JP2002113827A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet which uses a material other than vinyl chloride resin, has scratch resistance in addition to proper flexibility, abrasion resistance, heat resistance, and chemical resistance, is excellent in receiving properties during the film making of a resin, can be produced easily at a high speed, and can be supplied inexpensively. SOLUTION: The decorative sheet has at least a layer of a resin composition in which 500-1,500 ppm of a silica type anti-blocking agent is added into highly crystalline homo-polypropylene at least 95% in isotacticity (boiling decane extraction residue percentage) and 5 or below in molecular weight distribution MWD (ratio of weight average molecular weight Mw to number average molecular weight Mn, Mw/Mn).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to wood-based boards,
The present invention relates to a decorative sheet to be used as a decorative board by bonding to a surface of an inorganic board, a metal plate or the like with an adhesive.

[0002]

2. Description of the Related Art Conventionally, a vinyl chloride resin sheet has been most commonly used as a decorative sheet used for the above-mentioned applications. However, in recent years, it has been said that vinyl chloride resin causes hydrogen chloride gas, which causes acid rain, and dioxin, which is a highly toxic substance, during incineration. There was also a problem, and it came to be regarded as a problem from the viewpoint of environmental protection. Under such circumstances, a decorative sheet using a resin instead of the vinyl chloride resin has been demanded.

[0003] Accordingly, decorative sheets using resins such as polyethylene, polypropylene, polyethylene terephthalate, ethylene-vinyl alcohol copolymer, and acryl as resins instead of vinyl chloride resins have been proposed. Among them, there have been proposed many decorative sheets using polypropylene, which are provided with moderate flexibility required for decorative sheets, abrasion resistance, heat resistance, chemical resistance, and the like, and are provided at low cost. Polypropylene has some difficulty in scratch resistance and improvement is desired.

On the other hand, the present inventors have found that the isotacticity (boiling decane extraction residual ratio) is 95% or more, and the molecular weight distribution MWD (the ratio of the weight average molecular weight Mw to the number average molecular weight Mn Mw / Mn). ) Was found to improve scratch resistance by using a high crystalline homopolypropylene having 5 or less (Japanese Patent Application No. 11-105298). However, a resin having such characteristics is liable to be taken off by the chill roll during film formation, and has a drawback in take-up property in film formation.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the prior art, and an object of the present invention is to use a material other than vinyl chloride resin. In addition to moderate flexibility, abrasion resistance, heat resistance, and chemical resistance, it also has scratch resistance, and has excellent take-up properties during resin film formation, can be easily produced at high speed, and can be supplied at low cost. It is to provide a decorative sheet.

[0006]

The above object of the present invention can be solved by the following means. In other words, the present invention relates to a high crystal having an isotacticity (boiling decane extraction residual ratio) of 95% or more and a molecular weight distribution MWD (ratio Mw / Mn of weight average molecular weight Mw to number average molecular weight Mn) of 5 or less. A decorative sheet comprising at least a layer made of a resin composition obtained by adding 500 to 1500 ppm of a silica-based antiblocking agent to homopolypropylene.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The decorative sheet of the present invention has an isotacticity (boiling decane extraction residual ratio) of 95% or more.
A high-crystalline homopolypropylene having a molecular weight distribution MWD (ratio Mw / Mn of weight average molecular weight Mw to number average molecular weight Mn) of 5 or less is mixed with a silica-based antiblocking agent in an amount of 5%.
It is important to have at least a layer to which 00 to 1500 ppm is added. That is, if the isotacticity (boiling decane extraction residual ratio) is less than 95% or the molecular weight distribution MWD (ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn) exceeds 5, superiority in scratch resistance is seen. I can't. If the silica-based anti-blocking agent is less than 500 ppm, the take-up property during film formation is not improved, and
If the content exceeds 500 ppm, the flexibility becomes poor, and whitening, cracking and the like occur at the time of bending.

[0008] As the high crystalline homopolypropylene,
It is desirable from the viewpoints of scratch resistance, whitening resistance, rupture resistance and the like to employ those having an initial flexural modulus of 1000 to 2500 MPa and a tensile elongation at break of 200% or more. Also, 10
In the range of not more than weight%, low density polyethylene, atactic polypropylene, ethylene-propylene rubber, styrene-butadiene copolymer rubber or hydrogenated product thereof, ethylene-propylene-diene monomer copolymer rubber, olefin-based thermoplastic elastomer, etc. And the softness of the rubber composition can be blended to improve flexibility and impact resistance.

