JPS5941794B2 - Method for manufacturing decorative material with uneven surface - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a decorative material having an uneven surface, and more particularly to a method for manufacturing a decorative material having an uneven surface with excellent sharpness of the foam suppressing portion and hardness of the surface.

Decorative materials, which are made by covering base materials such as paper, woven fabrics, non-woven fabrics, metals, and wood with resin sheets printed with various designs, are used for a variety of purposes such as wallpaper, wall materials, flooring materials, and automobile interiors. It is used.

In order to further enhance the decorative effect of such decorative materials, and to obtain a high degree of repulsion and excellent texture, it is possible to use a foamed resin sheet as the resin sheet, and to make the surface of this sheet have an uneven surface that matches the design. It is being done. A method for obtaining such a decorative board is described in Japanese Patent Publication No. 43-28636. That is, this is a method in which a pattern is applied to the surface of a foamable resin composition using an ink containing an inhibitor that changes the decomposition temperature of the foaming agent, and then the composition is heated and foamed. Foaming is suppressed in the areas where the design is applied with ink containing an inhibitor, and the resulting areas become concave areas, while other areas undergo normal foaming and become convex areas. However, although the decorative material obtained by the above-mentioned method certainly has an excellent decorative effect, it has the disadvantages that the foaming suppressing part, that is, the concave part, is not formed sharply, and the surface hardness is insufficient. are doing.

Therefore, it is an object of the present invention that the foaming suppressing portion is sharp;
Another object of the present invention is to provide a method for manufacturing a decorative material having an uneven surface with improved surface hardness. That is, according to the present invention, a desired pattern is printed on the resin composition surface of a substrate coated with a polyvinyl chloride resin composition layer containing a foaming agent and a plasticizer, using an ink having a foaming suppressing effect, and then heated and foamed. In the method of forming an uneven surface by forming a foaming portion and a foaming suppressing portion, the resin composition further contains at least two peroxide crosslinking initiators and a reactive plasticizer in one molecule. There is provided a method for producing a decorative material having an uneven surface, which is characterized by containing a compound having the above-mentioned double bond. In the production of a conventionally known polyvinyl chloride foam decorative material having an uneven surface, the present invention further comprises adding a peroxide crosslinking initiator to a polyvinyl chloride resin composition before foaming, and adding two or more peroxide crosslinking initiators per molecule. This was done based on the knowledge that when a reactive plasticizer having a double bond is included, a decorative material having an uneven surface with improved sharpness of the foam suppressing portion and improved surface hardness can be obtained.

In the present invention, the reason why a decorative material having an uneven surface with improved sharpness of the foam suppressing part and improved surface hardness is obtained is probably because the reactive plasticizer having two or more double bonds in one molecule is This is thought to be because it not only acts as a plasticizer for vinyl chloride resin, but also causes a crosslinking reaction with polyvinyl chloride in the presence of a crosslinking initiator, thereby making the resin structure stronger. The compound having two or more double bonds in its molecule, which is used as a reaction plasticizer, can be easily incorporated into the resin in the same manner as general plasticizers. Examples of compounds having two or more double bonds in one molecule used as a reaction bending plasticizer in the present invention include p-quinonedioxime and p-p-
Quinone dioxime compounds such as dibenzoylquinone dioxime, ethylene glycol acrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropene trimethacrylate and methyl methacrylate. methacrylate compounds, diaryl fumarate,
Allyl compounds such as diaryl phthalates, tetraaryloxyethanes and triaryl cyanurates, maleimides, phenylmaleimides and N,N'-
These include maleimide compounds such as m-phenylenehismaleimide, as well as maleic anhydride and divinylbenzene. Particularly preferred compounds are diaryl phthalates. Note that diaryl phthalate polymers can also be used as reactive plasticizers. The amount of plasticizer used in the reaction is 5 to 3 parts by weight per 100 parts by weight of polyvinyl chloride resin.
0 parts by weight, preferably 10 to 20 parts by weight. As the crosslinking initiator used in the present invention (3, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-tantane hydroperoxide, di-t-butyl peroxide, i-
Butylcumyl peroxide, 2,5-dimethyl-2,5
-di(t-butyloxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t
-butylperoxy-3,5,5-trimethylhexanoate, 1-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, and the like.

The blowing agents used in the present invention include azodicarbamide, P,p'-oxybis(benzenesulfonyl hydrazide), P,p'-oxybis(benzenesulfonyl semicarbazide), azobisisobutyronitrile, N,N
ξdimethyl-N,N5-dinitrosoterephthalamide,
Examples include diazoaminobenzene.

Furthermore, the ink having a foaming suppressing effect used in the present invention contains an organic acid such as maleic acid, fumaric acid, adipic acid, or 1,2-phthalic acid, which has the effect of increasing the expansion temperature of the foaming agent. It can be made into ink.

The above-mentioned reactive plasticizers, crosslinking initiators, foaming agents, and inks having a foaming inhibiting effect can be used in suitable combinations.

Further, the foaming conditions may be those suitable for an ink having a foaming agent and a foaming suppressing agent. As explained above, according to the method of the present invention, crosslinking is initiated when a decorative board having an uneven surface is prepared by heating and foaming a foamed resin composition printed with a desired pattern using an ink having a foaming suppressing effect. The crosslinking reaction between the plasticizer and polyvinyl chloride in the presence of the agent makes the resin structure tough, resulting in a decorative material with an uneven surface that improves both the sharpness of the foam suppressing area and the hardness of the surface. is obtained.

Hereinafter, specific examples of the present invention will be shown.

Example 1 A plastisol having the following composition was coated on a release paper and heated at 120° C. for 1 minute to form a sheet with a thickness of 0.2 mm.

A desired pattern was printed on the surface of this sheet using ink containing maleic anhydride. The printed resin layer was then heated at 200° C. for 2 minutes to foam. the result,
A decorative material was obtained that had an uneven surface with a sharp bulge-suppressing portion and improved surface hardness. PVC
100 parts by weight plasticizer (DOP)
26〃Reaction l Plasticizer 20〃(Diallyl phthalate) Foaming agent (AZH) 3〃Stable h(
FL-23) 2 (ZnO)
1 Titanium white
10 parts cross-linking initiator (Kayahexa YD) 3
Example 2 Reaction The amount of plasticizer (diallyl phthalate) is 10% by weight? The test was conducted in the same manner as in Example 1, except that the amount was reduced.

Claims (1)

[Claims] 1. A desired pattern is printed on the coated surface of a substrate coated with a polyvinyl chloride resin composition layer containing a foaming agent and a plasticizer using an ink that has a foaming suppressing effect, and then heated and foamed. In the method of forming an uneven surface by producing a foamed portion and a foamed-inhibited portion, the resin composition further comprises 1 as a peroxide crosslinking initiator and a reactive plasticizer.
A method for producing a decorative material having an uneven surface, characterized by containing a compound having two or more double bonds in the molecule. 2. The method for producing a decorative material having an uneven surface according to claim 1, wherein the compound having two or more double bonds in one molecule is diallyl phthalate.