JPH01318658A - Durable floor material - Google Patents

Abstract

PURPOSE:To obtain a wear-resisting floor material with a electrical high conductivity and high heat-resistivity by layering a layered sheet made by boding a conductive bridging polyvinyl chloride layer and a conductive non-bridging layer, an intermediate layer containing conductive carbon and a dimensional stability base cloth. CONSTITUTION:A conductive bridging polyvinyl chloride paste resin layer 1 containing a white or hypochrome conductive metal oxide (stannic oxide or the like) 4 and a conductive fiber (stainless steel fiber or the like) 5 and a conductive non-bridging polyvinyl chloride resin layer 2 are bonded together and thereby a layered sheet 3 is formed. A conductive intermediate layer 6 containing conductive carbon 7 and dimensional stability mesh-shaped base cloth 8 made from glass nonwoven fabric or the like are layered in a layer and, at the same time, the layered sheet 3, the intermediate layer 6 and the base cloth 8 are press-fitted together to form a layer. With such structure, a floor material with high heat-resistivity and high durability, capable of releasing positively static electricity generated on the floor surface, can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention provides a durable flooring material that actively releases static electricity generated on the floor surface to the outside of the system.

(Prior art) Conventionally, operating rooms, IC factories, chemical manufacturing factories, chemical laboratories, combustible material warehouses, etc. have required flooring materials with durability, wear resistance, and solvent resistance, as well as measures against static electricity hazards. was.

Although a manufacturing method for a durable flooring material has been disclosed in JP-A-58-183254, no flooring material with sufficient durability and high conductivity has been known so far.

(Problems to be Solved by the Present Invention) An object of the present invention is to provide a durable conductive flooring material that actively provides an escape route for static electricity in addition to heat resistance, abrasion resistance, and solvent resistance.

(Structure of the Invention) □The present invention is constructed for the above-mentioned purpose, and comprises a white or light-colored conductive metal oxide that is colored and concealed with a pigment, crosslinked with a crosslinking agent, or a combination of the oxide and a conductive fiber. A laminated sheet consisting of an opaque high-density thermally crosslinked conductive polyvinyl chloride paste resin surface layer and a conductive non-crosslinked polyvinyl chloride resin layer, a conductive intermediate layer containing conductive carbon, and a dimensionally stable base fabric. The gist is a durable flooring material characterized by being laminated with.

The present invention will be explained below based on the drawings.

FIG. 1 is a cross-sectional view of the durable flooring material of the present invention.

1 is a crosslinked conductive PvC paste resin layer (hereinafter referred to as crosslinked 270
2 is a conductive non-crosslinked resin layer (hereinafter referred to as a non-crosslinked layer).

The crosslinked PVC layer 1 and the non-crosslinked layer 2 are firmly adhered to form a laminated sheet 3.

The conductive crosslinked PVC layer 1 is made by blending 30 to 100 parts by weight of a plasticizer with 100 parts by weight of PvC paste resin, and further coloring with a pigment, and adding 0.5 to 0.5 to 100% of dimercaptothiadiazole, dithiol-S-triazine derivative, etc. as a crosslinking agent. 5 parts by weight are blended, and other crosslinking aids such as strong basic amines, heat stabilizers, etc. are blended, and the mixture is heated at 150 to 250°C for 2 to 5 minutes.

The resulting crosslinked resin layer is crosslinked to a higher crosslinking density than the transparent crosslinked PvC resin that has conventionally been used as a flooring surface layer.

The pigment is added to the extent that it colors the PVC paste layer and hides the base layer.

The white or light-colored conductive metal oxides added to the crosslinked 270 layer of the laminate sheet of the present invention include conductive zinc oxide, conductive titanium oxide, conductive tin oxide, and conductive antimony oxide. Conductive tin oxide and conductive titanium oxide are preferred.

Conductive tin oxide (a) Tin oxide (hereinafter referred to as S n O2) powder is white and has conductivity, but it also contains antimony (
When Sb) is contained, the conductivity is further improved.

It must also be thermally stable. and (b) In order to prevent the transparency and color tone of the pigment from being impaired even when the powder is mixed, it is necessary to satisfy that the powder to be mixed does not absorb light, that is, has a white color. The conductive fine powder is prepared by mixing tin chloride (hereinafter referred to as 5nC1) and antimony chloride (hereinafter referred to as 5bC1) in one or a mixture of alcohol, hydrochloric acid aqueous solution, and acetone.
A solution consisting of a solution of

It can be produced by adding sb gold-containing Sn○ to precipitated water in heated water, or by firing SnO2 powder and sb compound, or by mixing Sn compound and sb compound and then firing. It is manufactured by a known method such as the method.

