JPH0311620B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a decorative sheet material and a method for producing the same, and more specifically, it is useful as an interior material for buildings such as houses, for example, as a wall covering material. The present invention particularly relates to a foamed decorative sheet material with excellent scratch resistance and scratch resistance, and a method for producing the same.

(Prior Art) Conventionally, various wall covering materials have been widely used for the interior of buildings such as houses, such as wall decoration, and more than 90% of these wall covering materials are wallpapers made of polyvinyl chloride resin. Currently, it is produced and used in an amount close to 200 million square meters.

The above-mentioned polyvinyl chloride wallcovering materials are roughly divided into non-foamed types and foamed types. It is characterized by the three-dimensional texture created by the pressed pattern.

Among foam-based wall covering materials, there are low-foam products with a foaming ratio of 2 to 3 times, and high-foam products with a foam ratio of 6 to 8 times.Comparing these, the higher the foam, the more the three-dimensional texture increases. , is welcomed as a luxury item.

(Problems to be Solved by the Invention) Although the above-mentioned highly foamed product has the above-mentioned advantages because it is foamed at a high magnification, since it is a highly foamed product, it inevitably has a low surface strength. for example,
When children touch walls or hit furniture or fixtures, the surface can easily be scratched, ripped off, or in extreme cases even torn, which is a problem with scratch resistance. .

Various methods have been devised to solve these problems and impart scratch resistance and scratch resistance to highly foamed wall covering materials, and the specific methods can be roughly divided into the following three methods.

(1) A method of applying a hard coating to the surface.

(2) A method of laminating a thin film with excellent scratch and scratch resistance on the surface.

(3) A method of suppressing the foaming ratio and increasing the thickness of the foamed synthetic resin layer accordingly.

In the method (1) above, a resin solution forming an essentially hard film such as polymethyl methacrylate is applied to the surface of the foamable synthetic resin layer before foaming and dried to form a film, followed by foaming; After foaming and embossing, there is a method in which a film is formed by applying the above-mentioned resin solution only to the convex portions of the squeeze pattern, but in the former case, the thicker the film, the better the scratch resistance and scratch resistance. It has the disadvantage that it is difficult to obtain a highly foamed product and it is difficult to form a clear squeeze pattern.If the coating is made thinner, sufficient scratch resistance and scratch resistance cannot be obtained. There is a problem that the two types of shibori-pressed patterns are not compatible.

In the case of the latter method, a film is formed after the high foaming process and the embossing pattern, so the scratch resistance and scratch resistance of the convex parts of the embossing pattern are improved, but the concave parts remain low in scratch resistance and scratch resistance. However, there is a problem in that the scratch resistance and scratch resistance are not improved as a whole.

In method (2) above, acrylic resin film is often used, but since this method is a method of laminating the film in a squeeze pattern, it cannot be used for deep squeeze patterns that are characteristic of highly foamed products. At best, it can only be applied to smooth satin-dyed shibori with shallow grooves and similar shallow shibori patterns.

In the case of method (3), a product with better scratch resistance and scratch resistance than methods (1) and (2) can be obtained, but
The product will inevitably be a low-foam product, which will not have the lightness and luxury feel characteristic of high-foam products, and will also be disadvantageous in terms of cost.

Therefore, we would like to provide a decorative sheet material that is a highly foamed product that has an excellent three-dimensional texture, a luxurious feel, and excellent scratch resistance and scratch resistance on the surface, and has a clear squeezed pattern with deep grooves, and its advantages. There is a demand for the development of a manufacturing method.

(Means for Solving the Problems) The present invention has been made in view of the above background, and when obtaining a highly foamed decorative sheet material, only the surface portion of the foamable synthetic resin layer is foamed. By forming a squeezed pattern and crushing it to form a high-density coating, and then foaming the entire surface, even highly foamed decorative sheet materials have excellent scratch and scratch resistance. The present invention was completed by discovering that a decorative sheet material having the following characteristics can be obtained.

