JPS60192616A - Polyvinyl chloride sheet of flat plate with fill-up pattern - Google Patents

Abstract

PURPOSE:To make possible intentional designing of wear-resistant free pattern by a method wherein the cavity on a pattern of a polyvinyl chloride resin sheet is filled up with plasticizer dispersing element of polyvinyl chloride paste resin of a different color and said plasticizer dispersing element is heated and welded. CONSTITUTION:The cavity of a sheet or plate that is embossed or unevenly patterned is filled up with plasticizer dispersing element of prepared polyvinyl chloride paste resin and then the sheet or plate is heated at least at gelling temperature to gel the paste sol. Due to this gelling, the paste sol is hardened, and solves and adheres tightly to the sheet or plate. The color tone of the plate or the paste sol can be selected freely by adding pigment and/or dispersing colored vinyl chloride powder or grain in the sol.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyvinyl chloride resin sheet or flat plate having an embedded pattern formed by a forming method that allows for arbitrary designs.

Intaglio printing, rotary screen printing, valley sheet printing, congolium process, and non-uniform blending of colorants are well-known methods for creating patterns on the surface of polyvinyl chloride sheets. Each method is used depending on the situation. All of these methods have been established as effective techniques for enhancing the decorativeness of PVC sheets and increasing their commercial value, but these pattern forming techniques are not always satisfactory from the viewpoint of physical properties or market demands. It's not something you should do.

For example, as a method of applying patterns to vinyl chloride flooring,
There are the heterogeneous blending method and the convolium process.

The former is a method in which a coloring agent is scattered in a mixture of polyvinyl chloride resin as a base material and inorganic powder such as calcium carbonate, and a marble pattern is formed on the sheet surface during the process of forming the sheet.

Due to the nature of this technology, the coloring material is unevenly dispersed inside the sheet, so the marble pattern will not disappear due to surface abrasion, but it is not possible to design arbitrary patterns.

On the other hand, the latter Convolium process involves printing a pattern on a semi-gelled sheet of vinyl chloride paste resin containing a foaming agent using an ink containing a foaming inhibitor, and then printing the pattern at a temperature above the decomposition temperature of the foaming agent. This is a technology in which the sheet is heated to foam and a chemically embossed pattern is formed on the surface of the sheet.

The feature of this method is that it is possible to design any pattern, but on the other hand, because the chemical embossing technique relies on foaming the sheet, the mechanical strength of the sheet, especially its abrasion resistance, is reduced and the surface smoothness is reduced. Gender is also lost. In order to compensate for these drawbacks, a non-foaming transparent surface protective layer called a top coat is usually provided with a thickness of about 200 microns, but this process is based on the top coat.

Since the printing method is used for hontsuri, once the surface protective layer is worn away, the pattern will disappear in a short period of time.

Furthermore, from the viewpoint of market needs, there are cases in which it is extremely difficult to apply the current pattern forming techniques as described above, as in the following example.

BACKGROUND ART Recently, sheet-like flooring materials that are made by adding a large amount of conductive powder such as carbon black or metal powder to vinyl chloride resin have been attracting attention.

Such conductive flooring materials are used to prevent electrostatic damage to advanced electronic equipment such as combinators or medical equipment. Therefore, flooring materials used for this purpose need to have conductive or at least non-static functions, but sheet flooring materials for this purpose have both conductive function and economic efficiency. Taking this into consideration, it is reasonable to use carbon black as a conductive material. However, the problem in this case is that the surface color of the sheet becomes monochromatic black due to the addition of carbon black.

If we try to apply the above-mentioned floor tile marble pattern formation technology or convolium process for the purpose of forming a pattern on the surface of a sheet containing a large amount of carbon black, it will be extremely difficult to maintain the decorative effect or conductivity. Involves high technical difficulty. In particular, the Convolium process cannot be used as a surface decoration technique because the surface protective layer becomes an insulating layer and the conductive function is lost.

For this reason, conventional pattern forming techniques are inadequate as techniques for forming patterns on the surface of carbon black-added grooved polyvinyl chloride sheets.

