JP2001038864A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a decorative sheet with appropriate flexibility, wear resistance, heat resistance, chemical resistance as well as scratch resistance and additionally, being inexpensive and excellent take-off properties by using a non-chlorine type resin with no environmental problem and no influence to human body except vinyl chloride resin. SOLUTION: A resin layer 1 consisting of a resin compsn. comprising 70-90 wt.% highly crystalline polypropylene with an isotacticity (a residue of boiling decane soluble part) of at least 95% and 10-30 wt.% polypropylene with an MFR provided by JIS K 6760 of 10-40 g/min and with a bending initial modulus of 10,000 kgf/cm2 is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to decorative sheets used for interior materials of buildings, surface materials of fittings, surface materials of home electric appliances, etc., and more particularly to wood-based boards, inorganic boards, metal plates and the like. The present invention relates to a decorative sheet which is used as a decorative board by being bonded to the surface of a sheet through an adhesive.

[0002]

2. Description of the Related Art Conventionally, polyvinyl chloride sheets have been most commonly used as decorative sheets used for interior materials of buildings, surface materials of fittings, surface materials of home electric appliances and the like. However, in recent years, vinyl chloride resin is said to be a factor in the generation of hydrogen chloride gas, which causes acid rain, and dioxin, a highly toxic substance, during incineration when discarding decorative sheets. There is also a problem of bleed-out of the added plasticizer, which has been regarded as a problem from the viewpoints of environmental protection and effects on human bodies.

[0003] Under such circumstances, there has been a demand for a decorative sheet using a resin instead of a vinyl chloride resin.

Accordingly, decorative sheets using resins and copolymers such as polyethylene, polypropylene, polyethylene terephthalate, ethylene-vinyl alcohol, 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 appropriate flexibility, abrasion resistance, heat resistance, chemical resistance and the like required for decorative sheets and are provided at low cost.

[0005]

However, the polypropylene resin proposed above has some difficulty in the scratch resistance, and an improvement has been desired.

On the other hand, the present inventors have proposed isotacticity (a measure of stereoregularity of polypropylene resin,
The ratio of the solid portion remaining without being dissolved in a solvent (decane, heptane, hexane, or the like) boiling at normal pressure (760 mmHg). Here, the boiling decane soluble residue is 9)
5% or more, and initial flexural modulus 10,000 kgf /
It has been found that the use of a high-crystalline polypropylene having a size of at least ² cm ² improves the scratch resistance. However, a resin having such characteristics has a remarkably poor spreadability and has a drawback in take-up property in film formation. Was.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to use a non-chlorine-based resin other than a vinyl chloride resin which does not affect the environment and the human body. It is an object of the present invention to provide a decorative sheet which has scratch resistance in addition to excellent flexibility, abrasion resistance, heat resistance, and chemical resistance, is inexpensive, and has excellent take-up properties.

[0008]

According to the present invention, there is provided a high-crystalline polypropylene having an isotacticity (boiling decane-soluble residue) of 95% or more.
0 to 90% by weight, M defined in JIS K 6760
The polypropylene having a FR of 10 g / 10 min or more and 40 g / 10 min or less is comprised in the range of 10 to 30% by weight, and has a layer made of a resin composition having an initial flexural modulus of 10,000 kgf / cm ² or more. It is a decorative sheet to be made.

According to the present invention, high crystalline polypropylene and MF having excellent scratch resistance can be obtained without using a vinyl chloride resin.
R (melt flow rate indicating the fluidity of the melt) is 10
By forming a decorative sheet in which a layer blended with polypropylene having appropriate spreadability of not less than g / 10 min and not more than 40 g / 10 min, that is, take-up property during film formation, is laminated, moderate flexibility, abrasion resistance and heat resistance are obtained. A decorative sheet having scratch resistance in addition to water resistance and chemical resistance can be obtained.