That is, the present invention consists of two inventions, and the first invention consists of a backing material and a foamed synthetic resin layer with a surface squeeze pattern formed on the surface thereof, and the surface portion of the foamed synthetic resin layer is made of foamed resin. A second invention is a decorative sheet material characterized by forming a crushed layer, and the second invention comprises: a) forming a foamable synthetic resin layer on the surface of the backing material; b) a portion close to the surface of the foamable synthetic resin layer; c) pressing the partially foamed layer to crush the foamed layer and forming a squeeze pattern on the surface; and d) heating the whole to foam the foamable synthetic resin layer. A method for producing a decorative sheet material, characterized by:

Next, the present invention will be explained with reference to FIG. 1, which schematically shows one embodiment of the decorative sheet material of the present invention.

The decorative sheet material 10 of the present invention, as schematically shown in FIG.
A feature is that the surface portion of the foamed synthetic resin layer 2 serves as a crushed layer 3 of foamed resin.

That is, conventional highly foamed decorative sheet material 1
In contrast, in the decorative sheet material 10 of the present invention, there were problems in the scratch resistance and scratch resistance of the surface because the entire foamed synthetic resin layer was highly foamed. Although it is a highly foamed decorative sheet material 10, its surface portion has a crushed foam layer 3, that is, a low foamed to non-foamed state, so it is a highly foamed product with good surface scratch resistance and scratch resistance. This is a decorative sheet material 10.

In the example shown in the first diagram, a crushed layer 3 and a foamed layer 2 are shown in the drawing.
Although the two are clearly distinguished from each other, this is shown for convenience of explanation, and in reality, the crushed layer 3 and the foamed layer 2 are not separate layers but a continuous phase. In reality, the foaming ratio is the lowest on the surface of the crushed layer 3 (it may be non-foamed), and as it approaches the foaming layer 2, the foaming ratio increases little by little, and then reaches the foaming layer 2. .

The decorative sheet material 10 of the present invention has the basic structure as described above, but a thin film 4 of non-foamed resin may be further formed on the surface of the crushed layer 3, and such a thin film 4 may be formed. As a result, the scratch resistance and scratch resistance of the decorative sheet material 10 are further improved, and the presence of the thin film 4 allows the partially foamed layer 22 (FIG. 4) to be well crushed, resulting in deep grooves. This provides the effect that the stamped pattern 5 can be easily formed.

Next, the method for manufacturing the decorative sheet material 10 of the present invention will be described. The method for manufacturing the decorative sheet material 10 of the present invention comprises steps as shown in FIGS. 2 to 5.

First, in the first step a, a backing material 1 similar to that used in conventional decorative sheet materials,
For example, a foamable synthetic resin layer 21 is formed on a backing material 1 such as paper, woven fabric, nonwoven fabric, plastic sheet, wood, metal, or other sheets.

In particular, when a fine and coarse material such as a non-woven fabric or a woven fabric is used as the backing material 1, it is also preferable to perform a filling treatment or the like or to provide a thin resin layer or the like in advance. Further, these backing materials 1 may be elongated or tile-shaped, and their shape, thickness, etc. are not particularly limited.

Foamable synthetic resin layer 2 formed on the backing material 1
1 is a polyvinyl chloride resin such as polyvinyl chloride, vinyl chloride-ethylene copolymer, vinyl chloride-vinyl acetate copolymer, polyolefin resin such as polyethylene or polypropylene, polyvinyl acetate,
Vinyl acetate-ethylene copolymer, acrylic resin,
It is a layer containing a blowing agent in a thermoplastic resin such as NBR, MBS, ABS, polyester, polyamide, polyurethane, or a mixture thereof.As a blowing agent, azodicarbonamide or P,P'-oxybisbenzene sulfur is used as a blowing agent. Any blowing agent known in the art can be used, such as nylhydrazide.

Of course, the above-mentioned foamable synthetic resin layer 21 also contains colorants, plasticizers, stabilizers, fillers, antistatic agents,
Any additives such as lubricants may be included.

The above-mentioned foamable synthetic resin layer 21 can be formed from any conventionally known resin and by any method, but a particularly preferred method in the present invention is a method using polyvinyl chloride or vinyl chloride and other monomers. This method uses a paste sol or organosol made of a polyvinyl chloride resin such as a copolymer.