Therefore, for surface decoration of plastic flooring materials using carbon black as a conductive material, it is necessary to develop a pattern forming technique based on a new idea in place of the conventional method. For example, Patent Publication No. 50-24358 discloses that an upper resin sheet containing carbon black is scattered through the front and back surfaces to form a conductive part, and a conductive lower resin sheet containing carbon black is bonded together. There is a description of a conductive resin plate made of In addition, utility model public notice Sho-51-
27737, a small amount of a conductive substance compatible with the sheet material is sandwiched between two non-conductive polymer sheets, and an upper layer is formed so that the conductive substance can leached out at one point over an area of at least 25 cm from the surface. A conductive laminated plastic tile has been described which has a structure in which the back surface of the tile is provided with unevenness, holes are formed at appropriate intervals in the lower sheet, and the holes are filled with a conductive material so that the conductive layer comes into direct contact with the ground. ing.

The surface layer of a plastic tile with this structure is
It is said that it can be colored freely, and that an appropriate resistance value can be maintained by the interlayer made of a conductive material seeping into the surface layer.

In addition to these two sides, conductive flooring materials in which carbon black is connected, that is, conductive flooring materials that have a mesh pattern in which the carbon black sea phase is the sea phase and the colored resin portion is the island phase, have been commercialized. . In addition, the valley sheet printing method is a well-known method for adding patterns to the surface of vinyl chloride sheets, but as can be seen from the manufacturing method, these pattern forming methods do not allow intentional designs of patterns. Either it is not possible (Patent Publication No. 50-24358 or mesh pattern conductive flooring material with carbon black as the sea phase), or it is possible to intentionally design a pattern, but the control of conductivity is delicate and mass production is difficult. It is extremely difficult to create and select materials (Utility Model Publication Publication No. 5l-27737)
It is. In addition, in the valley sheet printing method, the printing device is attached after the engraving (embossing) roll of the embossing machine, printing ink is applied to the ridges of the engraving die, and the ink is transferred to the valleys (concave parts) of the sheet. It is a method of printing, and in principle it can be considered the same printing method as intaglio printing.

Therefore, it cannot be used in applications where surface wear is likely to occur, such as flooring.

In contrast, the present invention aims to create an arbitrary pattern that easily provides wear resistance on not only the surface of a normal polyvinyl chloride sheet but also the surface of a conductive polyvinyl chloride sheet without impairing its function. It provides technology that allows for creative design.

That is, the present invention is a polyvinyl chloride resin sheet with an embossed arbitrary pattern or a polyvinyl chloride resin sheet colored with a pigment or the like, or a polyvinyl chloride paste resin colored in a color different from that of the sheet or flat plate in the concave portion of the pattern. A polyvinyl chloride resin sheet or flat plate having an embedded pattern obtained by filling a plasticizer dispersion and then heating it to gel the polyvinyl chloride paste resin and simultaneously fusing it to the sheet or flat plate. Regarding.

The method for forming the polyvinyl chloride sheet or flat plate of the present invention will be explained below.

(1) A sheet or flat plate is formed by a normal vinyl chloride resin processing method such as calendering, hot pressing or extrusion molding.

(2) A flat metal mold or engraved square with an embossed pattern is pressed onto the sheet or flat plate in a semi-molten state by heating to transfer the embossed pattern. In this case, the depth of the embossing should not exceed the thickness of the vinyl chloride sheet or flat plate. The semi-molten state referred to herein is a state in which embossing can be easily performed during the pattern transfer process, but the sheet or flat plate itself or the embossed pattern is not deformed. Specifically, the optimum embossing temperature varies depending on the degree of plasticization of the vinyl chloride resin, the type and amount of filler such as inorganic powder, or processing speed, but the temperature range is preferably about 60°C to 150°C. However, when an appropriate smoother (framework) is used for embossing using a press method, the temperature can be raised to about 200°C. Embossing can also be performed by injection molding using an embossed flat metal mold.

(3) Fill the concave portions of the embossed sheet or flat plate with an uneven pattern with a plasticizer dispersion (paste sol; liquid) of polyvinyl chloride paste resin prepared in advance, and then fill the sheet or flat plate with at least The paste sol is gelled by heating at a temperature higher than the gelling temperature. This gelation solidifies the paste sol and firmly fuses it to the sheet or flat plate. The color tone of the sheet, flat plate or paste sol can be freely selected by adding pigments and/or by interspersing colored vinyl chloride powder or grains in the sol. Note that when the paste sol is filled into the concave portions of the sheet or flat plate, excess sol also adheres to the convex portions on the surface of the sheet or flat plate, but it is desirable to remove this adhered sol as much as possible.

