JP2001010008A - Decorative sheet and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet having a soft texture, in which adhesion can be ensured without a pretreatment such as a corona discharge, an ozone treatment, a plasma treatment or the like for improving the adhesion between a surface layer and a colored base layer and in which no whitening phenomenon develops at folding and stretching in the decorative sheet produced by laminating both the above layers to each other. SOLUTION: In a decorative sheet, which is produced by laminating a surface layer and a colored base material layer to each other, a composition including a saturated styrenic elastomer is employed for the surface layer and/or the colored base material layer. Between both the layers, an anchor coat agent consisting of a composition including the saturated styrenic elastomer or a printing ink is employed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet used for surface materials such as furniture and various building materials, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a soft vinyl chloride resin sheet has been generally used as a decorative sheet used for the above-mentioned applications. However, as is well known, harmful gases such as hydrogen chloride are generated during incineration of vinyl chloride resin, which causes acid rain and other pollutants. For this reason, a polyolefin resin or the like may be used instead of the vinyl chloride resin. However, there is a drawback that interlayer adhesion strength cannot be obtained when a laminate is used because there is no polar group as compared with the vinyl chloride resin. For this reason, the surface of the olefin resin sheet is subjected to a treatment such as a corona discharge treatment, an ozone treatment, a plasma treatment, and a primer treatment, and then the sheets are laminated by a dry lamination method via an adhesive, and a bonding method by a hot press. And a method in which a thermoplastic resin having adhesive properties is used for both the base sheet and the surface olefin resin sheet to laminate by multilayer melt coextrusion.

[0003]

However, when performing the surface treatment, not only is processing equipment required, but also the adhesion performance decreases over time or the number of work steps increases, the cost increases, and the lamination speed increases. Was difficult. Furthermore, in terms of shaping of the surface irregularities on the surface of the decorative sheet using an embossing roll or the like, there was a problem that the post-embossing after forming the sheet was inferior to the method of shaping during melt extrusion. On the other hand, in a method of laminating a thermoplastic resin having an adhesive property to both a base sheet and a surface olefin resin sheet and a polyolefin resin on the surface in a multilayer form by melt coextrusion, a plurality of extruders and complicated T
Since a die and the like are required, the equipment cost is increased, and the amount of resin used is increased, so that it takes time to replace the resin and clean the equipment, and also requires advanced processing techniques. Furthermore, decorative sheets using these olefinic resins have the disadvantage that they are whitened or delaminated when being bent or stretched, which is inherent to various types of processing.

[0004]

According to the present invention, the above-mentioned problems have been solved by the following method. That is, in a decorative sheet composed of a multilayer laminate in which a surface layer is laminated on a colored base layer, a resin containing a saturated styrenic elastomer is used for both or one of the surface layer and the colored base layer, and the two are bonded together. The above-mentioned problems can be solved by using a composition containing a saturated styrenic elastomer in an anchor coat layer or a printing ink layer used for improvement.

[0005] This method has excellent interlayer adhesion strength without pretreatment such as corona discharge treatment, ozone treatment, and primer treatment which are required when an olefin resin is used, and is indispensable for various kinds of processing. A decorative sheet without whitening or delamination during bending and elongation could be provided.

[0006] The decorative sheet of the present invention is obtained by laminating a surface layer on a colored base material layer. A resin sheet for the surface layer melt-extruded through an anchor coat layer or a printing ink layer may be laminated on the colored base material. Alternatively, it is also possible to finish by laminating a surface layer resin sheet previously formed into a sheet shape on a colored base sheet with a hot plate or a hot roll via an anchor coat layer or a printing ink layer.

[0007] After laminating, the surface layer is brought into contact with an embossing roll or a hot plate to give an embossed shape, and then the interior of the embossed portion is filled with a coloring material, ink, etc. by wiping to impart design properties, Can be given a variety of design appearances by printing a wood grain pattern or the like, or by applying a resin coat to improve durability performance against scratches, contamination, and the like.

