JPH0813740A - Decorative member - Google Patents

Abstract

PURPOSE:To prevent generation of a poison gas in the burning time, by providing a corona discharge process surface, on one side surface of a printed sheet formed of a resin which is made by neutralizing a copolymer of ethylene and an unsatulated carboxilic acid, so as to form a design layer. CONSTITUTION:From a copy sheet formed by laminating design layers 2 and heat adhesive resin layers in order on a basic sheet, a corona discharge process surface 4 is provided on the surface of a sheet to be printed 5, when necessary. In this case, the design layers 2 are copied when necessary, to a sheet 5 of ionomer made by neutralizing partially or perfectly a copolymer of ethylene and the theta and beta unsatulated carboxilic acids by using a metallic ion. The ionomer sheet 5 to form the surface layer of a decorative member K has an excellent antiabrasive and antimedicinal property, and it secures the durability of the design layers 2 provided through the sheet 5. Consequently, the printing effect is increased by using the ionomer sheet 5, and generation of a public hazard resulting from the chlorine can be prevented.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a decorative sheet,
Due to surface characteristics, especially design of pattern layer, abrasion resistance, chemical resistance, black smoke, secondary disasters due to hydrogen chloride gas, such as black smoke and hydrogen chloride gas, which occurs when incinerated and discarded, or when fire occurs. The present invention relates to a decorative material that constitutes a building member that does not generate corrosive strong acid gas or harmful gas.

[0002]

2. Description of the Related Art Conventionally, a printed sheet of a decorative material used for a construction member such as a light electric appliance, a floor material, a wall material, etc. can be flexibly and hard to soft adjusted by an amount of a plasticizer added. In addition, a sheet of polyvinyl chloride, which is excellent in embossing suitability for providing an uneven pattern, has been widely used. A sheet provided with a desired surface makeup is used by laminating it on a rigid body such as plastic or plywood.

Further, in a decorative sheet coated for improving the physical properties of the surface, after a desired design is formed on a base sheet, a plastic sheet as a surface layer is laminated,
Solvent-soluble varnish, thermosetting resin composition, or
Some of them have been coated with an ionizing radiation curable resin.
Then, in the case of applying the ionizing radiation-curable resin, the application surface was covered with a film having an uneven pattern, if necessary, and irradiated with ionizing radiation to form an uneven pattern layer on the surface of the decorative sheet.

[0004]

However, the polyvinyl chloride used in the surface layer of the decorative sheet of the prior art and the sheet to be printed has a problem of secondary disaster caused by black smoke and hydrogen chloride gas generated in the case of fire. There is a problem, and there is also a problem in that waste gas processing costs are generated due to the problems of hydrogen chloride gas generated when processing the waste, corrosion of the incinerator by chlorine gas, and strong acid gas. In order to reduce the problem, in order to reduce the amount of chlorine contained in the decorative sheet,
A method of using a transparent resin varnish for the surface layer of the printed decorative surface instead of the transparent vinyl chloride sheet has been used.

In this case, when the solvent-soluble resin varnish is applied as the transparent surface layer, it is easy to form a protective film on the surface only by drying the solvent, but the surface hardness, gloss and resistance It was not sufficiently satisfactory in friction resistance, chemical resistance, etc., and the shape of the coated surface was extremely limited. And, if polyvinyl chloride is used for the base material sheet, the above problems cannot be essentially solved.

The surface layer formed of a thermosetting resin composition has a certain degree of surface hardness and chemical resistance, but the condition is that the sheet on which the pattern is to be formed must withstand the curing temperature of the composition. There was a limit to the selection of sheet material. Then, there is a problem that it is difficult to apply it to general polyvinyl chloride and polyolefin. Further, the polyvinyl chloride sheet that has been conventionally used is a thermoplastic resin having excellent embossing suitability for providing an uneven pattern on its surface, whereas a polyolefin sheet such as polyethylene does not necessarily have embossing suitability and resistance. It was not a material suitable for wear resistance.

Further, the resin (hereinafter referred to as an ionomer) obtained by partially or completely neutralizing the copolymer of ethylene and α, β unsaturated carboxylic acid of the present invention with a metal ion has transparency, gloss, It has excellent wear resistance. However, there is a difficulty in film-forming suitability, it is difficult to avoid the generation of protrusions due to the gelled product, and there is a printing defect accompanying it,
In addition, there is a defect that the sheet surface lacks specular gloss.

The present invention is a decorative material which can form an uneven pattern layer having a surface shape and has an excellent surface gloss and a pattern layer and which is excellent in abrasion resistance. When it is incinerated, pollution caused by chlorine is not generated. The purpose of the present invention is to provide a cosmetic material which has a good printing effect by using a non-ionomer sheet and is free from foreign matters such as protrusions and has excellent surface properties.

