JPS623224Y2 - - Google Patents

Description

[Detailed explanation of the invention] This invention consists of a base material and polyvinyl chloride (hereinafter referred to as PVC).
The present invention relates to a heat-resistant PVC laminate in which a heat-resistant PVC top layer is coated on a heat-resistant PVC top layer that is bonded to an undercoat layer using an amine-curing adhesive. In recent years, PVC products such as flooring and wall materials have become more fashionable, and with this trend, flooring and wall materials have become widely used as a type of home interior design. As such a product, a laminate is provided in which a PVC undercoat layer is adhered onto a base material using an amine adhesive, and an ultraviolet curable PVC top layer containing a reactive plasticizer is coated thereon. However, since such laminates use amine-curing adhesives, unreacted amine compounds contained in the adhesive penetrate into the PVC top layer after a long period of time, causing reactivity in the top layer. It has the disadvantage that it reacts with phenolic polymerization inhibitors such as hydroquinone, which are included as polymerization inhibitors in plasticizers, causing it to turn brown. The inventors of the present invention have intensively investigated a laminate that does not have such drawbacks, and have found that when unreacted amine compounds contained in the adhesive penetrate into the PVC undercoat layer, they are captured and prevented from reacting with the polymerization inhibitor. A highly effective laminate was found by adding an effective blocking compound. That is, in the present invention, a base material and a PVC subbing layer containing at least one compound selected from silicon dioxide-based compounds are bonded using an amine-curing adhesive, and a heat-resistant This invention relates to a heat-resistant PVC laminate with improved surface discoloration, which is coated with a PVC top layer. The base materials used in this invention include commonly used concrete, plywood, iron plates, gypsum board, and noncombustible board.
Examples include wall clay. Of course, other materials may also be used. The PVC undercoat layer may be a single layer or a multilayer, and it can be made into a multilayer using only a foamed PVC composition, or it can be made into a multilayer using only a non-foamed PVC composition. However, a foamed PVC composition and a non-foamed PVC composition can be combined to form a multilayer structure. In addition, the PVC used in the PVC subbing layer of the present invention is one manufactured by a general polymerization method such as suspension polymerization, emulsion polymerization, or solution polymerization. Furthermore, the PVC undercoat layer contains at least one compound selected from compounds whose main component is silicon dioxide;
Plasticizers, stabilizers, fillers, blowing agents, pigments, etc. can be added as appropriate. Among these, it is preferable to add as many plasticizers and stabilizers as possible. The compound containing silicon dioxide as a main component that is added to the PVC undercoat layer of this invention is Kiyoword
600, Kiyoward 700 (all products of Kyowa Kagakusha), activated clay, clay, talc, etc. The amount of such compounds added may be relatively small;
It is usually 10 parts by weight or less per 100 parts by weight of PVC. As the amine curing adhesive in the present invention, an epoxy resin-amine or epoxy resin-polyamide adhesive is usually used. Epoxy resins include bisphenol A/epichlorohydryl type, novolac type, flame retardant type, ester type, polyether type, cycloaliphatic type, methyl substituted type, urethane modified type, phenyl oxide type, pentaerythritol type, and tetraepoxy. Examples include glycidylamine type and glycidylamine type. On the other hand, amines used as curing agents include aliphatic amines, aromatic amines, and modified amines.
Specific examples thereof include ethylenediamine, diethylenetriamine, tetraethylenetetraamine, m-phenylenediamine, and diaminodiphenylsulfone. Examples of polyamides include alkyldiamine condensates of dimers of fatty acids such as soybean oil and tung oil, and ethylenediamine and diethylenetriamine. The epoxy resin and the amine compound are usually used by mixing the epoxy group and the amino group in approximately equivalent amounts. Note that it is permissible to use other adhesives such as polyvinyl acetate emulsion, acrylic emulsion, etc. in combination with the epoxy-amine or polyamide adhesive. The heat-resistant PVC top layer may be substantially crosslinked. That is, the entire heat-resistant PVC resin top layer may be formed only of a crosslinked PVC composition, or it may be partially formed of a non-crosslinked PVC composition. Uniform crosslinking when the heat-resistant PVC overcoat layer is formed of only a crosslinked PVC composition
This may be a PVC layer or a crosslinked PVC layer mixed with crosslinked PVC chips. Heat-resistant
When a part of the PVC top layer is formed of a non-crosslinked PVC composition, there are cases where it is a crosslinked PVC layer mixed with non-crosslinked PVC chips, or a crosslinked PVC layer mixed with non-crosslinked PVC chips.
For example, it is a non-crosslinked PVC layer mixed with synthetic chips. Part of the heat-resistant PVC top layer is non-crosslinked PVC