Paste sol is made of polyvinyl chloride resin particles made into a fluid, highly viscous liquid with a liquid plasticizer, and organosol contains a mineral oil-based solvent such as mineral turpentine to adjust the viscosity of this paste sol. It is.

The amount of the foaming agent added to the paste sol or organosol is determined by the final expansion ratio of the foamable synthetic resin layer 21, but when the purpose is a highly foamed decorative sheet material 10 like the one of the present invention, ~
6phr (phr is part by weight added per 100 parts by weight of resin)
degree is suitable. In addition, if the amount of plasticizer used is too large, the final product will be too soft, resulting in insufficient scratch resistance and scratch resistance.If it is too small, the product will be hard and have poor texture, so the preferred range is 40 to 60 phr. That's about it. Further, in the case of a polyvinyl chloride resin, it is particularly desirable to add a stabilizer, and this stabilizer is preferably one that does not inhibit the foaming of the foaming agent, for example, a Ba-Zn-based liquid stabilizer. The coloring agent may be any dye, pigment, etc., but preferred ones are easily dispersible ones in which pigments are pre-dispersed in a liquid plasticizer and in the form of toner. Other additives as described above may be added as necessary.

The paste sol or organosol preferably has a viscosity of about 5,000 to 10,000 cps from the viewpoint of its coating properties, etc., and such viscosity adjustment can be carried out by
This is easily accomplished by adding a mineral oil solvent such as mineral spirits.

For coating onto the backing material 1, any conventionally known coating method such as a doctor roll coater or a reverse roll coater can be used. Instead, it may be formed partially, that is, in a pattern.

The thickness of the foamable synthetic resin layer 21 varies depending on the purpose of use of the final product, and cannot be determined unconditionally, but the thickness of the foamable synthetic resin layer 21 is approximately 6 to 8 times as high as the decorative sheet material 10.
In this case, if a paste sol containing a foaming agent of 3 to 5 phr is applied to the backing material 1, such as paper, to a thickness of about 0.18 to 0.25 mm, the final thickness will be about 1.5 to 2.0 mm (backing material A highly foamed decorative sheet material 10 (where 1 is 0.12 mm paper) is obtained.

When the above-mentioned coating material is heated to around 120℃ after coating, the paste layer absorbs the plasticizer and loses its fluidity, forming a so-called gel, resulting in the foamable synthetic resin layer 2.
It becomes 1.

Following the first step a, the second step b shown in FIG. 4 will be provided. This surface layer 4
This contributes to the purpose of further increasing the scratch resistance and scratch resistance of the final product and to the preferred form of the embossing pattern 5 in the third step (c). It is made of a non-foaming synthetic resin that can form a soft film so as not to hinder the formation of the pattern 5.

For example, it can be formed by applying and drying a resin solution that forms a soft film, such as acrylic resin, urethane-modified acrylic resin, or acrylic-modified vinyl chloride resin.

Particularly preferred is a one-component reaction type acrylic resin solution, which forms a crosslinked soft cured film, thereby forming a squeeze pattern 5 with excellent scratch resistance and scratch resistance. Any coating method may be used, but if the film is too thick, it will interfere with the formation of the squeeze pattern 5, so it is preferable to form a thin layer, for example, 30 to 50 g/m ² (solution). As the coating method, gravure coating method etc. is most suitable. 50-100 after application
A desired non-foaming resin coating 4 is formed by heating to about .degree.

The second step b mainly characterizes the method of the present invention, and in this step, only the surface portion of the foamable synthetic resin layer 21 formed above, for example, the foamable synthetic resin layer A partially foamed layer 22 is formed by foaming a surface portion of about 1/2 to 1/5 of the total thickness of the layer 21 . Such partial foaming treatment may be performed by any method, but for example, while the back side of the sheet having the foamable synthetic resin layer 21 is brought into contact with a conventional heating drum, the temperature of the heating drum is adjusted to The partially foamed layer 22 is continuously formed by heating at a temperature lower than the foaming temperature of the resin layer 21, for example 100 to 150°C, using an infrared heater or hot air to a temperature higher than the foaming temperature of the foaming agent. be able to.