A resin composition containing a saturated styrenic elastomer in one or both of the surface layer and the colored base material layer is used. The following are examples of the saturated styrenic elastomer used: styrene-ethylene-butylene-styrene (hereinafter referred to as SEBS), maleic anhydride-modified (hereinafter referred to as acid-modified) SEBS, and hydroxyl-modified SEB.
S, epoxy group-modified SEBS, styrene-ethylene-propylene-styrene (hereinafter referred to as SEPS), hydrogenated styrene-butadiene rubber (hereinafter referred to as HSBR), styrene-ethylene-butylene-olefin crystal (hereinafter referred to as SEBC). Styrene-ethylene-propylene-based (hereinafter referred to as SEP), styrene-ethylene-ethylene-propylene-styrene-based (hereinafter referred to as SEEPS).
And ), Hydrogenated styrene-vinyl polyisoprene-styrene (hereinafter referred to as HSVPS).

As the mixing resin used in combination with these, styrene-based resins and polyolefin-based resins can be cited, but among the polyolefin-based resins, polypropylene-based resins are desirable in terms of compatibility. Examples of the polypropylene type include a homopolymer type of polypropylene alone, a random type copolymerized with polyethylene, a three-dimensional type copolymerized with polyethylene and butene, an ethylene-propylene rubber modified type, and various other copolymer types.

The saturated styrenic elastomer and the resin for mixing are melt-mixed and then pelletized for use, or the mixture mixed by dry blending is kneaded by an extruder and directly melt-extruded into a sheet. it can. As the mixing ratio of the two, the amount of the saturated styrene elastomer is preferably 3% or more, and if it is 3% or less, the adhesiveness is not obtained and it is not appropriate. The resin for the surface layer, the anchor coat layer, and the colored base material layer have a weather resistance stabilizer for improving the weather resistance to ensure surface performance, an antistatic agent for antistatic, and a slip agent for blocking. And a coloring agent for coloring.

As the material of the colored base material layer, in addition to the resin sheet made from the composition containing the saturated styrenic elastomer, a colored paper or a resin sheet made of a polyolefin resin, polyester resin or the like can be used. Substrates and the like can be used. A printing pattern such as a wood grain pattern or a stone grain pattern is appropriately applied to these colored base materials by various printing methods such as gravure printing, offset printing, silk screen printing and the like, and used. As the material of the surface layer, in addition to a resin sheet made of a composition containing the saturated styrenic elastomer, a resin sheet having a surface property, for example, an acrylic resin, a polypropylene resin, a sheet made of polyester resin and the like. Can be used.

The coloring agent of the coloring base material layer includes inorganic pigments such as titanium white, zinc white, red iron oxide, and cobalt blue; organic pigments such as Hansa Yellow A, phthalocyanine blue and aniline black; other various metal pigments; Etc. are used. These are appropriately mixed in a resin and colored.

In order to improve the adhesion between the colored base material layer and the surface layer, it is necessary to apply and dry an anchor coat agent on the surface of the colored base material. A composition containing an acid-modified, hydroxyl-modified, or epoxy-modified saturated styrenic elastomer is desirable in consideration of adhesion to the material, and acid-modified SEBS is particularly desirable in terms of solubility in an organic solvent and adhesion. Further, when water resistance, heat resistance, adhesion, and the like are required, it is desirable that an isocyanate compound, an alkali metal compound, an amino compound, an epoxy resin, and the like be added to the acid-modified SEBS. Such a composition is used as an anchor coat agent in a state of being dissolved in an organic solvent.