(4) A polyvinyl chloride sheet or flat plate having an embedded pattern is obtained by the above operations, but if the paste sol adheres to the curved portion of the embossing, it solidifies and fuses and contaminates the surface. In such a case, it is removed by surface polishing or planing.

The basic operation of the present invention has been explained above, but the most important feature of the present invention is that vinyl chloride resin is used as the raw material resin for the sheet or flat plate, and the recesses of the surface embossing are filled with the same type of material as the sheet or flat plate raw material. The purpose is to fill the resin with a vinyl chloride paste resin plasticizer dispersion, heat and solidify it, and at the same time completely fuse it to a sheet or flat plate to form an embedded pattern. Therefore, appropriate selection of the sheet or flat plate material and the embedding resin is the most important requirement for making the present invention fully effective.First, the appropriate sheet or flat plate material is:
Polyvinyl chloride, graft copolymer resins of ethylene-vinyl ester copolymer resins such as ethylene-vinyl acetate copolymer resins and vinyl chloride, or graft copolymer resins of polyurethane resins and vinyl chloride, ethylene-vinyl chloride copolymer resins, Vinyl ester-vinyl chloride copolymer resin such as vinylidene chloride-vinyl chloride copolymer resin, vinyl acetate-vinyl chloride copolymer resin or vinyl propionate-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin and polyvinyl chloride. These are blends of resins, each alone or a blend of at least two or more resins selected from the resins listed above. In addition, for the purpose of imparting flexibility to sheets or flat plates, those commonly used as plasticizers for vinyl chloride, such as low molecular weight polyesters, dioctyl phthalate, dibutyl phthalate, and phthalate ester plasticizers.

Secondary plasticizers and flame retardant plasticizers such as chlorinated paraffin, xylenyl diphenyl phthalate can be used.

The embedding resin must be a vinyl chloride paste resin such as a polyvinyl chloride paste resin or a vinyl acetate-vinyl chloride copolymer paste resin, but the above plasticizers can be used as the plasticizer used in the paste/sol. That is, it is an essential condition of the present invention to use a polyvinyl chloride resin as the sheet or flat plate material and a polyvinyl chloride paste resin as the embedding resin, and the effects of the present invention may not be effective depending on the combination of resins other than these. It cannot be made to manifest. However, if necessary, for example, carbon plaque, carbon fiber, metal powder, conductive or semiconductive metal oxide or inorganic powder such as tin oxide, surfactant, polyethylene rubber, etc. Recalls or mixtures thereof may be added to the sheet or plate material. In addition, inorganic powder such as calcium carbonate or clay, iron oxide powder, wood powder, or heat stabilizer can be added to the material or the embedded material for the purpose of improving hardness, thermal stability, or economic efficiency.

Furthermore, for the purpose of reinforcing the sheet or flat plate, woven or non-woven fabrics made of organic fibers such as polyester, rayon, cotton, etc. and/or inorganic fibers such as glass fiber are laminated on the sheet or flat plate, or organic and/or non-woven fabrics are laminated on the sheet or flat plate. Single fibers can also be blended. In particular, in order to enhance the conductive effect of a conductive sheet or flat plate, it is necessary to make the grounding perfect. For this purpose, one or more thin metal wires are connected in the vertical or horizontal direction or in the vertical or It can also be embedded in both directions.

The sheets or flat plates of the present invention are particularly useful as flooring materials.

Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 Polyvinyl chloride (manufactured by Toyo Soda Kogyo ■ - 4-700D)
) per 100 parts by weight of dioctyl phthalate) (DOP)
Calcium carbonate 8 with 55 layers of evidence and an average particle size of 5 microns
0 parts by weight, 5 parts by weight of titanium oxide, and 4 parts by weight of a lead-based composite stabilizer (Stavinex 0G756 manufactured by Mizusawa Chemical Industry Co., Ltd.) was made into a sheet with a thickness of tlm using a calender, and then a polyester fiber fabric was prepared. Two of these sheets were heated and laminated with a cloth (ester cloth manufactured by Toyo Senki ■) interposed therebetween to produce a sheet with a thickness of 2.2 mm. Hold this sheet vertically 15
cm, cut to 15cm wide, size 20X
20cm, engraving depth [Set on top of the embossing die L81IjI. Furthermore, the size is 17 x 17. cm.