Further, conductive titanium oxide can be obtained, for example, by combining the conductive tin and titanium oxide.

The conductive metal oxide obtained above has an average particle size of 0.05 to 1.0 μm and is preferably added in an amount of 20 to 100 parts by weight per 100 parts by weight of the crosslinked PVC resin.

Furthermore, conductive performance is improved by adding conductive fibers onto the PvC crosslinked surface layer.

These conductive fibers are preferably white or light colored, but other conductive fibers may also be used.

Examples of conductive fibers include stainless steel fibers, conductive titanium oxide fibers, conductive antimony-containing fibers, metal-coated glass fibers and synthetic fibers such as polyester, glass fibers coated with conductive metal oxides such as nickel oxide, etc. Examples include synthetic fibers, indium oxide vapor-deposited fibers, fibers bonded with metal sulfides such as cadmium sulfide and copper sulfide (e.g. Thunderon, manufactured by Nippon Yoke Dose Co., Ltd.), and 0.2 to 5.0 m is suitable. 0.1 to 1 fiber per 100 parts by weight of PVC
It is desirable to add 5 parts by weight. By using the above-mentioned conductive metal oxide alone or in combination with the above-mentioned conductive fiber.

Since the surface layer does not darken, excellent conductivity can be obtained without damaging the original color of the surface layer.

The non-crosslinked layer 2 is formed of a synthetic resin such as PVC, and the crosslinked Pv
Both the C paste layer 1 and the intermediate resin layer 4 described below must have good adhesion. The non-crosslinked layer 2 can be formed by, for example, a method of pregelling a non-crosslinked PvC paste or a method of pregelling a non-crosslinked PvC paste.
obtained by calendering. The above-mentioned crosslinkable PVC paste solution is applied onto the obtained non-crosslinked layer and crosslinked by heating.

In this way, the laminated sheet 3 is obtained.

For example, the non-crosslinked layer may be made conductive by appropriately adding the above-mentioned white or light-colored conductive metal oxide 4, conductive fiber 5, conductive carbon black, conductive surfactant, or other conductive substance to the thermoplastic resin. Give.

The laminated sheet 3 must have sufficient flexibility. The laminated sheet 3 thus obtained has heat resistance, solvent resistance,
Highly wear-resistant, durable and conductive. The obtained laminated sheet is laminated onto a conductive intermediate M6 (hereinafter referred to as intermediate layer) by a calendering method or an extrusion method. The middle layer has fillers such as calcium carbonate, talc, and chalk in PVC.
100 to 500 parts by weight are blended to 100 parts by weight,
For the intermediate layer, the surface layer and the dimensionally stable base fabric are simultaneously bonded by thermocompression bonding, and the flooring material of the present invention can be laminated with high efficiency without the need for any other adhesive or the like.

10 to 50 parts of conductive carbon particles 71, such as Ketchen Black, are added to the intermediate layer based on 100 parts by weight of PvC resin, thereby imparting good conductivity.

The intermediate layer can contain a large amount of filler, which not only allows the product to be supplied at a low price, but also improves thermal conductivity, which can contribute to improving the heat resistance of the floor material surface.

The combination of the conductive laminated sheet 3 and the conductive intermediate layer 6 allows static electricity generated on the layer to be actively dissipated.

The dimensionally stable base fabric used in the present invention is preferably glass nonwoven fabric, glass net, linen cloth, polyester cloth, a mixed fabric thereof, or cheesecloth. A particularly preferable base fabric is a mesh-like base fabric, and the gap between the mesh Since the intermediate layer is exposed, a particularly effective conductive effect can be obtained.

Regarding the dimensionally stable base fabric, it is important to ensure the safety of the floor surface in places where accidents may occur during daily work such as factory floors, so the use of the stable base fabric in the present invention is important. This eliminates the problems of flooring, blistering, and curling, and increases the safety of factory floors.

The durable flooring material 9 of the present invention complies with the NFPA99 standard, and exhibits excellent electrical conductivity with both surface resistance and volume resistivity ranging from lXl0' to 1×10''Ω. Contains white or light-colored conductive metal oxides or metal fibers, so it maintains its fashionability while maintaining chemical resistance, abrasion resistance, and heat resistance 1 without impairing the original color of the surface material.
Significant electrical conductivity as well as dimensional stability are obtained.

The flooring material of the present invention exhibits excellent electrical conductivity by itself, but even better electrical conductivity can be obtained by laminating mesh-like base fabrics and applying them to the floor base using a conductive adhesive.