In addition, if necessary, for example, a heat stabilizer, a flame retardant, an ultraviolet absorber, a light stabilizer, a catalyst scavenger, a colorant,
Fillers, light scattering agents, gloss adjusting agents and the like can also be added. Hindered phenol, sulfur, hydrazine, etc. as heat stabilizers, aluminum hydroxide, magnesium hydroxide, etc. as flame retardants, benzotriazole, benzoate, benzophenone, triazine, etc. as UV absorbers Hindered amines and the like are typical examples of the stabilizer, and these can be added in any combination. In particular, since the decorative sheet of the present invention generally requires weather resistance, it is desirable to add an ultraviolet absorber and a light stabilizer in an amount of about 0.1 to 1% by weight per 100 parts by weight of the resin. .

An embodiment of the present invention will be described below with reference to the drawings. 1 to 3 show an example of a sectional view of a decorative sheet according to the present invention.

FIG. 1 shows an example of a decorative sheet according to the present invention. The decorative sheet has an isotacticity (boiling decane extraction residual ratio) of 95% or more and a molecular weight distribution MWD (weight average molecular weight Mw and number average molecular weight Mn). Mw / Mn) is 5
This is a single-layer decorative sheet composed of one resin layer 10 made of a resin composition obtained by adding 500 to 1500 ppm of a silica-based antiblocking agent to the following highly crystalline homopolypropylene.

The resin layer 10 may be manufactured by a known method such as a hot press method, a calender method, a T-die extrusion method, an inflation extrusion method, etc. In general, a polypropylene sheet is manufactured by a T-die extrusion method. Is preferably used. In that sense, the T-die extrusion method is preferred.

Further, if necessary, a concealing layer 30 may be provided so that a base material such as a wood board, an inorganic board, or a metal plate to be bonded to the back side of the decorative sheet is not seen from the surface, or the design may be improved. In order to apply, a pattern layer 20 representing an arbitrary pattern such as a grain pattern, a stone pattern, a sand pattern, an abstract pattern, or the like is also preferably performed.

The concealing layer 30 and the pattern layer 20 may be formed on the surface and / or the back of the resin layer 10 by gravure printing, intaglio printing, flexo printing, silk printing, electrostatic printing, ink jet printing, or the like. A known printing method is generally used, but is not necessarily limited to this. The ink used is also a known one, that is, a coloring agent such as a dye or a pigment is added to a vehicle, an extender,
In addition, plasticizers, stabilizers, waxes, greases, desiccants,
A hardening agent, a thickening agent, a dispersing agent, a filler and the like may be arbitrarily added, and the mixture may be sufficiently kneaded with a solvent, a diluent or the like.

As the binder for the above ink, for example, single or various modified products or mixtures of nitrified cotton, vinyl chloride-vinyl acetate copolymer, chlorinated polyolefin, polyvinyl butyral, polyurethane, polyamide, acryl, polyester and the like can be used. Any one of an aqueous type, a solvent type, and an emulsion type can be selected without any problem, and a one-part effect type or a two-part effect type using a curing agent can be arbitrarily selected. Further, it is also possible to use an ink using an ionizing radiation-curable resin that is cured by irradiation with ultraviolet rays or electron beams as a binder. Above all, when a two-component curable urethane-based resin, which is mainly composed of a resin precursor containing an active hydrogen group such as a polyol and is cured by adding an isocyanate curing agent, is used as an ink,
There is an advantage that the adhesiveness to a polyolefin-based resin such as the high-crystalline polypropylene is excellent.

The coloring agent added to the above-mentioned ink includes:
For example, condensed azo, insoluble azo, quinacridone, isoindolinone, anthraquinone, imidazolone, organic pigments such as phthalocyanine, carbon black, cobalt blue, ultramarine, navy blue, iron oxide, titanium dioxide, zinc oxide and other inorganic pigments, gold powder, Metal powder pigments such as silver powder, copper powder, aluminum powder, and bronze powder; pearl pigments such as titanium oxide-coated mica; bismuth oxychloride; In particular, it is desirable to use inorganic pigments such as titanium dioxide and iron oxide, metal powder pigments and the like, which are excellent in opacity, in the ink forming the hiding power 30.