Place a 1.2 m+ thick stainless steel spacer (frame) on top of the embossing mold. This embossed mold has a vinyl chloride sheet and a spacer integrated into it, and when pressed at a gauge pressure of 60 kg/Ctn' using a heat press maintained at a temperature of 160°C, an embossed pattern is created on the sheet. is transcribed.

On the other hand, 60 parts by weight of DOP, 50 parts by weight of calcium carbonate,
Barium-zinc heat stabilizer (manufactured by Adeka Argus Chemical Co., Ltd.)
(!-118) 3 parts by weight, 2 parts by weight of epoxidized soybean oil (Adeka Sizer 0-130F manufactured by Adeka Argus Chemical ■), and 0.3 parts by weight of red pigment in the recessed part of the embossed sheet. and then scrape off the excess sol. Then, the filling surface was heated to 200℃
The sol is heated with hot air for 90 seconds to gel the sol and at the same time fuse it to the sheet. After polishing the surface of the sheet with the embedded pattern obtained in this way, it was
It was cut to a size of 3 cm and subjected to a bending test using a constant speed tensile tester. The bonding strength between the paste resin and the sheet was examined by bending 30 times under the following conditions: maximum distance between chucks 10 cm, minimum distance between chucks 5 cm, test temperature 25°C, crosshead reciprocating speed 200 m, and 7 minutes. As a result, no peeling or cracking was observed, and it was confirmed that the paste resin was completely fused to the sheet.

Example 2 A sheet reinforced with a polyester fiber fabric having a thickness of 2.2 sn obtained in Example 1 was heated (approximately 90° C.) with an infrared heater, and then the roll spacing was 1.5.
An embossed sheet was prepared by roll-bonding with an embossing roll + having a carving depth of α6 mm and an m-plane roll kept at a temperature of 180°C. The embossed sheet thus obtained was treated according to the method described in Example 1, and then the pattern fusion properties of the sheet having the embedded pattern were tested according to the test method described in Example 1. As a result, it was found that the paste resin and No peeling or cracking was observed between the paste resin and the sheet, and it was confirmed that the paste resin was completely fused to the sheet.

Example 6 Polyvinyl chloride (Suron 700D manufactured by Toyo Soda Kogyo)
) 80 parts by weight of DOP per 100 parts by weight.

Iron oxide powder with an average particle size of 3 microns (FB manufactured by Ishihara Sangyo) 5
50 parts by weight, 50 parts by weight of clay, 15 parts by weight of chlorinated paraffin with 45% chlorine content (Toyo Barax Φ145 manufactured by Toyo Kaedatsu Kogyo), 4 parts by weight of lead-based composite stabilizer (Mizusawa Chemical Industry) Using a calendar, a mixture consisting of Stabinex 0G-756 (manufactured by Manufacturer) and 5 parts by weight of antimony trioxide (Atox S, manufactured by Nippon Prefecture) was heated to a thickness of 1.11111J.
A sheet of I was made, and then two of these sheets were heated and laminated with a polyester fiber fabric (ester cloth made by Toyo Senki ■) interposed therebetween to make a sheet with a thickness of 2.2 m. This sheet was treated in the same manner as in Example 1 (however, the pigment used in the paste resin was 1 part by weight of titanium oxide), and the fusion strength between the embedded paste resin and the sheet was measured by the test method described in Example 1. As a result of the test, no peeling or cracking was observed between the paste resin and the sheet, and it was confirmed that the paste resin was completely fused to the sheet. This result shows that the present invention is effective even for sheets containing a very large amount of inorganic powder.

Example 4 A sheet with an embedded pattern was made by the method described in Example 1 except that ethylene-vinyl chloride copolymer resin (Suro 41500 manufactured by Toyo Soda Kogyo ■) was used as the sheet material, and the paste resin and the sheet were combined. As a result of testing the fusion strength, it was confirmed that the paste resin was completely fused to the sheet, and the effectiveness of the present invention was not impaired in any way even if ethylene-vinyl chloride copolymer resin was used as the sheet material. .