The anchor coating agent is applied to the colored substrate at the time of lamination and then dried, or the one previously applied and dried is used as a colored substrate. Further, if the adhesion is ensured, the printing ink can also have a role as an anchor coating agent as a component similar to the anchor coating agent as in the third embodiment.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. Example 1 A 10% toluene solution of a mixture of 100 parts of an acid-modified SEBS and 5 parts of a hexamethylene diisocyanate buret body was formed by applying a pattern ink layer with a urethane resin-based ink to the surface of a 100 μm-thick polyolefin resin sheet colored with a pigment. Was applied to the surface of the printed sheet at an application amount of 3 g / m ² (dry conversion), dried to form an anchor coat layer, and 70 parts of polypropylene resin and 30 parts of SEBS were extruded from an extruder having a T-die on the surface. The mixture was extruded at a temperature of 220 ° C., cast so that the transparent surface layer after cooling and solidification had a thickness of 0.05 mm, and then pressed against a base sheet with a cooling roll with embossing and a nip roll,
Simultaneously with cooling and solidification, the surface gloss and the grain conduit emboss were transferred to obtain a decorative sheet of Example 1.

Example 2 A 60-μm-thick polyester resin sheet colored with a pigment was coated with a pattern ink layer using a urethane resin-based ink, and 100% of acid-modified SEBS and 10% of 5 parts of hexamethylene diisocyanate burette were used. The toluene solution was applied on the surface of the print sheet at a coating amount of 3 g / m ² (dry conversion) and dried to form an anchor coat layer. Next, a mixture of 70 parts of polypropylene resin and 30 parts of HSBR was extruded at a temperature of 220 ° C. from an extruder having a T-die installed on the surface of the anchor coat layer, and the mixture was cooled and solidified so that the thickness of the transparent surface layer became 0.05 mm. It was rolled and pressed against the base sheet with a cooling roll having embossing and a nip roll to cool and solidify, and the surface gloss and grain embossing were transferred to obtain a decorative sheet of Example 2.

EXAMPLE 3 63 parts of a polypropylene resin, 30 parts of an acid-modified SEBS, and 7 parts of titanium oxide were melt-mixed, and then a pelletized mixture was extruded at a temperature of 220 ° C. from an extruder equipped with a T-die, and cooled and solidified. Was 0.1 mm, and was rolled up with a cooling roll to obtain a colored base material. A pattern was printed on the colored substrate with a printing ink containing acid-modified SEBS as a medium to obtain a printed substrate. 70 parts of polypropylene resin and SEB
S30 parts of the mixture was extruded at a temperature of 220 ° C. and cast so that the thickness after cooling and solidification became 0.05 mm, and then the mixture was pressed against a base sheet with an embossing cooling roll and a nip roll to cool and solidify, and simultaneously The decorative sheet of Example 3 was obtained by emboss transfer of gloss and wood grain conduit.

Example 4 A transparent acrylic resin film having a thickness of 100 μm was used as a surface layer, and a pattern ink layer was formed on the transparent acrylic resin film with a urethane resin-based ink.
Part, hexamethylene diisocyanate buret body 5
Part of a 10% toluene solution of the mixture was applied to the surface of the ink layer at a coating amount of 3 g / m 2 (dry conversion), and then dried to form an anchor coat layer. The colored resin for extrusion was extruded at a temperature of 220 ° C. from an extruder equipped with a T-die, and the thickness after cooling and solidification was set to 0.1.
It was then cast to a thickness of 0.6 mm, and then pressed against a base sheet with a cooling roll and a nip roll to obtain a decorative sheet of Example 4.

Comparative Example 1 A decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that the polypropylene resin alone was used as the extruded resin instead of the polypropylene resin / SEBS mixed resin.

Comparative Example 2 A decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 2 except that a urethane resin-based adhesive was used as an anchor coating agent.

The decorative sheets obtained as described above were tested and evaluated for adhesion, folding whitening property, elongation property and three-dimensional formability. The results are shown in the table.