[0009]

In order to achieve the above object, the decorative material of the present invention is a decorative material in which a pattern layer is formed on one surface of a sheet to be printed formed of an ionomer. Further, a print-receiving sheet made of the above-mentioned ionomer is provided on one surface of the support, and a pattern layer is further configured in order.

The present invention is a decorative material K, as shown in FIG. 1, in which one surface of a printing target sheet 5 is subjected to corona discharge treatment, if necessary, and a pattern layer 2 is provided on the treated surface 4.
Further, as shown in FIG. 2 (a), the pattern layer 4 is formed on the base sheet 1.
As shown in FIG. 2 (b), a corona discharge treated surface 4 is provided on the surface of the printing target sheet 5 from the transfer sheet T formed by laminating the thermal adhesive resin layer 3 and the thermal adhesive resin layer 3 in order. The decorative material K is formed by providing the pattern layer 2 through the base sheet 1 and peeling off the base material sheet 1. The resin layer of the printed sheet 5B made of an ionomer formed on one surface of the support 6 shown in FIG.
Directly or from the transfer sheet T shown in FIG. 3 (b),
This is a decorative material K in which a pattern layer 2 is provided on a printed sheet 5.

As shown in FIG. 3 (b), the print-receiving sheet 5B provided on the support 6 and the thermal adhesive resin layer 3 of the transfer sheet T are laminated so as to be in contact with each other, and the pattern layer is formed by heating and pressing. When the decorative material K is formed by thermally transferring 2, the support 6 and the base material sheet 1 are finally peeled off after the thermal transfer process, but the sheet to be printed 5 and the protective sheet for the pattern layer 2 are formed. It can also be used as In addition, the support 6 is used when the pattern layer 2 is provided on the printed sheet 5 having a low softening temperature,
When the printing is performed, the sheet is suppressed from being softened and stretched by the drying temperature, and acts to provide the accurate pattern layer 2. Further, from the transfer sheet T to the pattern layer 2
It is intended to prevent the sheet to be printed from being softened by the heat at the time of thermal transfer of the sheet and causing troubles such as poor running.

The ionomer used in the printed sheet of the present invention is preferably a resin obtained by partially or completely neutralizing a copolymer of ethylene and an α, β unsaturated carboxylic acid with a metal ion. Common metal ions are Na ⁺ , Cu ⁺⁺ , A
Examples thereof include g ⁺ and Zn ⁺⁺ , but Zn ⁺⁺ and Na ⁺ are preferable. In addition, the acid component in the copolymer of ethylene and α, β unsaturated carboxylic acid includes acrylate acid, methacrylic acid, etc., but the acrylic acid copolymer has an ionization degree of 30.
-60% is preferable. Those having a low ionization degree have poor embossing suitability, and those having a high ionization degree have poor film forming suitability.

The ionomer film is formed by blow molding with a circular die (inflation method), melt extrusion molding with a T die (T die method), or melt extrusion coating. The sheet obtained by blow molding with a circular die has a problem that the gloss and transparency are slightly inferior because it is cooled by air, and there is a problem that a fish eye-shaped protrusion is precipitated due to the gelation product contained in the ionomer. It has the advantage that changes can be made arbitrarily.

Melt extrusion molding using a T-die has excellent gloss and transparency due to rapid cooling by a cooling roll, and depending on the surface condition of the cooling roll, the uneven pattern layer of the sheet can be formed at the time of molding. Further, it is a method suitable for forming a film on the support according to claim 2 of the present invention. The thickness of the printed sheet is 30 ~ which does not hinder the printing and post-processing of embossing.
It is performed at 200 μm. In order to strengthen the adhesion to the thermal adhesive resin layer of the transfer sheet or the ink that forms the pattern layer,
It is preferable to perform corona discharge treatment on the side of the printed sheet that is adhered to the pattern layer.

In the corona discharge treatment, a high voltage corona is generated when a high voltage is applied at a high frequency to the gap between the electrode directly connected to the high voltage and the silicon-coated metal roll. When the sheet travels at a constant speed here, ozone and nitric oxide react with each other to generate a carbonyl group or the like, which becomes hydrophilic. At the same time, a rough surface with numerous holes is formed on the surface by arc discharge, and a low molecular weight material on the surface of the sheet is treated to improve the adhesiveness of printing ink or the like and strengthen it. Effective corona discharge throughput is 46-50 dynes / cm. If it is 50 dynes / cm or more, blocking may occur during winding, or pinholes may occur in the sheet due to arc discharge. When it is 46 dyne / cm or less, the adhesion of the printing ink may lack stability, and at the same time, sufficient adhesive force with other sheets may not be obtained by post-processing.