At this time, the degree of foaming of the partially foamed layer 22 can be changed by variously adjusting the temperature difference between the heating drum and surface heating, heating time, etc. Of course, in this process, the surface part is not completely foamed and the lower part is not completely foamed.
In reality, the degree of foaming across the thickness of the layer is continuous, with the degree of foaming being greater towards the surface and being lower closer to the backing material 1, and the present invention is of course applicable to such a situation. It also includes.

In the third step c, as shown in FIG. form 5. In this step c, as a result of the surface portion of the foamable synthetic resin layer 21 being foamed, the squeeze pattern 5 is very well formed.
is formed.

On the other hand, if the surface portion 22 is not foamed, that is, if it is embossed in the state shown in the second and third figures, the good embossing pattern 5 will not be formed because the foamable synthetic resin layer 21 is thin. , even if it is forcibly formed, if the whole is foamed afterwards, the formed squeeze pattern 5 will be averaged and a deep squeeze pattern 5 will be created.
is something that cannot be obtained. Furthermore, if such embossing treatment is performed after the entire foamable synthetic resin layer 21 has been foamed, the foamed layer is soft, so the foamed layer may be crushed and lose its desirable appearance, or the surface quality may deteriorate. Such scratch and scratch resistance cannot be achieved.

Further, in this step c, the embossing pattern 5 is formed by the pressure of the embossing roll, and the foamed portion 22 is crushed, so the surface portion of the embossing pattern 5 is in a low-foamed or non-foamed state. Since the crushed layer 3 having the squeeze pattern 5 becomes the surface layer of the final product, its scratch resistance and scratch resistance are significantly improved compared to conventional highly foamed products. Of course, the embossing process in step c is performed continuously following the second step b, and the temperature during embossing may be the same as in the prior art.

In the fourth step d, the sheet having the squeeze pattern 5 obtained in the third step c is heated as a whole,
This is a process of foaming the foamable synthetic resin layer 21 as a whole, for example, by continuously heating it in a heating furnace heated to about 150 to 250°C for a retention time of about 30 seconds to 5 minutes. The foaming agent that was not foamed in the third step c is foamed to obtain the decorative sheet material 10 of the present invention as shown in the first figure.

(Operation/Effect) In the first invention of the present invention as described above, the backing material 1
The decorative sheet material 10 of the present invention is highly foamed by forming a desired squeeze pattern 5 on the surface of the foamed synthetic resin layer 2 formed above, and by making the surface a crushed layer 3 of foamed resin. Even when used as a product, sufficient surface scratch resistance and scratch resistance can be achieved due to the presence of the crushed layer 3, and the problem of inferior scratch resistance and scratch resistance of conventional highly foamed decorative sheet materials can be overcome. Well resolved.

Further, according to the second invention of the present invention, the above-mentioned third
By employing step c, since the foam layer 22 is partially present at the time of embossing, the squeeze pattern 5 with deep grooves can be easily formed, and the crushed layer 3 produced by the embossing can be When the entire foam is foamed, there is no further foaming (even if it foams, it is only a small amount), so the depth of the squeeze pattern 5 is not softened by the entire foaming, and a clear squeeze pattern 5 with deep grooves is formed. The decorative sheet material 10 is maintained as it is, and furthermore, since these surface crushing layers 3 act as a skin layer of the entire foamed product, a highly foamed decorative sheet material 10 with greatly improved surface scratch resistance and scratch resistance can be easily provided. be done.

Further, in a preferred embodiment of the present invention, by providing a thin non-foamed resin layer 4 on the outermost layer from the beginning, the entire squeeze pattern 5 is completely covered, thereby improving the scratch resistance and scratch resistance of the final product. In addition to further improving the properties, other properties such as scratch resistance and stain resistance are further improved.

Although the present invention has been described above, mainly targeting polyvinyl chloride resin wall covering materials, the present invention is not limited to such polyvinyl chloride resin wall covering materials, and other thermoplastic resins can also be used. Moreover, the application is not limited to wall covering materials, but is also useful as an automobile interior material, furniture exterior material, clothing, bags, and other materials.