Figure 2 is a diagram of the manufacturing process of the flooring material of the present invention, in which the above-mentioned conductive titanium oxide, conductive zinc oxide, conductive tin oxide, and other white or light-colored conductive substances and metal fibers are blended into the PvC paste. , further colored with a pigment, blended with 0.5 to 5 parts by weight of dimercaptothiadiazole, dithiol-s-triazine derivatives, etc. as a crosslinking agent, and blended with other crosslinking aids such as strong basic amines, heat stabilizers, etc. 150-250℃
Heat for 2 to 5 minutes. The obtained crosslinked resin layer is crosslinked to an extent that the crosslinking density is higher than that of the transparent crosslinked PvC resin layer that has been conventionally used as a floor material surface layer.

The pigment is added to the extent that it colors the PvC paste layer and hides the base layer.

The non-crosslinked layer 2 is made of synthetic resin such as PVC, and the crosslinked layer 27
Both the layer 0 and the intermediate resin layer 6 described below must have good adhesion.

The non-crosslinked resin layer 2 can be obtained, for example, by pregelling a non-crosslinked PVC paste or by calendering PVc. The above-mentioned crosslinkable PVC paste solution is applied onto the obtained non-crosslinked layer and crosslinked by heating. In this way, the laminated sheet 3 is obtained. The laminated sheet 3 must have sufficient flexibility. The crosslinked PVc layer 1 of the obtained laminated sheet 3 has high heat resistance and solvent resistance. The highly crosslinked layer 1 is colored with a pigment that has a hiding power and is opaque, so even if the crosslinking density is increased above the transparent surface layer of the conventional PVC crosslinked flooring material that has tobacco resistance, discoloration due to heating is observed. figure,
It has a desirable appearance as a flooring material, and no whitening is observed even when moisture is attached.

It is not affected by the color of the base of the non-crosslinked layer 2.

The non-crosslinked layer 2 firmly adheres the crosslinked FJVC layer 1 and the conductive intermediate resin layer (hereinafter referred to as intermediate layer) 6.

In the present invention, the conductive metal oxides, conductive fibers, and other conductive substances described above are appropriately added to the non-crosslinked layer to impart conductivity.

When the obtained laminated sheet 3 passes through the pressure rolls 11, 11', the intermediate layer 6 extruded from the extruder 10, for example, is pressed against the intermediate layer by residual heat while the intermediate layer 6 is not cooled.

At this time, the intermediate layer is extruded at 160 to 190 DEG C. and uniformly formed to a desired thickness, usually 0.5 to 3 nn.

Further, while the extruded resin layer 4 is not cooled, the dimensionally stable base fabric 8 is also applied to the laminated sheet 3 by the pressure roll 7' due to residual heat.
are crimped almost simultaneously.

In the present invention, the laminated sheet 3 and the intermediate layer 6 may be laminated using a calender.

By the manufacturing method of the present invention, a floor material 9 having excellent conductivity can be obtained with high efficiency.

Moreover, since the surface layer is a white or light-colored conductive metal powder or metal fiber, the surface does not become black as in the case of carbon black, and the fashionability is maintained.

The cross-linked resin layer of the present invention is 50% of that of conventional tobacco-resistant natural flooring materials.
It is desirable to have a crosslinking density higher than or equal to that of transparent Pv
When C-paste oil is cross-linked by heating to this extent, thermal discoloration will inevitably occur, but if it is colored with pigments and made opaque, the discoloration caused by heating will be hidden, and unlike conventional tobacco-resistant natural flooring materials, it will not whiten due to water absorption. Does not occur. Furthermore, the colored crosslinked resin of the present application has good heat resistance, solvent resistance, and chemical resistance, and exhibits excellent durability.

The non-crosslinked portion of the surface layer is in close contact with the crosslinked resin layer and exhibits good conductivity, and the non-crosslinked layer blends well with the intermediate layer when thermocompression bonding the surface layer and the intermediate layer. and the extruded resin layer to ensure strong adhesion.

Regarding the dimensionally stable base fabric 8, it is important that safety is ensured on the floor surface in places where accidents may occur during daily work such as factory floors, and the stable base fabric is used in the present invention. This eliminates the problems of flooring, blistering, and curling up, increasing the safety of factory floors.

In particular, a base fabric with large gaps such as a mesh is preferable because the conductive intermediate layer is exposed and even better conductivity can be obtained.

With the above-described configuration, the present application can efficiently manufacture a flooring material with high performance conductivity and durability that cannot be obtained by conventional flooring manufacturing methods.

(Effects of the invention) ■In the present invention, by combining a conductive laminated sheet and a conductive intermediate layer, the best electrical resistance values are a surface resistance of 4 x 10'Q and a volume resistance of 3 x 10 sΩ. A positive conductive effect can be obtained through the upper and lower conductive layers.