[0022]

[Table 1]

Test Evaluation Method Adhesion: Determined by peeling after boiling for 2 hours. 2. Folding whitening property: Judgment is made based on whether or not whitening occurs when the decorative sheet is bent at 180 degrees. 3. Extensibility: It is determined based on whether or not a whitening phenomenon is observed when a product bonded to a 12 mm steel plate is bent at a right angle, and whether or not there is peeling at a corner portion. 4. Three-dimensional formability: 30 × 30 cm ² , 18 mm thick, medium-density fiberboard, 3D outside R at the corner of 1
15 parts of a two-part emulsion adhesive on the core processed to
After applying 0 g / m ² , three-dimensional forming was performed by a vacuum press (membrane press) having a surface temperature of 130 ° C.

[0024]

[Function] Good adhesion between the surface layer and the colored base material layer because an anchor coating agent or a printing ink comprising a composition containing the same saturated styrenic elastomer as the components of the surface layer or the colored base material layer is used. Nature can be secured. The reason why the surface layer does not whiten during bending or elongation is that the mixed state of the mixed resin and the saturated styrenic elastomer is almost completely dispersed at a microscopic level, and that the component is flexible. Therefore, it is assumed that the whitening phenomenon unlike the polyolefin resin disappears.

[0025]

The decorative sheet according to the present invention uses an anchor coating agent comprising a composition containing a saturated styrene-based elastomer or a printing ink comprising the same component in order to improve the adhesion between the surface layer and the colored base material layer. Since the composition containing the saturated styrenic elastomer is used for the layer, the colored base material layer or the surface layer, and the colored base material layer, the two layers have excellent adhesiveness and do not peel off from the laminated surface. For this reason, surface treatments such as corona discharge treatment, ozone treatment, plasma treatment, and primer treatment for securing adhesion, which have been indispensable for laminating a polyolefin-based decorative sheet, are no longer necessary, and the process can be simplified. Cost reduction has also become possible.

Further, since the surface layer or the colored base material layer or both layers are composed of a resin layer composed of a composition containing the saturated styrenic elastomer, it has excellent towability and texture and can be avoided in a polyolefin decorative sheet. There is no whitening phenomenon during elongation during bending and elongation. For this reason, it can be used easily without any anxiety in so-called various secondary processing of the decorative sheet.

 ────────────────────────────────────────────────── ─── Continued on the front page F-term (reference) 4F100 AK04 AK04J AK07 AK07J AK12 AK12A AK12B AK12C AK12D AK12E AK12J AK51 AK80 AL01 AL05A AL05B AL05C AL05D AL05E AL09A AL09B AL09C AL09 BA00 BA10 BA03 BA10 BA10 EH232 EH462 EJ403 GB07 GB81 HB00 HB00C HB31D HB31E JK06 JK13 JK17 JL02 JL10C JN28

Claims (4)

[Claims] 1. A decorative sheet having a surface layer and a colored base material layer laminated via an anchor coat layer, wherein the anchor coat layer is composed of a composition containing a saturated styrene-based elastomer, and the surface layer and the coloring A decorative sheet comprising a composition containing a saturated styrenic elastomer in both or one of the base layers. 2. A decorative sheet having a surface layer and a colored substrate layer laminated thereon, comprising a composition containing a saturated styrene-based elastomer on both or one of the back surface of the surface layer and the surface of the colored substrate layer. A decorative sheet to which a printing ink is applied, and wherein a composition containing the saturated styrenic elastomer is used in both or one of the surface layer and the colored base material layer. 3. A composition comprising a saturated styrenic elastomer on the back surface of the surface layer or the surface of the colored base layer when the decorative sheet is laminated with the surface layer and the colored base layer via the anchor coat layer. A decorative sheet comprising a composition comprising a saturated styrenic elastomer on at least one of the surface layer and the colored base material layer. 4. When laminating a decorative sheet comprising a surface layer and a colored base material layer, a composition comprising a saturated styrenic elastomer on one or both of the back surface of the surface layer and the surface of the colored base material layer. A method for producing a decorative sheet, comprising performing printing with a printing ink comprising: and laminating a composition containing a saturated styrene-based elastomer on at least one of the surface layer and the colored base material layer.