JP2952050B2 - Method of manufacturing decorative sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a decorative sheet which has been subjected to mechanical embossing with a sharp uneven pattern with sharp edges.

[0002]

2. Description of the Related Art Conventionally, construction (ceiling material, wall material, floor material, etc.),
BACKGROUND ART As decorative sheets used for furniture, vehicles, electric appliances, footwear, bags, and the like, there are known decorative sheets provided with various uneven patterns on the surface of a base material in order to improve a decorative effect. Various methods are known as a method of applying this uneven pattern, for example, by partially printing a foaming inhibitor-containing ink on a foamable synthetic resin layer formed on a base material, and heating and foaming to form irregularities. There is a chemical embossing method to be applied, or a mechanical embossing method of embossing a foamed or non-foamed synthetic resin layer formed on a base material with an embossing roll to form irregularities. Of these, embossing of a foamed synthetic resin layer by a mechanical embossing method has been widely adopted, for example, because it is possible to provide a concavo-convex pattern excellent in a sense of volume and softness.

[0003]

In recent years, there has been a tendency to increase the number of decorative sheets provided with designs having a more natural feeling, and the above-mentioned uneven pattern has changed from a rounded soft touch to an edged one. What is needed is a sharp and sharp feel.

[0004] Such a sharp textured uneven pattern,
In order to apply by the above-mentioned mechanical embossing method, it is necessary to sufficiently press the embossing roll or the like against the synthetic resin layer, or to sufficiently soften the synthetic resin layer by heating the embossing roll or the like prior to the embossing step. .

At this time, when the synthetic resin layer is a foamed synthetic resin, air in closed cells contained in the foamed synthetic resin layer at the pressing portion such as an embossing roll or the foamed synthetic resin layer to be softened by heating is expanded. As a result, the air bubbles grow large, and eventually, an air puncture (that is, a secondary foaming phenomenon) occurs, and a burst mark is left on the surface.

In order to provide a decorative sheet having a sharp embossed pattern by a mechanical embossing method without air puncturing, the present applicant firstly provided a base synthetic resin and a resin on the synthetic resin layer. On the other hand, a continuous porous surface-treated layer may be formed with an incompatible synthetic resin (see Japanese Patent Application No. 2-261111), or a continuous cell structure may be formed with microcapsules and a thermally decomposable chemical foaming agent. A technique has been proposed in which a foam layer is formed (see Japanese Patent Application No. 2-261112) and mechanical embossing is performed from these layers.

According to the present invention, there is provided a method for producing a decorative sheet provided with a sharp uneven pattern with sharp edges by a mechanical embossing method by means different from the above-mentioned prior proposals without generating the above-mentioned air puncture. The purpose is to provide.

[0008]

According to the production method of the present invention, in order to achieve the above object, 95 to 60 parts by weight of a vinyl chloride resin for paste and 5 to 40 parts by weight of a vinyl chloride suspension polymer are coated on a substrate. A layer made of a vinyl chloride resin composition containing a part and an appropriate amount of a chemical foaming agent is provided, and the layer is subjected to mechanical embossing directly or via a printing layer and / or a surface treatment layer. In this case, the above-mentioned vinyl chloride suspension polymer is characterized in that the average particle size is 80 to 130 μm, and the particle size of 150 μm or more is 5% by weight or less.

As the substrate in the method of the present invention, paper, woven fabric, non-woven fabric, knitted fabric, synthetic resin sheet, composite materials thereof and the like can be used, and the kind thereof is not particularly limited. Further, a base material having various characteristics such as flame retardancy may be used depending on the application.

In the method of the present invention, first, on the above-mentioned substrate,
A layer made of a vinyl chloride resin composition containing 95 to 60 parts by weight of a vinyl chloride resin for paste, 5 to 40 parts by weight of a vinyl chloride suspension polymer, and an appropriate amount of a chemical foaming agent is provided.

The above-mentioned vinyl chloride resin for paste is usually called a paste resin, which can be made into a plastisol by blending a plasticizer, and can be made of vinyl chloride alone, or of vinyl chloride and ethylene, propylene or vinyl acetate. Emulsion polymerization method in which radical polymerization of methacrylate, maleic acid ester, methyl methacrylate, methacrylic acid ester, acrylic acid ester, higher vinyl ether, etc. is generally performed using a water-soluble polymerization initiator, or an oil-based polymerization initiator is used. Then, using a homogenizer or the like, a polymer obtained by a micro-suspension polymerization method in which these monomers are mechanically and uniformly dispersed in water and polymerized, and further, an acrylic resin, vinyl acetate, Resin, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, urethane tree Vinyl chloride resin and the like blended with other synthetic resins and the like. These can be used alone or in combination of two or more. The vinyl chloride resin for a paste obtained by the above polymerization method is very fine polymer particles, and the particles are generally about 0.02 to 10 μm.