Example 5 Polyvinyl chloride (manufactured by Toyo Soda Kogyo 5-1 Ron 700)
D) 100 parts by weight, 50 parts by weight of DOP, carbon black (Ketjen Black EC manufactured by Lion Akzo)
) 8 parts by weight, antimony trioxide (Atox S manufactured by Nippon Prefecture), 5 parts by weight, and lead-based composite stabilizer (Mizusawa Chemical Industry ■)
A compound consisting of 4 parts by weight of Stabinex 0G-756) manufactured by Toyo Co., Ltd. was thoroughly mixed using a super mixer, then melt-kneaded using hot rolls to make a sheet with a thickness of 2111 mm. It was reinforced by laminating and reinforcing fibers (made of ester cloth) by heat fusion. Next, the opposite side of the reinforcing surface was embossed using the method described in Example 1, and the same vinyl chloride paste sol described in Example 1 (however, the pigment used was 1 part by weight of titanium oxide) was applied to the embossed recesses of the sheet. After filling the filling surface with 2
The sol was heated with hot air at 00° C. for 90 seconds to gel the sol and simultaneously fuse it to the sheet. The sheet having the embedded pattern thus obtained was subjected to a bending test according to the test method described in Example 1. As a result, no peeling or cracking was observed between the paste resin and the sheet, and it was confirmed that the paste resin was completely fused to the sheet.

Comparative Example 1 Low density polyethylene (PETROCENE 20 manufactured by Toyo Soda Kogyo ■)
5) 25 parts by weight of calcium carbonate having an average particle size of 5 microns were added to 100 parts by weight, and after thoroughly kneading these with a hot roll, a sheet having a thickness of t 2 iu+ was prepared using a hot press. A polyester fiber fabric (ester cloth made by Toyo Sensai Koji) was sandwiched between these two sheets, and this was set on the same embossing mold as used in Example 1, and the engraving depth was 8 m by heat pressing. , 2m thick
7 pieces were obtained. The embossed sheet thus obtained was filled with a sol of vinyl chloride paste resin having the composition described in Example 1, and treated under the same conditions as described in Example 1. The strength of the fusion bond between the sheet and the paste resin was investigated.

As a result, part of the paste resin peeled off from the sheet surface at the third bending time. The fusion of the paste resin to the polyethylene sheet surface was incomplete and was judged to have no practical value.

Patent Applicant: Toyo Soda Koso Co., Ltd. Procedural Amendment June 4, 1980 Mr. Kazuo Wakasugi, Commissioner of the Agency for Special Bacteria 1 Indication of Case 1989 Patent Application No. 47168 2 Name of Invention Polyvinyl chloride with embedded pattern Telephone number (585) 3-11 4. Supplementary IF Order Daily Voluntary 6. Claims of the specification to be amended and Detailed Description of the Invention column 7. Contents (1) The claims of the specification are amended as shown in the attached sheet.

(2) 7 lines from the bottom of page 11, [Spacer-1 is corrected to be "spacer."

(3) In the statement on page 14, line 8, "chlorinated paraffin" is corrected to "chlorinated paraffin."

(a) In the 7th line from the bottom of page 15, "inorganic single fiber" is corrected to "inorganic short fiber."

(6) 9 lines from the bottom of page 16, "0G756" is changed to "
Corrected to oG-756j.

(6) In the 11th line from the bottom of page 22, "pincer" is replaced with "
``Hammer,'' he corrected.

2. Scope of Claims (1) A polyvinyl chloride resin sheet with an embossed arbitrary pattern or colored with a pigment or the like, or polyvinyl chloride whose concave part of the pattern is colored in a color different from that of the sheet or flat plate. A polyvinyl chloride resin sheet having an embedded pattern obtained by filling a plasticizer dispersion of a paste resin and then heating it to gel the polyvinyl chloride paste resin and simultaneously fusing it to the sheet or flat plate. flat plate.

(2) A flat metal mold with an embossed pattern or an engraved roll made of metal or a material that does not deform due to heat is pressed onto the sheet or flat plate that is in a semi-molten state by heating to create an embossed pattern on the sheet or flat plate. The polyvinyl chloride resin sheet according to claim 1, which uses a polyvinyl chloride resin sheet or a flat plate on which an embossed pattern has been applied by a transfer method or by an injection molding method using a flat metal mold having an embossed pattern. Or a flat plate.