[0010]

Embodiments of the present invention will be described below. In the decorative sheet of the present invention, the high crystalline polypropylene having an isotacticity (boiling decane soluble residue) of 95% or more is 70 to 90% by weight, preferably 75 to 85% by weight, and the MFR is 10 g / 10min or more and 40g /. 10mi
It is important to provide a layer of a resin composition in which the polypropylene of n or less is in the range of 10 to 30% by weight, preferably 15 to 25% by weight, and the initial flexural modulus is 10,000 kgf / cm ² or more. It is.

That is, the isotacticity is 95%
Less than or initial flexural modulus of 10,000 kgf / cm
^If it is less than ² , superiority in scratch resistance is not seen. Also,
If the proportion of polypropylene is less than 10% by weight, the take-up property at the time of film formation is not improved, and if it exceeds 30% by weight, the superiority of scratch resistance is not seen. Further, the MFR is 10 g / 10 mi.
If it is less than n or more than 40 g / 10 min, the viscosity balance with the high-crystalline polypropylene is lost, and there is a possibility that unevenness in the sheet surface may occur.

In general, it is essential to add an ultraviolet absorber and a light stabilizer to a decorative sheet because weatherability is also required. However, the ultraviolet absorber and the light stabilizer are kneaded with the polypropylene to obtain a high concentration. Can be adopted in which a master batch is prepared and mixed with highly crystalline polypropylene immediately before film formation. By using this method, it is possible to adjust the amount of the ultraviolet absorber and the light stabilizer depending on the required weather resistance. Further, it is necessary to knead the ultraviolet absorber and the light stabilizer into high crystalline polypropylene occupying 70 to 90% by weight. There is also a merit that it can be used in a so-called general-purpose form without any.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. 1 to 3 show an example of a sectional view of a decorative sheet (1) according to the present invention. FIG. 1 shows a single-layer type decorative sheet (1) comprising one resin layer (10) according to the present invention. The method for producing the resin layer (10) may be a known method such as a hot press method, a calender method, a T-die extrusion method, or an inflation extrusion method. Generally, a T-die extrusion method is preferably used for a polypropylene sheet. Can be In that sense, the T-die extrusion method is preferred.

If necessary, a concealing layer (30) may be provided to prevent the woody board, the inorganic board and the metal plate from being visible from the surface.
It is also preferable to apply a pattern layer (20) such as a sand pattern or an abstract pattern.

The concealing layer (30) and the pattern layer (2)
As a forming method of 0), a known printing method such as gravure printing, intaglio printing, flexographic printing, screen printing, electrostatic printing, or inkjet printing is generally used on the front surface and / or the back surface of the resin layer (10). Yes, but not necessarily. Also used inks are known ones, that is, coloring agents such as dyes or pigments in the vehicle,
Add extender pigment, plasticizer, stabilizer, wax,
It may be formed by arbitrarily adding a grease, a desiccant, a curing agent, a thickener, a dispersant, a filler, and the like, and sufficiently mixing them with a solvent, a diluent, or the like.

Further, a concealing layer (30) and / or a pattern layer (20) are formed on an arbitrary substrate (not shown) by the above-mentioned method or the like. After laminating with the resin layer (10) by a wet laminating method, an extruding laminating method, or the like, a method of transferring an concealing layer (30) or a pattern layer (20) or both by peeling an arbitrary base material can also be used. .

In the case where a T-die extrusion method is used as a method for producing the resin layer (10), the resin layer (10)
Can be directly colored and formed into an extruded film to give a hiding 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, a master batch pellet in which a resin and a high-concentration pigment are melt-mixed and pre-dispersed is used. There is a master batch method of producing and dry blending with a normal resin that is not colored in an extrusion hopper, and the method is not particularly limited. The pigments may be those commonly used, but inorganic pigments such as titanium oxide, ultramarine blue, cadmium pigments, and iron oxides are particularly desirable in consideration 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. In addition, as a method of applying the pattern layer (20), a master batch pellet, a wood powder, a glass powder, or the like, in which a high-concentration pigment is melt-mixed and pre-dispersed with a resin having different flow characteristics from the resin, is added. Extrusion film formation and the resin layer (1)
0) There is a method of forming a pattern layer (20) on itself. Of course, it is also possible to use the above-mentioned printing method, transfer method and the like together with the method of forming a color concealment and a pattern on the resin layer (10) itself.

