JPH0446923Y2 - - Google Patents

Description

[Detailed explanation of the invention] (Industrial application field) This invention is used for packaging bags for spare tires of automobiles and other vehicles using rubber tires, for furniture with casters used in general homes and store exhibition areas, and for covering casters such as display stands. Related to decorative sheets for packaging that come into direct contact with rubber products such as shoes. (Prior art and problems) Conventional soft polyvinyl chloride sheets or leather have advantages such as vivid coloring, durability, and water resistance, so they are used for chairs, bags, automobile interior materials, and other walls. It is widely used as an interior material, and by taking advantage of its advantages, it is used as a cover for automobile spare tires and as a cover for casters attached to furniture and display equipment to enhance interior and exterior effects. However, while the above-mentioned soft polyvinyl chloride sheet or leather has excellent advantages as mentioned above, it cannot be used from the back side for decorative sheets such as spare tire covers and caster shoes that are in contact with rubber products from the back side. The dirt stains the surface of the polyvinyl chloride layer constituting the surface decorative layer in a black to brownish color, making it unsightly and significantly reducing the decorative effect. However, rubber products that do not cause such contamination No sheet for covering products is available on the market at the time of this application. Therefore, in the past, only a limited number of colors were available, such as low-brightness grayish brown, dark red, and black, in which this contamination was not noticeable, and the range of choices for colors, patterns, etc. was narrow. The cause of this contamination is the anti-aging agents added to rubber products, and the main anti-aging agents are amines and their derivatives, which are caused by primary amines, secondary amines, and amine-aldehyde reactions. thing,
There are amine-ketone reactants, amine-phenol reactants, etc., and these anti-aging agents migrate from the back side of the polyvinyl chloride sheet or leather that comes into contact with the rubber product, and further penetrate into the surface. However, anti-aging agents have the property of changing color from black to dark brown in the atmosphere. Therefore, it is known that the surface of the soft vinyl chloride sheet or leather tire cover becomes discolored and contaminated. Conventionally, urethane sponge and aluminum foil were pasted on the back side of soft polyvinyl chloride sheet or leather to prevent the migration of anti-aging agents, or colored non-woven fabric was used instead of soft polyvinyl chloride leather, or black soft polyvinyl chloride was used. As a countermeasure, they used vinyl chloride leather. However, there were problems such as high cost and lack of freedom in color and decoration. On the other hand, the applicant's company found that the ethylene-vinyl alcohol copolymer film had an excellent effect of preventing the penetration of the anti-aging agent from penetration, but when this film leaked into water, the effect was found to be excellent. It was found that the death toll was significantly reduced, and it was also found that it could not be used as is. (Problem to be solved) This invention proposes that even if the rubber products mentioned above are coated, the rubber anti-aging agent contained therein will not penetrate to the surface, and even if used in particularly moist conditions, the anti-aging agent will not be able to penetrate the surface. The purpose is to prevent the agent from penetrating and to prevent the decorative surface of the decorative surface layer from being contaminated, and the purpose is to provide the market with a decorative sheet for covering rubber products that satisfies these points. (Technical means to solve the problem) This invention has a surface decorative layer made of soft polyvinyl chloride,
The middle layer is an ethylene-vinyl alcohol copolymer,