(3) Conductive material obtained by adding carbon black, carbon fiber, metal powder, surfactant, polyethylene glycol, conductive or semiconductive metal oxide, inorganic powder, or a mixture thereof to polyvinyl chloride resin. 1. A polyvinyl chloride resin sheet or flat plate according to claim 1 or 2, which uses a polyvinyl chloride resin sheet or flat plate having an antistatic function.

(Claims 1 to 4) using a polyvinyl chloride resin sheet or flat plate reinforced by laminating organic and/or inorganic fiber fabrics or non-woven fabrics or blending organic and/or inorganic staple fibers. The polyvinyl chloride resin sheet or flat plate according to any one of Item 3.

(5) Claim No. 1 in which one or more thin metal wires are embedded in a conductive or non-electrostatic polyvinyl chloride resin sheet or flat plate in the vertical direction or in both the vertical and horizontal directions for the purpose of grounding. The polyvinyl chloride resin sheet or flat plate according to item 5.

(6) Polyvinyl chloride A/, vinylidene chloride-vinyl chloride copolymer a resin, graft copolymer resin of ethylene-vinyl ester copolymer resin and vinyl chloride, or graft copolymer resin of polyurethane resin and vinyl chloride, ethylene , -Pinyl chloride copolymer resin, vinyl ester-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin and blend with polyvinyl chloride, each alone or a blend of at least two or more resins, into a sheet or flat plate. A polyvinyl chloride resin sheet or flat plate according to any one of claims 1 to 3 used as a material.

Claims (6)

[Claims] (1) Plasticizer dispersion of a polyvinyl chloride paste resin colored in a different color from the sheet or flat plate in the recessed areas of the pattern on a transparent or pigment-colored polyvinyl chloride resin sheet or flat plate with an embossed pattern. A polyvinyl chloride resin sheet or flat plate having an embedded pattern obtained by filling the body, heating the resin, gelling the polyvinyl chloride paste resin, and simultaneously fusing it to the sheet or flat plate. (2) A flat metal mold with an embossed pattern or an engraved roll made of metal or a material that does not deform due to heat is pressed onto the sheet or flat plate that is in a semi-molten state by heating to create an embossed pattern on the sheet or flat plate. The polyvinyl chloride resin sheet according to claim 1, which uses a polyvinyl chloride resin sheet or a flat plate on which an embossed pattern has been applied by a transfer method or by an injection molding method using a flat metal mold having an embossed pattern. Or a flat plate. (3) Conductive material obtained by adding carbon black, carbon fiber, metal powder, surfactant, polyethylene glycol, conductive or semiconductive metal oxide, inorganic powder, or a mixture thereof to polyvinyl chloride resin. The polyvinyl chloride resin sheet or flat plate according to claim 1 or 2, which uses a polyvinyl chloride resin sheet or flat plate having a static or antistatic function. (4) Claims 1 to 4 which use a polyvinyl chloride resin sheet or flat plate reinforced by laminating organic and/or inorganic fiber fabrics or non-woven fabrics or blending organic and/or inorganic single fibers. The polyvinyl chloride resin sheet or flat plate according to any one of Item 3. (5) For the purpose of grounding, connect one or more thin metal wires to a conductive or non-static polyvinyl chloride resin sheet or flat plate in the vertical or horizontal direction, or in the vertical or horizontal direction.
A polyvinyl chloride resin sheet or flat plate according to claim 3, which is embedded in both horizontal directions. (6) Polyvinyl chloride, vinylidene chloride-vinyl chloride copolymer resin, graft copolymer resin of ethylene-vinyl ester copolymer resin and vinyl chloride, or graft copolymer resin of polyurethane resin and vinyl chloride, ethylene-vinyl chloride copolymer resin Patent claims for polymer resins, vinyl ester-vinyl chloride copolymer resins, blends of ethylene-vinyl acetate copolymer resins and polyvinyl chloride, each alone or a blend of at least two or more resins as sheet or flat plate materials A polyvinyl chloride resin sheet or flat plate according to any one of items 1 to 3.