In some cases, a concave pattern (40) is formed on the resin layer (10), and a filling ink is buried in the concave section to obtain a feeling of touch on the surface and further design. Providing a top coat protective layer (50) is also preferably performed.

The method of forming the concave pattern (40) may be a normal hot-press embossing method, and is not limited at all. When a T-die extrusion method is used as a method for manufacturing the resin layer (10), a method of forming a concave pattern on the surface of a chill roll for cooling and solidifying a molten resin is generally used. It is also preferable to embed the ink in the recesses provided and to provide a protective layer on the outermost surface. However, these methods employ a wiping process and a top coat process which are performed on a conventional vinyl chloride resin decorative sheet. There is no problem at all.

In FIG. 3, a pattern layer (20) and a concealing layer (30) are formed on the back surface of the resin layer (10), and a concave pattern (40) is formed on the resin layer (10), and Ink is embedded and the top coat protective layer (5
0), and a non-hiding resin layer (70)
1 shows an example of a decorative sheet (1) according to the present invention provided with a sheet.

As described above, two resin layers (10, 70) are provided as described above in order to emphasize specific physical properties, or to obtain a more luxurious feeling by giving a three-dimensional feeling and a solid feeling. Is also suitably performed.

As a method of laminating the resin layer (10) shown in FIG. 3, a heat laminating method of applying heat and pressure, a dry laminating method of applying an adhesive and a wet laminating method are used. There are an extrusion lamination method in which the other resin is melt-extruded from a T-die on a base material, and a co-extrusion method in which both resins are melt-extruded from a T-die. Among these, the extrusion lamination method is the best in productivity, so this extrusion lamination method is preferable.

In the present invention, the resin composition according to the present invention is used for at least one of the resin layer (10) and the non-concealing resin layer (70). The other resin is preferably the above-mentioned resin, but is not particularly limited thereto. Examples include polypropylene, polyethylene, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, polystyrene, ABS, polymethyl methacrylate, polymethyl acrylate, and polybutyl acrylate other than those described in claim 1. , Polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane, polyamide, nylon 6, nylon 66 and the like. Also, paper can be used other than resin.

As described above, even in the decorative sheet (1) having two resin layers, the concealing layer (30), the pattern layer (20), and the concave pattern (40) can be provided as necessary. These forming methods have no problem with the above-mentioned method.

In FIG. 2, a pattern layer (20) is applied to the surface of the colored concealing resin layer (60), a transparent resin layer (10) is bonded, and a concave pattern (10) is formed on the transparent resin layer (10). 40) shows an example of a decorative sheet (1) according to the present invention, in which ink is embedded in recesses thereof, and a top coat protective layer (50) is provided on the outermost surface.

Although not shown, the resin layer (10)
May be a decorative sheet comprising three or more layers.

[0027]

Next, the present invention will be described in detail with reference to examples. <Example 1> Isotacticity (boiling decane-soluble residue) is 97% and initial flexural modulus is 20,000 kgf / c.
was subjected to corona treatment on the sheet surface of the thick 70μm that the addition of inorganic pigments 6 wt% to impart opacity to the high crystalline polypropylene m ^2, subjected to a pattern using an ink of urethane gravure method, Further, a urethane-based anchor coating agent was applied at 1 g / m ² by a gravure method and dried by heating to obtain a base sheet.

A resin comprising 70% by weight of the above-mentioned transparent high-crystalline polypropylene and 30% by weight of polypropylene having an MFR of 20 g / 10 min was interposed between a chill roll and a rubber roll having a concave pattern formed from a T-die via the base sheet obtained above. Extrusion with a thickness of 70 μm, simultaneous formation of a concave pattern and lamination, embedding of wiping ink in the concave part, and a urethane top coat of 5 g / m ^{2 on the} outermost surface
It was applied to obtain a decorative sheet. The machine was operated at a line speed of 40 m / min.