■Since white or light-colored conductive metal oxides and metal fibers are used in the surface crosslinking layer, there are no drawbacks such as darkening of the surface of the flooring material, and the design can be freely exhibited.

- The present invention not only provides excellent electrical conductivity, but also has excellent chemical resistance, heat resistance, abrasion resistance, and fashionability. A flooring material that simultaneously has these characteristics can be obtained.

■Even with a relatively small amount of expensive conductive powder or conductive fibers, remarkable conductivity effects can be obtained.

Example A PVC conductive non-crosslinked sheet of Formulation A was formed on a thin sheet, and a crosslinked PVC paste of Formulation B was applied to a thickness of 0.5 mm on this non-crosslinked sheet, and crosslinked by heating at 220°C for 2 minutes. A laminated sheet was obtained. The obtained laminated sheet was peeled off from the release sheet.

*2 l,8-diazabicyclo(5,4,0)-undecene-7 18% of the conductive intermediate layer of compound C was added to this laminated sheet.
The mixture was kneaded at 0°C and extruded to a thickness of 1.5 mm.

Through this intermediate resin layer, the above laminated sheet and a dimensionally stable base fabric of a mesh-like woven fabric of polyester and hemp were simultaneously pressed with a pressure roll using residual heat to obtain a durable flooring material of the present invention.

The flooring material of the present invention exhibited the performance shown in Table 1. however,
The surface resistance was determined by placing 30 NFPA99 electrodes on the flooring material and measuring the resistance between the electrodes, and measuring the volume resistance by placing the flooring material on top and bottom with the same electrodes and measuring the resistance between them.

Comparative Example 1 Conductive titanium oxide and metal-coated glass fiber were removed from Formulation A of Example 1, and conductive titanium oxide was removed from Formulation B.
In addition, a flooring material was produced in the same manner as in Example 1 using a formulation in which the antistatic plasticizer was changed to ordinary DOP and Ketchen Black was removed from formulation C.

Comparative Example 2 An antistatic agent was added to the PVC composition of the surface layer of a conventional PvC sheet flooring material and kneaded to obtain a conductive flooring material.

Obtained Comparative Example 1. Comparative Example 2 was tested under the same conditions as the Example. The results are shown in Table 1.

Compared to the flooring material of the present invention, the conventional durable flooring material of Comparative Example 1 had high surface resistance and volume resistivity and low conductivity.

Moreover, the conductivity of Comparative Example Y was low even when compared with the product of the present invention, and in particular, the heat resistance and abrasion resistance were low.

[Brief explanation of the drawing]

FIG. 1 is a sectional view of the durable flooring material of the present invention, and FIG. 2 is a diagram showing the manufacturing process of the flooring material. 2 is a conductive crosslinked layer with 270 layers, 2 is a conductive non-crosslinked layer, 3 is a laminated sheet, 6 is a conductive intermediate layer, and 8 is a dimensionally stable base fabric. Written amendment to the above procedures (voluntary) 1. Indication of the case 1986 Patent application No. 1497382, Name of the invention Durable flooring material3, Person making the amendment Relationship to the case Patent applicant Higashia Rioca 5-125 Tsukaarioka, Itami City Toyo Toyo Linoleum Co., Ltd.4 , date of amendment order: 5, number of claims increased by amendment 6, content of amendment subject to amendment 1, "Low profit" on page 16, line 9 of the specification changed to "releasability"
I will correct it. 2. The row of Comparative Example 1 in Table 1 on page 19 of the specification will be corrected as follows. that's all

Claims (1)

[Claims] 1. Color concealed with a pigment and crosslinked with a crosslinking agent,
and consists of a white or light-colored conductive metal oxide, or an opaque high-density thermally crosslinked conductive polyvinyl chloride paste resin surface layer containing the oxide and conductive fibers, and a conductive non-crosslinked polyvinyl chloride resin layer. A durable flooring material comprising a laminated sheet, a conductive intermediate layer containing conductive carbon, and a dimensionally stable base fabric. 2. The durability according to claim 1, wherein the white or light-colored conductive metal oxide is at least one of conductive zinc oxide, conductive titanium oxide, conductive tin oxide, and conductive antimony oxide. sexual flooring. 3. As conductive fibers, stainless steel fibers, conductive titanium oxide fibers, conductive antimony-containing fibers, metal-coated glass fibers, metal-coated synthetic fibers, metal oxide-coated glass fibers, metal oxide The durable flooring material of claim 1, wherein the durable flooring material is at least one of a synthetic fiber coated with a compound and a fiber bonded with a metal sulfide. 4. The durable flooring material according to claim 1, wherein the dimensionally stable base fabric is in the form of a mesh.