The support used in the present invention is selected from materials having a softening temperature that does not melt and cut by heat when forming an ionomer film, and in some cases, a plastic film layer is provided on paper or aluminum foil having no thermoplasticity. Can also be formed. For example, a stretched or unstretched sheet of polyester, polyamide, polypropylene, or the like,
It is cellophane or the one that is pasted or coated on paper. The concavo-convex pattern formed on the support is applied to the surface layer of the sheet to be printed, and the pattern layer can be seen through the concavo-convex pattern layer.

The base material sheet used for the transfer sheet has excellent printability among materials that can be used for ordinary transfer sheets and does not melt and cut due to heat during transfer. For example, there is a stretched or unstretched sheet of polyester, polyamide, polypropylene, or the like, or a laminate of these and paper. And the thickness is 5 to the extent that printing is not hindered.
It is preferable that the thickness is as thin as 50 μm because there is no heat unevenness when transferring the pattern layer and a uniform adhesive can be formed.

The ink used in the pattern layer of the transfer sheet of the present invention may be any ink that has an appropriate releasability from the base sheet.
The releasability of the pattern layer is determined by the color-developing material of the base sheet and the ink. Linear polyester, polyvinyl butyral, ethyl cellulose, rosin derivative, vinyl chloride / vinyl acetate copolymer, chlorinated polyethylene, chlorinated polypropylene. The color developing agent can be appropriately selected from the above.

The heat-adhesive resin layer used for the pattern layer of the transfer sheet of the present invention is to thermally bond to the sheet to be printed to transfer and bond the pattern layer. Linear polyester, acrylic, polyurethane, vinyl chloride. Vinyl acetate copolymer,
It can be selected from chlorinated polyethylene and chlorinated polypropylene.

When printing directly on the ionomer, an ink having an acrylic urethane resin, which is adhesive to the resin, as a binder is used. In order to stabilize the adhesion, it is possible to print by providing a primer layer on the printing target sheet. As the material for the primer layer, linear polyester, chlorinated polyethylene, chlorinated polypropylene, two-component reactive polyester / isocyanate or polyether / isocyanate varnish can be selected and used.

[0021]

As described above, according to the present invention, an elaborate pattern layer is transferred from a transfer sheet, if necessary, to an ionomer sheet which is a chlorine-free plastic sheet. Therefore, it has a finely printed pattern layer. The ionomer sheet forming the surface layer of the decorative material has excellent abrasion resistance and chemical resistance, and acts so as to have durability of the pattern layer provided through the sheet.

The support acts so as not to cause dimensional change (elongation) of the ionomer sheet during heating or sticking of the molten ionomer layer during printing or thermal transfer on the ionomer resin sheet. The release surface of the ionomer, which is the sheet to be printed on the support, from the support is specular and glossy, and there is no protrusion due to gelation that tends to occur on the ionomer sheet. Acts to form. Further, when the support is provided with an uneven pattern, an uneven pattern layer is imprinted on the sheet to be printed, and the pattern layer can be seen three-dimensionally through the uneven pattern. And, when it is incinerated or discarded, it does not generate harmful gas such as hydrogen chloride.

[0023]

EXAMPLES Next, examples of the decorative material of the present invention will be described with reference to the drawings.

Example 1 In FIG. 1, as the ionomer, Himilan 1 manufactured by Mitsui Dupont Chemical Co., Ltd.
652 was formed into a film having a thickness of 80 μm by an inflation method, and one side of the sheet was subjected to a corona discharge treatment of 50 dynes / cm,
A printed sheet 5 having a corona discharge treated surface 4 was prepared.
The corona discharge treated surface 4 of the sheet 5 is gravure-printed to print a marble pattern as a pattern layer 2 with an ink using an acrylic urethane type color-developing agent to form a decorative material K of the present invention as shown in FIG. did. On the pattern layer 2 of the decorative material K, the chlorinated polypropylene thermal adhesive layer 3 of 10 g / m ² (solid content,
Hereinafter, the coating amount will be described as a numerical value in terms of solid content. Although not shown, the thermal adhesive layer 3 and a colored polyolefin having a thickness of 1.5 mm are coated at 100 ° C. for 20 kg.
A floor material was formed by pressure bonding under the condition of / m ² . The pattern layer of the flooring material was glossy and durable because it could be seen through the ionomer layer. Further, when the floor material was burned, the generation of corrosive gas such as hydrogen chloride due to chlorine was almost still generated.

