JPH04356537A - Laminated material - Google Patents

Abstract

PURPOSE:To provide a laminated material in which the adhesion between the PVC layer of poor adhesion and the ultraviolet-curing resin is improved by forming an ultraviolet-curing resin coating layer prepared by polymerizing a specified monomer on the surface of a film containing such a specified monomer and polymerizing the monomer contained in the film. CONSTITUTION:A laminated material prepared by forming an ultraviolet-curing resin coating layer obtained by polymerizing an ethylenically unsaturated monomer and/or its oligomer on the surface of a film containing polyvinyl chloride, a plasticizer and an ethylenically unsaturated monomer and/or its oligomer, and polymerizing the monomer and/or the oligomer contained in the film. Examples of the curable monomers used include acrylic esters having one to several functional groups in the molecule and methacrylic acid. As the oligomers, photopolymerizable oligomers such as epoxy acrylate and urethane acrylate usually used for ultraviolet-curable coating materials are desirable.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention provides a laminated material that significantly improves the adhesion between an ultraviolet ray (hereinafter abbreviated as UV) cured resin layer and a synthetic resin such as polyvinyl chloride (hereinafter abbreviated as PVC) containing a plasticizer. This is what we provide.

0002

BACKGROUND OF THE INVENTION Conventionally, ultraviolet curing paints have been widely used in various fields as pollution-free, resource-saving, and energy-saving surface modifiers. On the other hand, PVC resin is also used in various fields, needless to mention here, and its surface is also modified with UV-curable paint.

However, when it is applied to a soft PVC resin molded product containing a plasticizer, there is a problem in that adhesion is difficult. For this reason, attempts have been made to improve adhesion by changing the composition of UV-curable paints, but satisfactory performance has not yet been achieved. This is because in the conventional coating method of UV curable resin, it is necessary to sacrifice the inherent properties of the UV curable resin coating, such as stain resistance and chemical resistance.

0004

SUMMARY OF THE INVENTION The object of the present invention is to obtain a laminated material with improved adhesiveness between a PVC layer, which originally had poor adhesiveness, and a UV cured resin.

[0005]

[Means for Solving the Problems] The present invention is an invention that solves the above-mentioned problems, and is an invention in which the film surface contains polyvinyl chloride, a plasticizer, and a monomer and/or oligomer having an ethylenically unsaturated group. A laminated material characterized by forming an ultraviolet curable resin coating layer obtained by polymerizing monomers and/or oligomers having unsaturated groups, and polymerizing the monomers and/or oligomers in the film. shall be.

[0006] In the present invention, an uncured UV curable monomer or oligomer is blended into a PVC film in advance, a UV curable resin is applied thereon, and UV rays are irradiated. By curing these UV-curable resins at the same time, it is possible to achieve unprecedented adhesion between the UV-curable resin coating and the soft PVC resin. The laminated material in the present invention is used with the surface of the film adhered to another base material.

[0007] A description will be given below according to the drawings. FIG. 1 is a cross-sectional view of the laminated material of the present invention. Reference numeral 1 denotes a base material, and any conventionally used base material such as metal, synthetic resin, wood, slate board, etc. may be used as the base material. The surface of the base material 1 is made of resin such as PVC containing a plasticizer. However, as a base material, PVC has a plasticizer of 5 to 200% for PVC.
It is preferable to use a resin layer containing PV
The composition and hardness of a C floor tile or the like or the composition and hardness of a soft foam base material such as a cushion floor may be used. 2 is a film containing PVC and a plasticizer;
It contains a resin containing a plasticizer such as, and a monomer and/or oligomer.

In the present invention, UV-curable monomers having ethylenically unsaturated double bonds include acrylic esters or methacrylic esters having one to several functional groups in the molecule, such as methoxypolyethylene glycol methacrylate, Photopolymerizable monomers and oligomers such as polyethylene glycol dimethacrylate, 2,2-bis{4-(methacryloxypolyethoxy)phenyl}propane, tripropylene glycol diacrylate, and trimethylolpropane trimethacrylate are commonly used for UV-curable paints. Photopolymerizable oligomers such as epoxy acrylate, urethane acrylate, and polyester acrylate that are commonly used are suitable.

Note that the PVC film 2 does not need to contain a photopolymerization initiator;
Addition of 1 to 10% by weight is desirable because the adhesion of the UV-cured resin layer of the resulting laminate is further improved.

As the photopolymerization initiator, an acetophenone type such as diethoxyacetophenone, a benzoin ether type such as isopropyl benzoin ether, a benzyl ketal type such as benzyl methyl ketal, a ketone type such as hydroxycyclohexyl phenyl ketone, benzophenone, etc. can be used.

A UV curing resin coating layer 3 is formed on the surface of the PVC film 2. The UV-curable resin coating layer 3 in the present invention contains the oligomer and/or monomer having the ethylenically unsaturated double bond, a photopolymerization initiator, and optionally additives such as a matting agent and a pigment. It is thought that the UV curable resin is irradiated with UV, and the resin of the UV curable resin coating layer is cured, and reacts and bonds with the monomer and/or oligomer in the PVC film at the boundary 4, and as a result, the coating layer 3 and the PVC The adhesion strength of Film 2 has been improved, and UV rays can be removed from any surface that was previously not bonded.
Even the cured resin coating layer is bonded to the film, so
The disadvantage of sacrificing the basic performance of the UV coating due to excessive consideration of adhesion to the film is eliminated. In this way, the laminated material 5 of the present invention having a UV-cured resin layer on the surface of the base material 1 is obtained.