Next, the present invention will be explained in more detail with reference to Examples. Note that % and % are based on weight unless otherwise specified.

Example 1 Polyvinyl chloride resin (Zeon 135, manufactured by Nippon Zeon,
Average degree of polymerization = 1500, average particle size 75 μm) 100 parts plasticizer (DOP) 45 parts blowing agent (azodicarbonamide) 5 parts colorant (toner) Appropriate amount Mineral spirits Appropriate amount Adjust the amount of mineral spirits in the above formulation By doing so, a paste sol with a viscosity of 6000 cps (25°C) was obtained.

The above paste sol was uniformly coated onto a 0.12 mm thick backing paper using a doctor blade coater to a thickness of 0.2 mm, and then passed through a heating furnace at 100° C. to gel the paste sol layer. Next, one-component curable acrylic resin paint (manufactured by Dainichiseika Industries, LM-402 solid content 30%)
was applied uniformly using a gravure coater at a rate of 30 g/m ² (solution) and dried at 80° C. for 1 hour to form a surface layer.

Next, the back side of this sheet is brought into contact with half the circumference of a heating drum at 130 to 140°C, and the front side is heated to 180 to 200°C using an infrared heater. ) was foamed. When the cross section of this foam was examined under a microscope, it was found that up to about 1/3 of the entire surface was foamed to 2 to 3 times its size, about 1/3 of the area near the backing material was unfoamed, and the middle 1/3 was foamed to 2 to 3 times its size. Slight foaming was observed at around /3.

Subsequently, the partially foamed layer was embossed with a clearance of 0.5 mm using a preheated clearance embossing roll to form a squeeze pattern on the surface. When the sheet was cut in this state and the cross section was observed under a microscope, it was found that most of the foam layer had been crushed.
Next, send it to a foaming furnace heated to 180 to 200℃, about 10
A decorative sheet material of the present invention was obtained by heating and foaming for a minute. The final foamed decorative sheet material had an overall expansion ratio of 6 to 8 times.

The decorative sheet material of the present invention obtained as described above had excellent scratch resistance, scratch resistance, and stain resistance, and was particularly useful as a wall covering material.

[Brief explanation of drawings]

FIG. 1 is a diagram schematically showing a cross section of the decorative sheet material of the present invention, and FIGS. 2 to 5 are diagrams schematically showing the method of the present invention. 1: backing material, 2: foam layer, 3: crush layer, 4: surface layer, 5: squeeze pattern, 21: foamable synthetic resin layer, 22: partially foam layer.

Claims (1)

[Scope of Claims] 1. Consisting of a backing material and a foamed synthetic resin layer having a surface squeeze pattern formed on its surface, the surface portion of the foamed synthetic resin layer is a crushed layer of foamed resin. and decorative sheet materials. 2. The decorative sheet material according to claim 1, wherein a non-foamed resin thin film layer is formed on the surface of the squeeze pattern. 3. The decorative sheet material according to claim 1, wherein the foamed synthetic resin layer is made of a polyvinyl chloride resin. 4. The decorative sheet material according to claim 1, wherein the foamed synthetic resin layer has a foaming ratio of 5 times or more. 5 a Step of forming a foamable synthetic resin layer on the surface of the backing material, b Step of foaming a portion of the foamable synthetic resin layer near the surface, c Pressing the partially foamed layer to crush the foamed layer and at the same time 1. A method for producing a decorative sheet material, comprising the steps of: forming a squeezed pattern; and d) foaming the foamable synthetic resin layer by heating the entire body. 6. The method for producing a decorative sheet material according to claim 5, further comprising the step of forming a non-foamable resin thin film layer on the surface of the foamable synthetic resin layer formed in step a. 7. The method for producing a decorative sheet material according to claim 5, wherein the foamable synthetic resin layer is made of a polyvinyl chloride resin. 8. The method for producing a decorative sheet material according to claim 5, wherein the foaming ratio of the foamed synthetic resin layer is 5 times or more.