(Example 2) As a base sheet 1, an untreated stretched polypropylene film 25 μm was coated with a linear polyester ink to form a pattern layer 2 having a stone pattern, and a thermoadhesive resin layer 3 was made of chlorine which is a thermoplastic resin. Polypropylene 5
A transfer sheet T shown in FIG. 2 (a) was formed in which g / m ² was provided in order. Next, a treated surface 4 of a single-sided corona discharge treated film of Himilan 1652, manufactured by Mitsui Dupont Co., Ltd., which was made by an inflation method as a printed sheet 5 made of an ionomer, and a thermal adhesive resin layer of the transfer sheet. 3 is laminated so as to be in contact with each other, and the pattern layer 2 is formed on the ionomer sheet 5 by passing the laminated sheet under the conditions of a roll temperature of 130 ° C. and a pressure of 5 kg / m ² , and the base material shown in FIG. 2 (b). The decorative material K of the present invention excluding the sheet 1 was constructed. Since the decorative material has an elaborate pattern layer formed from the transfer sheet through the ionomer layer 5, the pattern layer is transparent and glossy, and its surface is excellent in abrasion resistance and chemical resistance. Met. Further, when the decorative material was burned, the generation of corrosive gas such as hydrogen chloride was small.

(Example 3) As shown in FIG. 3 (a), as a support 6, a printed sheet 5 made of Himilan 1652 with a thickness of 100 μm was formed on one surface of 25 μm of polyester by a T-die method by corona discharge treatment. The sheet to be printed 5B provided on the support 6 in the bonded state, which was subjected to No. 4, was formed. Next, the thermal adhesive resin layer 3 of the transfer sheet T used in Example 2 was changed to linear polyester from chlorinated polypropylene, and the thermal adhesive resin layer 3 and the corona discharge treated surface of the ionomer of the sheet to be printed 5B were treated. 4 are laminated so as to be in contact with each other, and the pattern layer 2 is formed on the ionomer sheet 5 by passing the laminated sheet under the conditions of a roll temperature of 150 ° C. and a pressure of 5 Kg / m ² , and the base sheet 1 and the support 6 are formed. The decorative material K of the present invention shown in FIG. Since the ionomer surface, which is the print-receiving sheet 5 of the decorative material, is cast from the polyester sheet surface, the sheet can be thermally transferred at a higher temperature than in the case of Example 2 using the sheet as a support. It is excellent in mirror-like luster without any protrusion. Further, since the delicate pattern layer 2 formed by the transfer sheet T was seen through the ionomer layer, it had a transparent feeling and gloss, and the surface thereof was excellent in abrasion resistance, chemical resistance and durability. When the decorative material was burned, no corrosive gas such as hydrogen chloride was generated.

[0027]

The pattern layer of the decorative material provided on the transparent sheet made of an ionomer so as to be seen through the ionomer layer is excellent in abrasion resistance, chemical resistance and durability. The pattern layer formed by the transfer printing method is provided on a decorative material by printing on a sheet having excellent printability. Therefore, the pattern layer is highly accurate as a printed matter. In particular, the ionomer layer provided on the support has a mirror-like three-dimensional effect without projections due to foreign matter on the surface. In addition, by using a support having an uneven pattern, it is possible to form an uneven pattern layer on the surface of the ionomer layer that is not affected by foreign matter. Furthermore, the laminate made of a material containing no chlorine did not generate corrosive gas such as hydrogen chloride due to chlorine even when burned.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of a decorative material of the present invention.

FIG. 2 (a) is a schematic cross-sectional view of a transfer sheet of a decorative material of the present invention. (b) A schematic cross-sectional view showing the step of transferring the pattern of the decorative material of the present invention.

FIG. 3 (a) is a schematic sectional view showing a print-receiving sheet provided on a support. (b) A schematic sectional view showing a step of transferring a pattern onto a printing target sheet provided on a support.

[Explanation of symbols]

 1 Base Material Sheet 2 Design Layer 3 Thermal Adhesive Resin Layer 4 Corona Discharge Treatment Surface 5 Printed Sheet 5B Printed Sheet Provided on Support 6 Support K Cosmetic T Transfer Sheet

Claims (2)

[Claims] 1. A pattern layer is formed on one surface of a printed sheet formed of a resin obtained by partially or completely neutralizing a copolymer of ethylene and an α, β unsaturated carboxylic acid with metal ions. A cosmetic material characterized by that. 2. A decorative material comprising a printed sheet made of the resin according to claim 1 provided on one side of a support, and a pattern layer in that order.