JPH0142291B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a vinyl chloride-based hard sheet or film. More specifically, the tensile strength
400Kg/cm2 or ^more , the height of the surface unevenness is 1μ
The purpose of the present invention is to provide a vinyl chloride-based hard erasable sheet or film which is controlled to a thickness of ~45μ, has excellent tactility and decorative properties, and has good thermal stability. Vinyl chloride resin is widely used in various fields because it is inexpensive, easy to process, and has excellent physical properties. However, in recent years, there has been a tendency to dislike the plastic luster of vinyl chloride resin molded products, and molded products with uneven surfaces to eliminate the rips have come to be preferred. Particularly in the field of calendar sheets, there is a strong demand for erasable surfaces, and erasable sheets have been produced using acrylic coating, embossing, and the use of large amounts of fillers. However, acrylic painting has the disadvantages of high painting costs and high product costs, and embossing requires installing a grain roll, and as the grain wears out, the grain roll must be replaced one after another. The drawback was that the cost was high and the product cost was high. Furthermore, when a large amount of filler is used, it is easy to cause unevenness in the enamel state, resulting in a high defect rate and lower productivity, and it is difficult to increase the tensile strength to a level that does not cause any practical problems, that is, 400 kg/cm ² or more. It was difficult. There have also been reports of hard sheets made from cross-linked vinyl chloride resin, but cross-linked vinyl chloride copolymers have a high melting temperature, which increases the processing temperature, making the resin more likely to burn, and sometimes causing damage to calender rolls. Such phenomena occurred, and it was not possible to put it into practical use industrially. In view of this situation, the present inventors conducted extensive research and found that 3 to 80 parts by weight of a crosslinked vinyl chloride copolymer crosslinked with bisphenol A-modified diacrylate, and vinyl chloride resin or vinyl chloride copolymer. If a resin composition containing a resin composition consisting of 97 to 20 parts by weight of a polymer is used as an essential component, it can be processed without impairing processability such as an increase in melting temperature, and has a thickness of 0.01 to 1.5 mm and a high tensile strength. The inventor discovered that it is easy to maintain 400Kg/cm ^{2 or more of 400Kg/cm 2 or} more, and invented the hard erasable sheet or film of the present invention in which the height of the surface unevenness is controlled to 1 to 45μ. . The sheet or film referred to in the present invention is for vehicles,
It is used for various parts that require special faded patterns in the fields of packaging containers, gardening, building materials, toys, stationery, lighting, clothing, etc. When used for a specific purpose, sheets or films may be punched out with a frame mold and used as molds, but they may also be made into various parts through secondary processing such as vacuum forming. It may also be used by laminating it to materials such as plastic, wood, metal, and inorganic materials such as plasterboard. The sheet or film of the present invention is manufactured by the calender roll method normally used for processing vinyl chloride resin, but it can also be produced by inflation molding,
It is also easy to manufacture using extrusion techniques such as T-die extrusion molding. When manufacturing the sheet or film of the present invention, a plasticizer of 25 parts by weight or less may be used for the purpose of improving processability, but if more than 25 parts by weight is used, the hard sheet of the present invention will become soft. Otherwise, it becomes impossible to produce the film and physical properties such as tensile strength are impaired. In order to improve processability, it is particularly good to blend the plasticizer with the crosslinked vinyl chloride copolymer in advance and then blend the vinyl chloride resin therein. In the present invention, various heat stabilizers, lubricants, fillers, reinforcing agents, ultraviolet absorbers, antioxidants, pigments, and processing aids used when processing vinyl chloride resins and vinyl chloride copolymers are used. etc. can be added freely depending on the purpose of use of the sheet film,
Thermoplastic resins such as chlorinated polyethylene, ethylene-vinyl acetate copolymer, ABS resin, AS resin, MBS resin, urethane resin, acrylic resin, or rubber such as NBR, CR, and EPR may be added. However, if the amount of these additives used is too large, physical properties such as tensile strength will be impaired, so it is preferably 20 parts by weight or less per 100 parts by weight of the resin composition used in the present invention. The crosslinked vinyl chloride copolymer used in the present invention can be easily obtained by polymerizing vinyl chloride using bisphenol A-modified diacrylate as a crosslinking agent. If the amount of such a crosslinked vinyl chloride copolymer used in the sheet or film of the present invention is too large, the tensile strength will drop significantly, making it impossible to increase the tensile strength to 400 kg/cm ² or more.