<Example 2> Normal polypropylene having an isotacticity (boiling decane-soluble residue) of 93% and an initial flexural modulus of 8000 kgf / cm ² was used as a base sheet. A decorative sheet was obtained in the same manner as in Example 1, except that the ratio of crystalline polypropylene to polypropylene was 90% by weight to 10% by weight.

Comparative Example 1 A decorative sheet was obtained in the same manner as in Example 2 except that the resin extruded from the T-die was only high crystalline polypropylene.

Comparative Example 2 A decorative sheet was obtained in the same manner as in Example 2 except that the ratio of the high-crystalline polypropylene to the polypropylene extruded from the T-die was 65% by weight to 35% by weight.

Each of the decorative sheets obtained in Examples 1 and 2 and Comparative Examples 1 and 2 was bonded to a wooden substrate using a urethane-based adhesive, and the scratch resistance was evaluated by a coin scratch method. Further, after preparing the decorative sheet for evaluation, the line speed of the machine was increased, and the limit line speed at which unevenness in thickness occurred was observed. Table 1 shows the results of these evaluations.

[0033]

[Table 1]

As is clear from Table 1, Examples 1 and 2
Needless to say, the sheet obtained in this manner was a decorative vinyl chloride sheet, and was excellent in scratch resistance and take-up properties.

On the other hand, the sheet obtained in Comparative Example 1 has a sheet speed of 40 to 50 m / min at a machine line speed of 50 m / min.
Periodic thickness unevenness of 110 μm was observed. In addition, the sheet obtained in Comparative Example 2 was found to have a scratch as if it were scoured by a coin scratch with a load of 2 kgf.

[0036]

As described above, the present invention has the following effects. That is, high crystalline polypropylene having an isotacticity (boiling decane soluble residue) of 95% or more is 70 to 90% by weight, and MFR is 10 g / 10 mi.
By providing a layer made of a resin composition having a polypropylene of n or more and 40 g / 10 min or less in a range of 10 to 30% by weight and having an initial flexural modulus of 10,000 kgf / cm ² or more, the layer is excellent in scratch resistance and composition. It is possible to obtain a low-cost decorative sheet having take-off property and high productivity at the time of film formation. Further, since a vinyl chloride resin is not used, it is possible to provide a decorative sheet that does not have a risk of affecting the environment and the human body during incineration.

Therefore, the present invention exhibits an excellent practical effect as an environmentally friendly decorative sheet.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing one embodiment of a decorative sheet according to the present invention in a side cross section.

FIG. 2 is an explanatory view showing another embodiment of the decorative sheet according to the present invention in a side cross section.

FIG. 3 is an explanatory view showing another embodiment of the decorative sheet according to the present invention in a side cross section.

[Explanation of symbols]

 1 decorative sheet 10 resin layer 20 pattern layer 30 concealing layer 40 concave pattern 50 topcoat protective layer 60 colored concealed resin layer 70 non-concealed resin layer

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shigenori Kato 1-5-1, Taito, Taito-ku, Tokyo Inside Toppan Printing Co., Ltd. (72) Inventor Takashi Ikeda 1-1-5-1, Taito, Taito-ku, Tokyo F-term in Toppan Printing Co., Ltd. (Reference) 2E110 AB23 BA04 BA05 BB04 BB23 GA32W GA32X GA32Z GB43Z 4F071 AA20 AA88 AA89 AF05 AF20 AH03 BB06 BC01 4F100 AK07A AL05A BA02 CA13 CA13A CA13H EH46 JEJBJJB01J01B01A01

Claims (1)

[Claims] 1. A highly crystalline polypropylene having an isotacticity (boiling decane-soluble residue) of 95% or more is 70 to
90% by weight, MFR specified in JIS K 6760
Is 10 g / 10 min or more and 40 g / 10 min or less, and comprises a layer made of a resin composition having a flexural initial elastic modulus of 10,000 kgf / cm ² or more. Makeup sheet.