This is a decorative sheet for covering rubber products, characterized in that a synthetic resin layer made of polyvinyl alcohol is laminated and integrated with a soft polyvinyl chloride layer on the back side. (How to use) To use this device constructed as described above, the surface decorative layer is used as the front surface and the opposite back surface is in contact with the rubber product. For example, when used as a cover for a spare tire or a shoe for a caster, the outer side is used as a decorative surface layer. (Effects) In this device constructed and used as described above, the back surface as a water-resistant protective layer comes into contact with the rubber product directly or through the backing base fabric, and is not contaminated by the anti-aging agent in the rubber product. However, since the above-mentioned anti-aging agent does not penetrate into the ethylene-vinyl alcohol copolymer etc. of the intermediate layer, the surface decorative layer is not contaminated by the anti-aging agent at all and maintains clear color and brightness for a long time. Hold. Furthermore, although the mechanism by which the polyvinyl alcohol or ethylene-vinyl alcohol resin layer described above prevents contamination due to the discoloration caused by the rubber anti-aging agent is not clear, the polyvinyl alcohol or vinyl alcohol among the constituent materials of the copolymer is not clear. While water and steam can easily penetrate, organic solvents,
Excellent barrier properties against organic compounds (e.g. amines) and gases. Furthermore, even if the rubber product or the sheet of this invention gets wet from rainwater or cleaning water, both the front and back layers of the sheet are covered with a polyvinyl chloride layer that has excellent water-blocking properties. , the intermediate copolymer, etc. are not exposed to a high moisture atmosphere. Therefore, even if the cover of a car spare tire or the shoe of a caster gets wet, both the front and back sides are covered with a soft polyvinyl chloride layer, so moisture is blocked by this layer, and the polyvinyl chloride layer on the back side is covered with a soft polyvinyl chloride layer. Even if the anti-aging agent penetrates through and reaches the interface between this and the intermediate layer, moisture is not supplied to this intermediate layer, so the anti-aging agent does not penetrate through this intermediate layer. The soft polyvinyl chloride layer that is the surface layer of this sheet is completely inhibited and can withstand long-term use without being contaminated by the rubber anti-aging agent. It can be widely used as a surface covering material for conventional rubber products, such as a surface covering material for rubber molded products. (Example) This invention will now be explained based on a typical example. Example 1 (See Figure 1) Reference numeral 10 denotes a surface decorative layer made of a soft polyvinyl chloride layer with a thickness of 0.2 mm to 2 mm, and an intermediate layer 11 made of ethylene-vinyl alcohol with a thickness of 4 μ to 20 μ (microns). A polymer layer 11 is formed, and a soft polyvinyl chloride layer 12 on the back side is formed with a thickness of 0.1 mm to 0.2 mm, and in some cases, a backing base fabric 13 such as a plain woven fabric or knitted fabric is laminated. It is formed in one piece. An example of a method for manufacturing these sheets is to coat one side of the film of the ethylene-vinyl alcohol copolymer layer 11 with a 30 g/m ^secondary adhesive (AD527 manufactured by Toyo Morton Co., Ltd.) 14, and then print a pattern on it. A soft polyvinyl chloride film 10 for the surface decorative layer with a thickness of 0.2 mm is laminated with 100
After passing through heated rolls at a temperature of 50°C, they are held and brought into close contact by a holding roll whose surface temperature is 50°C or less. Next, the back surface of the ethylene-vinyl alcohol copolymer film 11 is coated with an adhesive 15 made of the same material by the same method, and a plain soft polyvinyl chloride film 12 is laminated thereon. Immediately after applying approximately 15 g/m ² adhesive (manufactured by Kanebuchi Chemical Co., Ltd., Karabikku, L-H) 17 to the backing base fabric 13, the back sides of the laminated sheets were overlapped and heated to 130°C. The backing base fabric 13 is pressed onto the circumferential surface of the heating drum, the adhesive is dried, and the resin of the entire sheet is heated, and the sheet separated from the heating drum is further heated from the surface side with an infrared heater. At least 10 soft polyvinyl chloride layers
is softened, a squeeze roll is applied to the surface of the soft polyvinyl chloride layer 10, and a back-up roll is applied to the side of the backing base fabric 13 and pressed to form an appropriate squeeze pattern 1 on the sheet surface.
6. How to use Embodiment 1 To use Embodiment 1 constructed as described above, use it so that the backing base fabric 13 is in contact with the rubber product. Effects of Example 1 In addition to achieving the effects of this invention, there are other benefits as well.