Moreover, the height of the peaks of the surface irregularities exceeds 45μ, which is not preferable. Also, if the amount is too small, the elimination effect will be poor.
Moreover, the height of the peaks of the surface irregularities is less than 1 μm, which is not preferable. Therefore, in the present invention, the crosslinked vinyl chloride copolymer is used in an amount of 3 to 80 parts by weight, and the vinyl chloride resin or vinyl chloride copolymer is used in an amount of 97 to 20 parts by weight. Vinyl chloride copolymers include ethylene-vinyl chloride copolymers, propylene-vinyl chloride copolymers, vinyl acetate-vinyl chloride copolymers, copolymers of alkyl acrylate and vinyl chloride, and copolymers of alkyl vinyl ether and vinyl chloride. One or more copolymers may be used, and ethylene-vinyl chloride copolymers and vinyl acetate-vinyl chloride copolymers are particularly preferred from the viewpoint of processability and production cost. Vinyl chloride resin is a polymer of vinyl chloride alone, and any commonly used resin may be used, but it is particularly preferable that the average degree of polymerization is
Something between 400 and 1300 is good. As mentioned above, the hard elideable sheet or film of the present invention has a tensile strength of 400 kg/cm ² or more, the height of the surface unevenness is controlled to 1 μ to 45 μ, and has excellent tactility, decorative properties, etc. Therefore, it is extremely valuable in practical terms. In addition, the manufacturing method can use the equipment used for manufacturing vinyl chloride hard sheets and films as is, and has good productivity. Next, embodiments of the present invention will be described in more detail in Examples, but these are not intended to limit the scope of the present invention in any way. Note that the measurements were performed as follows. (1) Tensile strength: From the sheet in accordance with JIS-K6734
JIS No. 1 dumbbells were punched out and tested using a tensile testing machine. The tensile speed was 50 mm/min. (2) Height of surface unevenness: Measured using a surface roughness meter DEKTAK manufactured by Japan Vacuum Technology KK. (3) Blackening time: The sheet was placed in a gear oven controlled at 200°C and taken out every 15 minutes to determine the time until it turned black. (4) Preparation of sheet: A resin compound prepared according to the formulation shown in Table 1 was put into a roll controlled at 180°C and kneaded for 5 minutes to obtain a sheet with a thickness of 0.4 mm. This sheet was subjected to various tests. (5) Crosslinked vinyl chloride copolymer (): 200 parts of ion-exchanged water, 0.2 parts of partially saponified polyvinyl acetate, 0.03 parts of azobisisobutyronitrile, 2.0 parts of bisphenol A-modified diacrylate, 100 parts of vinyl chloride.
A portion of the mixture was charged into a reactor and polymerized for 10 hours to obtain a crosslinked vinyl chloride copolymer. This was used in Examples 1-6. Crosslinked vinyl chloride copolymer (): Ion exchange water
200 parts, partially saponified polyvinyl acetate 0.2 part, azobisisobutyronitrile 0.03 part, diallyl phthalate
0.5 parts of vinyl chloride and 100 parts of vinyl chloride were charged into a reactor and polymerized for 10 hours to obtain a crosslinked vinyl chloride copolymer. This was used in Reference Example 1. Crosslinked vinyl chloride copolymer (): Ion exchange water
200 parts of partially saponified polyvinyl acetate, 0.2 parts of azobisisobutyronitrile, 2.0 parts of tetraethylene glycol diacrylate, and 100 parts of vinyl chloride were charged into a reactor and polymerized for 10 hours to form a crosslinked vinyl chloride copolymer. I got it. This was used in Reference Example 2. The results are shown in Table-1 and Table-2.

【table】

[Table] As can be seen from Table 2, each example is Comparative Example 1,
Compared to 2, 3, and 4, the height of the surface unevenness is
It is controlled to 1 μ to 45 μ, and Comparative Example 1,
Compared to Comparative Examples 2 and 4, the extinguishing state is better. or,
A comparison of Examples 2, 7, and 8 shows that when a crosslinked vinyl chloride copolymer using bisphenol A-modified diacrylate as a crosslinking agent was used, the thermal stability was better than in other cases. I understand.

Claims (1)

[Scope of Claims] 1. 3 to 80 parts by weight of a crosslinked vinyl chloride copolymer crosslinked with bisphenol A-modified diacrylate, and 97 to 80 parts by weight of a vinyl chloride resin or a vinyl chloride copolymer.
A resin composition having a resin composition of 20 parts by weight as an essential component is calendered or extruded, and the thickness is 0.01 to 1.5 mm, and the tensile strength is 400 mm.
Kg/cm ² or more of vinyl chloride-based rigid sheet or film. 2. The sheet or film according to claim 1, wherein the height of the ridges of the surface irregularities is 1 μ to 45 μ.