As a method of forming the concealing layer 30 and the pattern layer 20, in addition to the above-described printing method, the concealing layer 30 and / or the pattern layer 20 are formed on an arbitrary substrate by the above-described method and the like. After laminating with the resin layer 10 by a hot lamination method, a dry lamination method, a wet lamination method, an extrusion lamination method, or the like to be described later, an arbitrary base material is peeled off, and the concealing layer 30 or the pattern layer 20 or both are removed from the resin layer. A method of transferring the image to the front surface, the rear surface, or both of them may be used.

As a method of manufacturing the resin layer 10, T
When a die extrusion method is used, the resin layer 10 may be directly colored and extruded to form a film, thereby providing a shielding effect. As a coloring method, a dry color method using a fine powder colorant obtained by treating a pigment with a dispersing aid or a surfactant,
There is a masterbatch method and the like in which a masterbatch pellet prepared by preliminarily dispersing a resin and a high-concentration pigment by melt-kneading the resin and dry-blending with an uncolored ordinary resin in an extrusion hopper is used. It is not limited.

The types of pigments used in the above method may be those commonly used, but inorganic pigments such as titanium oxide, ultramarine blue, cadmium pigments and iron oxide are particularly preferred in view of heat resistance and weather resistance. Further, among organic pigments, phthalocyanine pigments, quinacridone pigments and the like can be used. The ratio and color of the pigment are appropriately determined in consideration of the degree of concealment and design, and are not particularly limited. As a method of forming a pattern on the resin layer 10, a master batch pellet, a wood powder, a glass powder, or the like, in which a high-concentration pigment is melt-kneaded and pre-dispersed in a resin having different flow characteristics from the resin, is added and extruded. There is a method of forming a pattern on the resin layer itself by forming a film. Of course, the method of applying color hiding and / or a pattern to these resin layers themselves and the above-described printing method, transfer method, and the like can be used in combination.

In some cases, in order to obtain a feeling of touch on the surface and a further sense of design, a concave pattern 4 is formed on the resin layer.
In addition, it is also preferable to apply 0, bury a filling ink (wiping ink) in the concave portion, and to provide a top coat protective layer 50 on the outermost surface to further improve the surface properties.

The method of forming the concave pattern 40 may be a normal hot-press embossing method, and is not limited at all. When the T-die extrusion method is used as a method for manufacturing the resin layer 10, a convex pattern obtained by inverting the concave pattern 40 is applied to the surface of the chill roll for cooling and solidifying the molten resin, and simultaneously with cooling and solidifying the molten resin. Depressed pattern 4 on its surface
The method of forming 0 is common. It is also preferable to embed the wiping ink in the recesses of the recessed pattern 40 and to provide the top coat protective layer 50 on the outermost surface. However, these methods are performed with a conventional vinyl chloride resin decorative sheet. There is no problem with the wiping process and the top coat process.

The material used for the top coat protective layer 50 is not particularly limited in the present invention, and may be, for example, polyurethane, acrylic, acrylic silicon, or the like.
It can be appropriately selected from various synthetic resins such as fluorine-based, epoxy-based, vinyl-based, polyester-based, melamine-based, aminoalkyd-based, and urea-based resins. In addition, the form can be any of aqueous, solvent-based, and emulsion types.
The curing method may be any one of a one-part curing type, a two-part curing type, and an ionizing radiation curing type. Among them, two-part urethane resin using isocyanate curing agent is suitable for workability, price,
Most desirable from the viewpoint of the cohesive force of the resin itself. The isocyanate curing agent can be appropriately selected from various known ones, but considering weather resistance, hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPD
It is desirable to use an aliphatic or alicyclic polyisocyanate compound such as I).

If necessary, the top coat protective layer 50 may contain an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a coloring agent, a filler, a gloss control agent, a lubricant, 1 selected from various additives such as flame retardants, antibacterial agents, and fungicides
More than one species can be added. Examples of the lubricant include hard inorganic particles such as alumina, silica, silicon carbide, and silicon nitride. Examples of the antibacterial agent include inorganic compounds such as zeolite or apatite containing antibacterial metal ions such as silver, copper, and zinc. And organic antibacterial agents such as 2- (4-thiazolyl) -benzimidazole and 10,10-oxybisphenoxalazine. Top coat layer 5
It is appropriate that the thickness of 0 is usually about 2 to 10 μm.