Since the backing base fabric 13 is attached to the back side, the rubber product hardly comes into direct contact with the soft polyvinyl chloride resin layer 12 on the back side, so the penetration of the anti-aging agent is reduced and there is no contamination of the surface. be. Example 2 (See Figure 2) The front decorative layer 10 and the soft polyvinyl chloride layer 12 on the back side of Example 1 were made into foam layers, and there was no other difference from Example 1, and the same reference numerals are used. are the same constituent parts and have the same functions and effects. The foam layer may be one of the decorative layer 10 and the soft polyvinyl chloride layer 12 on the back surface. The ethylene-vinyl alcohol copolymer 11 in Examples 1 and 2 described above was produced by first making a copolymer of ethylene and vinyl acetate, and then replacing the acetate groups with alcohol groups, so that the ethylene-vinyl alcohol copolymer 11 was completely produced. In this specification, even if the resin does not form an ethylene-vinyl alcohol copolymer and some acetate groups remain, and the resin is in a state like an ethylene-vinyl alcohol-vinyl acetate terpolymer, shall fall within the scope of ethylene-vinyl alcohol copolymers. Example 3 The intermediate layer 11 of Example 1 was made of polyvinyl alcohol instead of the ethylene-vinyl alcohol copolymer, but the other components were the same as those of Example 1. The method of use is the same as in Example 1. Effects of Example 3 Also in this example, the polyvinyl alcohol of the intermediate layer 11 is a single layer, and the aforementioned anti-aging agent for rubber does not permeate in a dry state, but polyvinyl alcohol is hydrophilic and when wet with water. On the other hand, the anti-aging agent also dissolves in water, and there is a risk that it will penetrate and penetrate the water-swollen polyvinyl alcohol mentioned above, but the back side is also coated with a waterproof protective layer of soft polyvinyl chloride to block moisture. Therefore, the third embodiment also has the same effect as the first embodiment. Experimental Example Next, the results of a comparative test between Example 1, which is a representative example of the present invention, and a conventional product will be explained. (1) Test method In order to set the tested leather in the Sunshine weather meter, cut the leather, which is a type of decorative sheet from Example 1, into a size of 6.5 x 16 cm, and cut an unused motorcycle tire into a 4 x 6 cm size. Cut it to size, place it on the base material side (back side) of this leather, then place a stainless steel wire mesh cut to a size of 6.5 x 16 cm on top of it, wrap the tire and sandwich it, and connect the leather and wire mesh with a needle and thread. sew together. The leather surface side of this sample was irradiated with ultraviolet rays for 300 hours at 83°C using a sunshine weather meter (see Figure 3). After the condition of no shower application and the condition of shower application, the leather was taken out, the surface was wiped with a dry cloth, and the state of contamination on the leather surface was visually determined. (2) Sample Invented product No. 1 No. 2 No. 1 with the same structure and material as those shown in Example 1, with the intermediate layer 11 made of ethylene-vinyl alcohol copolymer having a thickness of 15 μm Comparative product (conventional product) with the structure of No. 1 excluding the soft polyvinyl chloride layer 12 of the waterproof protective layer on the back side No. 3 Intermediate layer 11 of ethylene-vinyl alcohol copolymer in the structure of No. 1 and adhesive Excluding layers 14 and 15 (3) Judgment Criteria Grade 1... Tire marks remain extremely black Grade 2... Tire marks are quite noticeable Grade 3... Tire marks are easily recognizable Grade 4... ...Status where contamination is slightly discernible Grade 5...Status where there is no contamination at all (4) Test results [Table]

[Brief explanation of the drawing]

The figures relate to this invention: Fig. 1 is an enlarged longitudinal cross-sectional view of Example 1, Fig. 2 is an enlarged longitudinal cross-sectional view of Example 2, and Fig. 3 shows the test piece and rubber product used in the experimental example. It is a longitudinal side view showing a state. In the figure, numerals 10... surface decorative layer (soft polyvinyl chloride layer), 11... intermediate layer (ethylene-vinyl alcohol copolymer), 12... soft polyvinyl chloride layer.

Claims (1)

[Scope of Claim for Utility Model Registration] 1 Laminated with a front decorative layer as a soft polyvinyl chloride layer, an intermediate layer as a synthetic resin layer of ethylene-vinyl alcohol copolymer or polyvinyl alcohol, and a back surface as a soft polyvinyl chloride layer. 1. A decorative sheet for covering rubber products, characterized in that the sheet is integrated with a rubber product. 2. The decorative sheet for covering rubber products according to claim 1, wherein the decorative sheet is sewnable. 3. The decorative sheet for covering a rubber product according to claim 1, wherein the integration of the layers is achieved by adhesion using an adhesive.