As is well known, the above-mentioned vinyl chloride-based suspension polymer refers to vinyl chloride or another monomer copolymerized with vinyl chloride, and a polymer (that is, a vinyl chloride-based polymer). Polymer) is a vinyl chloride-based polymer obtained by a suspension polymerization method of dispersing and polymerizing in a liquid phase (generally, water) in which both are hardly dissolved. The particle size is about 70 to 200 μm, which is as large as several tens to several hundred times the particle size of the above-mentioned vinyl chloride resin for pastes. In the method of the present invention, particularly, the average particle size is 80 to 200 μm. 13
5% by weight having a particle size of 0 μm and a particle size of 150 μm or more
Use the following: Because, in the method of the present invention, as described later, the suspension polymer is used to make the layer of the vinyl chloride resin composition into open cells, and if the average particle size is too small, the open cells will not be formed. If the layer is too thin, on the contrary, if the layer is too thin, irregularities due to the large-diameter suspension polymer may appear too much, resulting in a poor surface state of the layer.
In addition, as the synthetic resin constituting the vinyl chloride-based suspension polymer, the same as the above-mentioned vinyl chloride-based resin for pastes can be mentioned, and these vinyl chloride-based suspension polymers can be used alone or in combination of two or more Can be used.

The vinyl chloride resin for paste and the vinyl chloride suspension polymer contain a plasticizer, a solvent, and the like, and can be made into a paste. Examples of the plasticizer include di-2-ethylhexyl phthalate (DEP) and diisononyl phthalate (DIN).
P), general phthalate plasticizers represented by butyl benzyl phthalate (BBP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), dioctyl adipate (DOA), Dioctyl sebacate (DO
S), a general fatty acid ester plasticizer represented by dioctyl azelate (DOZ), a trimellitate plasticizer represented by trioctyl trimellitate (TOTM), tricresyl phosphate (TCP) ) And other plasticizers such as epoxy plasticizers, polyester plasticizers such as polypropylene adipate, and general plasticizers such as chlorinated paraffin. These can be used alone or in combination. It can be mixed and used.

The mixing ratio of the above-mentioned vinyl chloride resin for paste and the vinyl chloride suspension polymer to the plasticizer is appropriately selected in accordance with the kind of the plasticizer and the like. The plasticizer is preferably used in an amount of about 20 to 100 parts by weight based on 100 parts by weight of the total amount of the vinyl resin and the vinyl chloride suspension polymer.

The vinyl chloride resin composition in the method of the present invention is obtained by mixing the above-mentioned vinyl chloride resin for a paste and a vinyl chloride suspension polymer with 95-60: 5-4.
0 parts by weight are mixed. At this time, if the mixing ratio of the suspension polymer is too small, the layer of the composition cannot be made into continuous cells, and if it is too large, the layer is easily foamed. Not only is the shape of the layer distorted, the layer becomes wavy, but also the mechanical strength is reduced, the tensile strength, the tear strength and the like are reduced, and the elongation is also reduced. If the amount of the suspension polymer is too large, the polymer tends to settle.

In the method of the present invention, a chemical blowing agent is further mixed with the above composition. Examples of the chemical foaming agent include dinitrosopentamethylenetetramine, N, N'-
Dimethyl-N, N'-dinitrosoterephthalamide, benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), 3,3'-disulfone hydrazide diphenyl sulfone, toluene disulfonyl hydrazine, p
-Toluenedisulfonylhydrazide, p-toluenesulfonylsemicarbazide, azobisisobutyronitrile,
Examples include azodicarbonamide (ADCA) and diethyl azodicarboxylate. The mixing ratio of these chemical foaming agents may be appropriately selected depending on the desired degree of foaming of the layer of the composition, but generally, the total amount of the above-mentioned vinyl chloride resin for paste and the vinyl chloride suspension polymer is 100% by weight. The amount is selected from the range of 1 to 10 parts by weight per part.

Further, in the method of the present invention, a coloring agent, a stabilizer, a filler, a flame retardant, a fungicide, an antistatic agent and the like can be added in addition to the above-mentioned foaming agent.