Further, in consideration of the adhesiveness when the decorative sheet of the present invention is adhered to various substrates, a primer layer having easy adhesion may be provided on the back surface of the decorative sheet. For the primer layer, for example, urethane resin, acrylic resin,
An easily adhesive synthetic resin such as an ethylene-vinyl acetate copolymer resin, a vinyl chloride-vinyl acetate copolymer resin, or a polyester resin is used. Further, in consideration of prevention of blocking at the time of winding and improvement of adhesive force by an anchoring effect, for example, an inorganic filler such as silica, alumina, magnesia, titanium oxide, barium sulfate, and calcium carbonate may be added. . The appropriate thickness of the primer layer is usually about 0.1 to 3 μm.

FIG. 2 shows another example of the decorative sheet according to the present invention, in which a pattern layer 20 is applied to the surface of a colored concealing resin layer 60, and a transparent or translucent resin layer is formed on the pattern layer 20. This is a multi-layered decorative sheet provided with a top coat protective layer 50 on the outermost surface of the resin layer 10, a concave pattern 40 is formed on the resin layer 10, a wiping ink is embedded in the concave part.

In some cases, the resin layer 10 is provided in two or more layers (ie, a decorative sheet) in order to attach importance to certain physical properties, or to obtain a more luxurious feeling by giving a three-dimensional feeling and a solid feeling. It is also preferable to form a multilayer structure composed of three or more resin layers as a whole). In such a case, it is possible to express a three-dimensional design by providing the pattern layer 20 at a plurality of locations selected from the uppermost surface, the interlayer, and the lowermost surface of the two or more resin layers 10.

As a method of laminating the colored concealing resin layer 60 and the resin layer 10 and a method of laminating two or more resin layers 10, a heat lamination method in which heat and pressure are applied to each other,
Dry laminating method or wet laminating method in which an adhesive is applied, extruding laminating method in which one is used as a base material and the other resin is melt-extruded from a T-die, and co-extrusion method in which both resins are melt-extruded from a T-die Etc. Among these, the extrusion lamination method is preferred because the extrusion lamination method has the highest productivity.

In the decorative sheet of the present invention, at least one of the concealing resin layer 60 and the one or more resin layers 10 has an isotacticity (boiling decane extraction residual ratio) of 95% or more. And molecular weight distribution MWD
(Ratio Mw / weight-average molecular weight Mw to number-average molecular weight Mn)
Mn) is a high-crystalline homopolypropylene having a molecular weight of 5 or less, and a silica-based antiblocking agent is added at 500 to 1500 pp.
The resin composition to which m is added is used. It is desirable to use the same resin composition as the constituent resin of the other resin layers. However, the present invention is not particularly limited thereto, and the resin composition can be used in combination with a different kind of resin.

Examples of the above-mentioned different kinds of resins include polypropylenes other than those specified above, polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polystyrene, ABS, polymethyl methacrylate. , Polymethyl acrylate, polybutyl acrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane, polyamide, nylon 6, nylon 66 and the like. As a substitute for a part of the resin layer, paper, woven or nonwoven fabric, metal foil, or the like can be used.

When the isotacticity (boiling decane extraction residual ratio) specified in the present invention is 95% or more and the molecular weight distribution MWD (the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn) is 5 or less. To a certain high crystal homopolypropylene, 500 to 15
The layer made of the resin composition to which 00 ppm is added may be any layer selected from the concealing resin layer 60 and the one or more resin layers 10, but the excellent scratch resistance of the resin composition In order for the decorative sheet to exhibit its performance such as whitening resistance at the time of bending or bending, at least the outermost resin layer 10 is preferably a layer made of the resin composition, and the concealing layer 30 or the lowermost layer It is more desirable that all of the resin layer 10 provided above the pattern layer 20 of the above is a layer made of the resin composition.

As described above, in the decorative sheet composed of a laminate of a plurality of resin layers, the concealing layer 30 and the
Pattern layer 20, concave pattern 40, embedding of wiping ink into concave portion of concave pattern 40, top coat protective layer 5
0 or the like can be appropriately applied. These forming methods are the same as those in the case of the single-layer type decorative sheet described above, and have no problem.

FIG. 3 shows still another example of the decorative sheet according to the present invention. The decorative sheet is provided on the surface of a transparent or translucent non-concealing resin layer 70 in place of the colored concealing resin layer 60 in the above example. Applying a concealing layer 30 and a pattern layer 20, providing a transparent or translucent resin layer 10 on the pattern layer 20,
This is a multi-layer decorative sheet in which a concave pattern 40 is formed on the resin layer 10, a wiping ink is embedded in the concave section, and a top coat protective layer 50 is provided on the outermost surface.