When the composition is formed, it is preferred that the proportion of non-crosslinked PVC composition be as small as possible. Chips made of non-crosslinked PVC and chips made of crosslinked PVC are crushed pieces obtained by crushing molded objects such as plates or rods of non-crosslinked PVC compositions or crosslinked PVC compositions into unspecified shapes using a crusher such as a pelletizer. In addition to the finished pieces, cut pieces cut into a specific shape and size can also be used. Here, crosslinked PVC compositions refer to various types of compositions in which a phenolic polymerization inhibitor such as hydroquinone is dissolved in advance or added later in a mixture of PVC (suspension polymerized resin or emulsion polymerized resin), a plasticizer, and a stabilizer. A reactive plasticizer, an ultraviolet curable resin and/or a monomer, etc., for example, a reaction product of an acrylic acid or methacrylic acid ester of a polyhydric alcohol, and a polymerization initiator, or a diallyl phthalate monomer and/or a diallyl phthalate prepolymer, and a polymerization initiator, A non-crosslinked PVC composition refers to a heat-cured product or a UV-cured product containing a photosensitizer, and non-crosslinked PVC compositions include various reactive plasticizers, UV-curable resins, monomers, etc. from the above-mentioned crosslinked PVC resin composition. All can be colored in any color. In the present invention, a base material can be inserted between the base material and the PVC undercoat layer. Such underlayment is bonded to the substrate with an amine-curing adhesive, and to the PVC subbing layer with an amine-curing adhesive or other adhesive. This base material includes base fabrics such as woven fabrics, knitted fabrics, and non-woven fabrics; paper materials such as kraft paper and Japanese paper; synthetic resin sheets; synthetic resin leather; heat-resistant sheets such as asbestos sheets and glass fiber-containing PVC sheets, etc. Can be mentioned. As the synthetic resin sheet, in addition to various foamed or non-foamed synthetic resin films, a paper material with a foamed or non-foamed synthetic resin layer laminated on at least one side can also be used. As the synthetic resin leather, a woven fabric, a knitted fabric, a non-woven fabric, etc. with a synthetic resin layer laminated on at least one surface can be used. In addition, the synthetic resin layers to be laminated may be multi-layered or single-layered, and in the case of multi-layers, they may be made of only non-foamed synthetic resin layers or only foamed synthetic resin layers. However, it may also be a multi-layered structure in which a non-foamed synthetic resin layer and a foamed synthetic resin layer are combined. In addition, in the present invention, the laminate may be printed, and the printed layer is a PVC subbing layer and a heat-resistant layer.
Preferably, it is interposed between the PVC top layer and the PVC top layer. Of course, the printed layer can be applied over a heat-resistant PVC top layer. Such printing layers are typically formed with printing inks used for printing vinyl chloride resin products. Gravure printing to form the print layer,
In addition to general printing methods such as flexographic printing and screen printing, a thermal transfer printing method in which a pattern printed in advance on transfer paper is thermally transferred can also be applied. To intervene with a printed layer, for example, printing may be performed on the surface of the PVC undercoat layer, and a heat-resistant PVC top layer may be laminated on the surface, or a previously prepared sheet forming the heat-resistant PVC top layer may be used. It is also possible to print on one side of the sheet-like object and to laminate the sheet-like object so that the printed surface is in contact with the surface of the PVC subbing layer. In this case, printing may be applied to both the surface of the PVC undercoat layer and one side of the sheet material forming the heat-resistant PVC top layer. Further, in the laminate of the present invention, a thermosetting or ultraviolet curable paint layer can be provided on the surface of the heat-resistant PVC top layer, or irregularities can be formed on the surface using a texturing machine or the like. Next, some laminates of the present invention will be explained with reference to the drawings. In Figure 1, there is an amine-cured epoxy resin adhesive layer 2 on a substrate 1, on top of which a PVC subbing layer 3, a printed layer 4 on top of that, and a heat-resistant PVC top coat on top of that. A laminate with layer 5 is shown. In Fig. 2, in the laminate shown in Fig. 1, an amine-cured epoxy resin adhesive layer 2 and a PVC subbing layer 3 are shown.
A laminate is shown in which a base material 6 is inserted between.
Figure 3 shows heat-resistant PVC in the laminate shown in Figure 2.
A laminate is shown in which a thermosetting or ultraviolet curing paint layer 7 is coated on top layer 5. In Figure 4, the second
In the laminate shown in the figure, a laminate containing non-crosslinked PVC pieces 8 in a heat-resistant PVC top layer 5 is shown. FIG. 5 shows a laminate in which the heat-resistant PVC top layer 5 contains crosslinked PVC pieces 9 in the laminate shown in FIG. In addition, in the laminate shown in FIG. 1, when the additives to the PVC undercoat layer were as shown in the table below, the discoloration of the surface of the laminate was as shown in the table below. 【table】

[Brief explanation of the drawing]

1 to 5 are cross-sectional views of the laminate of the present invention. 1... Base material, 2... Amine-cured epoxy resin adhesive, 3... PVC undercoat layer, 4... Print layer, 5... Heat-resistant PVC top layer, 6... Base material, 7... Thermosetting or ultraviolet curing paint layer, 8... Non-crosslinked PVC small piece,
9...Cross-linked PVC piece.

Claims (1)

[Scope of utility model registration request] A base material and a polyvinyl chloride undercoat layer containing at least one compound selected from silicon dioxide-based compounds are adhered using an amine-curing adhesive, and a heat-resistant polychloride undercoat layer is bonded to the base material using an amine-curing adhesive. A heat-resistant polyvinyl chloride laminate with improved surface discoloration and coated with a vinyl top layer.