In the method of the present invention, the above-mentioned vinyl chloride resin composition is coated with the above-mentioned base material by an appropriate means such as a doctor knife method, a rotary screen method, a gravure method, an offset method, a flexo method, or brush coating. After coating on it, it is heated and foamed and cured to form a layer of the composition. The coating thickness at this time is not particularly limited, but if the coating thickness is too large,
Since the suspension polymer may settle between the coating step and the heat treatment step, the upper limit is 0.5 mm
It is preferable to set the degree.

After forming the layer as described above, the layer is sufficiently softened by heat treatment again if necessary, and a mechanical embossing means such as an embossing roll is pressed on the layer. Thereby, a sharp uneven pattern with sharp edges is formed, and the decorative sheet according to the method of the present invention is manufactured.

In the method of the present invention, the above composition is coated and then gelled, and the gelled layer is coated on the gelled layer by a rotary screen method, a gravure method, an offset method or other appropriate printing means. Can be formed, and the above-mentioned mechanical embossing can be performed through the printed layer. Further, in the method of the present invention,
On the above-mentioned printing layer, or in place of the above-mentioned printing layer, a surface treatment layer is provided by the above-mentioned printing means for the purpose of adjusting gloss (matting and polishing) and imparting antifouling properties, and thereafter, Mechanical embossing can also be applied.

In the method of the present invention, the above-mentioned vinyl chloride-based resin composition is coated on release paper, gelled, and then transferred onto the above-mentioned substrate via an adhesive.
Alternatively, it is also possible to form a layer of the composition by a so-called transfer method of transferring without an adhesive before gelling and then heating and foaming, followed by mechanical embossing.

[0022]

According to the method of the present invention, the foamed layer formed of a mixture of the vinyl chloride resin for paste and the vinyl chloride suspension polymer formed on the base material is formed of a mixture of the vinyl chloride resin for paste and the vinyl chloride suspension polymer. Are formed into open cells by the synergistic action of That is, as is well known, the foamed layer formed by using the vinyl chloride resin alone for the paste is a fine foamed cell, and the size and shape of the cell are uniformly uniform, and it is a very dense and beautiful closed cell layer. However, when a vinyl chloride resin for paste and a vinyl chloride suspension polymer are used in combination, in a group of dense closed cells having a uniform size and shape by the vinyl chloride resin for paste, the size of the vinyl chloride suspension polymer and Large and irregularly shaped cells penetrate and break the cell walls of uniform and dense closed cells to make cells communicate with each other. Layers made by using both vinyl chloride resin for paste and vinyl chloride suspension polymer Is an open-celled foam layer.

When the mechanical embossing means such as an embossing roll is sufficiently pressed against such an open-cell foamed layer and, if necessary, when the layer is heated and softened prior to the pressing of the mechanical embossing means, Even if the foam layer causes a secondary foaming phenomenon, the gas generated by the phenomenon is easily discharged out of the layer through the open cells in the layer. In addition, during the above-described pressing or softening by heating, air in the layer may expand or move, but this air is also easily released to the outside of the layer through open cells in the layer. Therefore, according to the method of the present invention, no air puncture occurs in the decorative sheet subjected to mechanical embossing, and no rupture mark is formed on the sheet surface. In addition, since air puncturing does not occur as described above, the method of the present invention can significantly increase the temperature of the heat treatment prior to the pressing by the mechanical embossing means. As a result, the layer to be pressed is sufficiently softened, and a sharp uneven pattern with sufficiently sharp edges can be easily formed.

[0024]

Example 1 A paste-like polyvinyl chloride composition having a composition A shown in Table 1 was coated on a flame-retardant backing paper 1 having a thickness of 0.15 mm shown in FIG. After heating at 160 ° C. for 1 minute to gel, heat it at 215 ° C. for 1 minute with a far infrared heater to foam, and immediately press the embossing roll to perform mechanical embossing. To produce a decorative sheet.

In this decorative sheet, as shown in FIG. 1, a foam layer 2 made of the above-mentioned polyvinyl chloride composition is formed on a flame-retardant backing paper 1, and formed on the surface of the foam layer 2. The edge 3 ′ of the uneven pattern 3 was sharp and had an extremely sharp feel. In addition, the foamed layer 2 had little gloss, had a calm matte tone, and did not show any rupture marks on the surface.

Example 2 As shown in FIG. 2, the flame-retardant backing paper 1 used in Example 1
A paste-like polyvinyl chloride composition composed of Formulation B shown in Table 1 was coated on a flame-resistant backing paper 1 having the same composition as described above with a doctor knife so as to have a thickness of 0.20 mm, and then at 160 ° C. for 1 minute. After heating and gelling, the printing ink was gravure printed, followed by 210 g in a foaming furnace.
C. for 1 minute to foam. Thereafter, heat softening treatment was performed at 180 ° C. for 30 seconds with a far-infrared heater, and the embossing roll was pressed to perform mechanical embossing, thereby producing a decorative sheet.