As described above, in the multi-layer type decorative sheet, the resin layer on the back side of the pattern layer 20 is not limited to the concealing property, and the concealing layer 30 is provided instead of the non-concealing property. This can supplement the concealment. The concealing layer 30
Without providing, by making all layers transparent or translucent,
It can also be used for applications that make use of the texture unique to a base material such as a wood base material bonded to the back surface of the decorative sheet.

[0034]

<Example 1> Isotacticity 95%,
A 70 μm thick film obtained by adding 6% by weight of an inorganic pigment to highly crystalline homopolypropylene having a molecular weight distribution of MWD = 5 and imparting a hiding property.
m, the surface of the sheet is subjected to a corona treatment, a pattern is formed by a gravure method using a urethane-based ink, and then 1 g of a urethane-based anchor coating agent is formed by a gravure method.
/ M 2 and dried by heating to obtain a substrate sheet.

As above, isotacticity 95
%, Molecular weight distribution MWD = 5, transparent high crystalline homopolypropylene with silica antiblocking agent at 1000 pp
The m-added resin is extruded from a T die between a chill roll and a rubber roll having a concave pattern through the base sheet at a thickness of 70 μm, and the concave pattern is applied and laminated at the same time, and the wiping ink is embedded in the concave section. A urethane-based top coat was further applied to the outermost surface at 5 g / m2 to obtain a decorative sheet. The line speed of the machine is 4
The test was performed at 0 m / min.

Comparative Example 1 A decorative sheet was prepared in the same manner as in Example 1 except that the amount of the silica-based antiblocking agent added to the transparent high-crystal homopolypropylene was 300 ppm. Obtained.

Comparative Example 2 A decorative sheet was prepared in the same manner as in Example 1 except that the amount of the silica-based antiblocking agent added to the transparent high-crystal homopolypropylene was 1800 ppm. Obtained.

The decorative sheets of Example 1 and Comparative Examples 1 and 2 thus obtained were bonded to a wooden substrate using a urethane-based adhesive, and the scratch resistance was evaluated by a coin scratch method. . The flexibility was evaluated by a V-cut method in which the cross section was cut into a V-shape from the wooden base material side and bent in an atmosphere at 5 ° C. In addition, after preparing the decorative sheet for evaluation, the line speed of the machine was increased, and the limit line speed at which the resin was removed to the chill roll was observed. Table 1 shows the results of these evaluations.

[0039]

[Table 1]

As is clear from Table 1, the decorative sheet of the present invention (Example 1) is, of course, a vinyl chloride-free decorative sheet, and is excellent in scratch resistance, flexibility and take-up property. Was.

On the other hand, in the case of the decorative sheet of Comparative Example 1, the resin was taken into the chill roll at a line speed of the machine of 50 m / min, and the high-speed productivity was poor. In the decorative sheet of Comparative Example 2, whitening was recognized in the V-cut test, and the secondary workability was poor.

[0042]

As described above, since the decorative sheet of the present invention does not use any vinyl chloride, there is no need to worry about environmental problems, and it is excellent in scratch resistance, flexibility and secondary workability. In addition, the film has excellent advantages that it has high productivity because of good take-up property during film formation, and can be manufactured efficiently and at low cost.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of a decorative sheet of the present invention.

FIG. 2 is a sectional view showing an example of the decorative sheet of the present invention.

FIG. 3 is a sectional view showing an example of the decorative sheet of the present invention.

[Explanation of symbols]

 10. Resin layer 20. Pattern layer 30. Hiding layer 40. Depressed pattern (wiping ink embedded) 50. Top coat protective layer 60. 70. Colored concealing resin layer Non-hiding resin layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/34 C08K 3/34 C08L 23/12 C08L 23/12 F-term (Reference) 2B002 AA03 AA16 BB06 2B250 BA03 DA01 EA11 4F100 AA20A AB01 AK07A AP00 AT00B BA02 CA17A CC00 GB08 GB81 HB00 HB00A HB21 HB31 JA07A JA11A JA20A YY00A 4J002 BB121 DJ006 DJ016 FD040 FD050 FD060 FD130 FD206 GL01

Claims (1)

[Claims] An isotacticity (residual boiling decane extraction ratio) of not less than 95% and a molecular weight distribution MWD (ratio Mw / Mn of weight average molecular weight Mw to number average molecular weight Mn) of 5%.
A decorative sheet comprising at least a layer made of a resin composition obtained by adding 500 to 1500 ppm of a silica-based antiblocking agent to the following highly crystalline homopolypropylene.