaction.

(c) In the case of a polymer or copolymer of a monomer having an epoxy group, an isocyanate group, or an aziridinyl group, the above-mentioned monomer having a hydroxyl group or monomer having a carboxyl group is subjected to an addition reaction.

(d) In the case of a polymer or copolymer of a monomer having a hydroxyl group or a carboxyl group, a monomer having an epoxy group or a monomer having an aziridinyl group, or a diisocyanate compound and a hydroxyl group-containing acrylic acid. An equimolar adduct with an ester monomer is subjected to an addition reaction.

The above reaction is preferably carried out while adding a trace amount of a polymerization inhibitor such as hydroquinone and blowing dry air.

(2) A compound having a melting point of 20 to 250°C and necessarily having a radically polymerizable unsaturated group. Specific examples include stearyl acrylate, stearyl methacrylate, triacryl isocyanurate, cyclohexanediol diacrylate, cyclohexanediol methacrylate, spiroglycol diacrylate, and spiroglycol dimethacrylate.

In the present invention, the above (1) and (2) can be used as a mixture, and a radically polymerizable unsaturated monomer can also be added to them. This radically polymerizable unsaturated monomer improves crosslinking density and heat resistance when irradiated with ionizing radiation, and in addition to the above-mentioned monomers, ethylene glycol diacrylate, ethylene glycol dimethacrylate, Polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol tetraacrylate, penta Erythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene glycol diglycidyl ether diacrylate, ethylene glycol diglycidyl ether dimethacrylate, polyethylene glycol diglycidyl ether dimethacrylate Acrylate, polyethylene glycol diglycidyl ether dimethacrylate, propylene glycol diglycidyl ether diacrylate, propylene glycol diglycidyl ether dimethacrylate, polypropylene glycol diglycidyl ether diacrylate, polypropylene glycol diglycidyl ether dimethacrylate, sorbitol tetraglycidyl ether tetraacrylate,
Sorbitol tetraglycidyl ether tetraacrylate, etc. can be used, and it is preferable to use 0.1 to 100 parts by weight based on 100 parts by weight of the solid content of the copolymer mixture. However, when curing by ultraviolet irradiation, benzoin ethers such as benzoquinone, benzoin, and benzoin methyl ether, halogenated acetophenones, and biacetyls may be used as sensitizers. Those that generate radicals can also be used.

The ionizing radiation curable resin layer is formed by applying an ionizing radiation curable resin diluted with a solvent by flow coating, roll coating, gravure coating, or the like, and then scattering the solvent by heat drying to form a solid film.

[Function] As shown in FIGS. 1 and 2, when heated and foamed, foaming of the foamable resin layer 2A in this region is suppressed in a region printed with a printing ink containing a foaming inhibitor, resulting in a concave portion. Since the ionizing radiation-curable resin layer 5A is thermoplastic, the concave portions 6 and convex portions are formed according to its irregularities. As a preferable example of this aspect, when a pattern is printed with the printing ink 4 containing a foaming inhibitor and a pattern is printed with the printing ink 3 that does not contain the foaming inhibitor, the portion of the printing ink 4 becomes a recess 6, and the printing ink is The part 3 becomes a convex part, and an emboss that matches the pattern is formed.

[Example] A foamable resin having the following formulation was prepared. (All parts are by weight.) PVC paste resin 100 parts DOP
70 copies DBP
30 parts Tt02
15 parts stabilizer (dibasic lead phosphite)
3-part blowing agent (ADCA type)
5 parts filler (aluminum hydroxide > 30
A total of 253 parts 80g/TIi flame retardant wallpaper base paper R80AF-10J Kudesumi National Policy Pulp) was coated with the above foamable resin on the entire surface to a thickness of 200g.
After coating and drying, apply PVC ink rN to the surface.
The pattern was printed with WPJ (Showa Ink), and the pattern was printed with salt-vinyl acetate ink rLIEJ (Moroboshi Ink) containing a foaming inhibitor.

The material shown in Figure 1 was prepared by applying an ultraviolet curable resin "Copimer" (Mitsubishi Yuka Fine Co., Ltd.) to a thickness of 3 μm over the entire surface.

The foamable resin layer was foamed by heating at 200° C. for 1 minute to form a foamed resin layer as shown in FIG. 2 with a foamed portion having a thickness of 600 μm.

As shown in Figure 3, this sheet was heated using a 160W high pressure mercury lamp.
/cm4 lamps at a speed of 10 m/min to crosslink and cure the ultraviolet curable resin layer.

As a result, as shown in FIG. 4, a textured decorative sheet 1q having an ultraviolet curable resin layer on its surface and having embossments that matched the pattern of the foaming inhibitor-containing ink and having good surface physical properties was obtained.

Effects of the Invention The uneven decorative material produced by the method of the present invention has excellent surface properties such as heat resistance, abrasion resistance, stain resistance, and solvent resistance because the surface layer is formed of an ionizing radiation-cured resin. There is. The embossing is symmetrical or asymmetrical to the pattern as desired, and has a high degree of design.

[Brief explanation of drawings]

1 to 4 are schematic cross-sectional views illustrating the steps of the method for manufacturing the uneven decorative material of the present invention. FIG. 2 shows the stage of heating and foaming, and FIG. Figure 4 shows the stage in which the sheet is irradiated with the ionized copper wire, and Figure 4 shows the finished uneven decorative material. 1...Base material

Claims (2)

[Claims] (1) A foamable resin layer containing a foaming agent is provided on the entire surface of the base material, and then printed with a printing ink containing a foaming inhibitor. After applying a hardened ionizing radiation curable resin layer to the entire surface,
The method is characterized in that a foamed resin layer is formed by heating and foaming, and at the same time, a portion printed with a printing ink containing a foaming inhibitor is made into a recess, and an ionizing radiation-cured resin layer is obtained by cross-linking and curing by irradiating with ionizing radiation. A method for manufacturing uneven decorative materials. (2) According to claim 1, the pattern is printed with a printing ink containing a foaming inhibitor, and the pattern is printed with a printing ink that does not contain a foaming inhibitor before and/or after that. manufacturing method.