In this decorative sheet, as shown in FIG. 2, a foam layer 2 made of the above-mentioned polyvinyl chloride composition is formed on a flame-retardant backing paper 1, and a gravure print layer 4 is formed on the foam layer 2. The edges 3 ′ of the concave-convex pattern 3 formed on the surfaces of the foam layer 2 and the print layer 4 were sharp and had an extremely sharp feel. Further, the foamed layer 2 has little gloss as in the case of Example 1,
It had a calm matte tone and no rupture marks on the surface.

Comparative Example 1 A decorative sheet was produced in the same manner as in Example 2 except that the paste-like polyvinyl chloride composition having the composition C shown in Table 1 was used. The decorative sheet obtained in this manner frequently suffered from secondary foaming in the pressing portion of the embossing roll, and had extremely many burst marks on the surface, and could not be commercialized.

Example 3 Two kinds of decorative sheets were produced in the same manner as in Example 1 except that the paste-like polyvinyl chloride composition composed of Formulations E and F in Table 2 was used. In each of these decorative sheets, similarly to the decorative sheet of FIG. 1 obtained in Example 1, the edge 3 ′ of the uneven pattern 3 formed on the surface of the foamed layer 2 is sharp and presents a sharp feel. And foam layer 2
Had a calm matte appearance with no rupture marks on the surface.

Comparative Example 2 Two kinds of decorative sheets were produced in the same manner as in Example 1 except that a paste-like polyvinyl chloride composition composed of Formulations D and G in Table 2 was used. In the decorative sheet using the composition of Formulation D, similarly to the decorative sheet obtained in Comparative Example 1, the secondary foaming phenomenon frequently occurred in the pressed portion of the embossing roll, and extremely many burst marks were formed on the surface. The decorative sheet using the composition of Formulation G has extremely poor surface smoothness of the gelled sheet, and also has unstable foam cells (so-called, easily settled), and none of them can be commercialized. Was.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

As described above in detail, according to the method of the present invention, a foam layer formed of a mixture of a vinyl chloride resin for paste and a vinyl chloride suspension polymer formed on a substrate is formed as an open cell layer. can do. This allows
In the method of the present invention, when mechanical embossing is performed on the layer directly or through a printing layer, and when the layer is heated and softened prior to the mechanical embossing, the foamed layer causes a secondary foaming phenomenon. Even so, the gas generated by the phenomenon can be easily discharged out of the layer through the open cells in the layer. In addition, air that expands or moves during the above-described mechanical embossing or heat softening can be easily released to the outside of the layer through open cells in the layer. As a result, in the method of the present invention, a sharp embossed pattern with sufficiently sharp edges can be easily formed by mechanical embossing without causing air puncture, and thus, without forming a burst mark on the sheet surface.

In addition, the foamed layer made of the mixture of the above-mentioned vinyl chloride resin for paste and the vinyl chloride suspension polymer has a calm matte appearance. Can be improved.

Further, the vinyl chloride suspension polymer is lower in cost than the vinyl chloride resin for the paste, and the chemical foaming agent is lower in cost than microcapsules. The cost of the product decorative sheet can be significantly reduced.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing one embodiment of a decorative sheet that can be produced by the method of the present invention.

FIG. 2 is an explanatory view showing another embodiment of a decorative sheet that can be produced by the method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base material 2 Layer by polyvinyl chloride composition 3 Uneven pattern by mechanical embossing 3 'Edge of uneven pattern 3 4 Printing layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI B32B 33/00 B32B 33/00 C08J 9/06 CEV C08J 9/06 CEV // C08L 27:06

Claims (2)

(57) [Claims] 1. A base material comprising a vinyl chloride resin 9 for paste.
A layer comprising a vinyl chloride resin composition containing 5 to 60 parts by weight, 5 to 40 parts by weight of a vinyl chloride suspension polymer and an appropriate amount of a chemical foaming agent is provided, and a printing layer and / or a surface treatment layer is formed directly on the layer. A method for producing a decorative sheet, characterized in that a mechanical embossing process is performed through the process. 2. A suspension of a vinyl chloride-based polymer,
2. The method for producing a decorative sheet according to claim 1, wherein the average particle size is 80 to 130 [mu] m, and the particle size of 150 [mu] m or more is 5% by weight or less.