FIG. 2 is a sectional view of another embodiment of the laminated material of the present invention, in which 1 is a base material containing a plasticizer, and 8 is a PVC material.
A transparent film in which the binder resin contains a monomer and/or oligomer having an ethylenically unsaturated double bond, and although the photopolymerization initiator does not need to be contained in the film, it is preferable that the photopolymerization initiator be contained.

A PVC paste printing ink layer 6 containing a large amount of plasticizer is formed between the transparent film 8 and the substrate 1. 3 is a UV-curable resin coating layer obtained by irradiating UV-curable monomers and/or oligomers containing ethylenically unsaturated double bonds.

[0014] When the laminated material of the present invention is laminated with the above base material, the difficulty in laminating a UV-cured resin film on layers conventionally printed with PVC paste ink containing a large amount of plasticizer is solved, and the layer becomes strong. Glued. In this way, for example, fashion flooring 7 is obtained. 4 is the boundary where the film and the UV curing resin coating layer are firmly laminated.

[0015]

[Example] PVC with the formulations of Examples 1 to 4 and Comparative Examples 1 to 3
A transparent film containing 45 parts by weight of plasticizer per 100 parts by weight of PVC was formed as a surface layer of a PVC sheet flooring material (Toli Cera Glow) having a printed pattern of PVC paste on the surface of the base material, and furthermore, each of Example 1 ~4, Comparative Examples 1~3 A UV cured resin coating layer having the composition was coated and then UV irradiated to obtain a laminated flooring material. The composition is shown in Tables 1 and 2.

[0016]

[Table 1]

[0017]

[Table 2]

A rubber piece was pressed against the obtained laminated material at 80° C. for 5 hours, and then the rubber piece was peeled off to examine the presence or absence of contamination. Regarding adhesion, cuts were made in a grid pattern on the UV resin-coated surface of the obtained laminated material, adhesive tape was pasted on it, and the adhesive tape was removed to examine the residual rate of the UV resin layer. . Furthermore, methyl ethyl ketone was rubbed onto the flooring materials of Examples 1 to 4 and Comparative Examples 1 to 3 obtained as a chemical resistance test. The results are shown in Table 3.

[0019]

[Table 3]

As shown in Examples 1 to 4 in Table 1, good results were obtained in both stain resistance and adhesiveness even when the types of monomers or oligomers in the transparent film and the UV-cured resin layer were changed. On the other hand, Comparative Examples 1 and 3 had good antifouling properties but poor adhesion, and Comparative Example 2 had poor antifouling properties.

Regarding chemical resistance, the flooring surfaces of Examples 1 to 4 were not affected at all. The present invention provides a durable floor sheet that is fully protected against scratches and stains.

[0022]

[Action] UV rays are applied on the surface of a film containing a plasticizer through a UV curing resin of monomers and/or oligomers containing ethylenically unsaturated double bonds and a synthetic resin base layer such as PVC resin containing a plasticizer. By laminating cured resin coating layers, a laminated material with high adhesive strength between the base material, film, and surface coating layer can be obtained. Even if a layer with a very high plasticizer content, such as PVC paste ink, is formed on the surface of the substrate, a good lamination function of the UV resin coating can be obtained.

The laminated material thus obtained is UV-resistant.
The resin coating layer does not peel off, has good abrasion resistance, stain resistance,
Cigarette resistance and chemical resistance are also good, and overall durability has been greatly improved. When such a laminated material was applied as a soft sheet flooring material, it could be used as a durable flooring material for heavy walking.

[0024]

[Effects of the Invention] ■ The lamination strength between the film and the UV-cured resin coating layer was high, and no peeling occurred.

(2) Improved stain resistance, solvent resistance, chemical resistance, etc.

(2) Overall durability was significantly improved.

(2) Even when used as a flooring material, a flooring material that is highly stain resistant and durable and is optimal as a flooring material for heavy walking was obtained.

■ Even if there is a PVC paste printed layer containing a large amount of plasticizer on the base material, a laminated material consisting of the film of the present invention and the UV resin coating layer is formed on top of it, and both layers are strongly laminated. The UV resin coating layer was not easily peeled off.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view of the laminated material of the present invention.

FIG. 2 is a sectional view of another embodiment of the laminated material of the present invention.

[Simple explanation of the sign]

1 Base material 2 Film 3 UV resin coating layer

Claims (3)

[Claims] Claim 1: Obtained by polymerizing a monomer and/or oligomer having an ethylenically unsaturated group on the surface of a film containing polyvinyl chloride, a plasticizer, and a monomer and/or oligomer having an ethylenically unsaturated group. A laminated material characterized by forming an ultraviolet curable resin coating layer and polymerizing monomers and/or oligomers in the film. 2. The laminated material according to claim 1, wherein a photopolymerization initiator is contained on the surface of the film. 3. The laminated material according to claim 1, wherein the film is formed on a pattern layer printed with an ink containing polyvinyl chloride and a plasticizer.