JPH072406B2 - Vinyl chloride resin laminated sheet for vacuum forming - Google Patents

Description

Detailed Description of the Invention

[Industrial field of application] The present invention relates to a vinyl chloride resin sheet for vacuum forming,
In particular, the present invention relates to a vinyl chloride resin sheet for vacuum forming, in which shrinkage of the sheet after vacuum forming is small. [Prior Art] Conventionally, as a polyvinyl chloride resin sheet for vacuum forming,
Sheets using vinyl chloride resin plastisol have been used because of softening of molded products. In order to form a sheet having a squeezing pattern using a vinyl chloride resin plastisol, a vinyl chloride resin plastisol composition is applied to a release paper having an uneven pattern, which is gelled and peeled from the release paper. The resulting vinyl chloride-based resin sheet has a clear transfer of the uneven pattern of the release paper, and can fully express even the fine unevenness of the diaphragm, which is suitable for interior materials for vehicles such as automobiles. [Problems to be Solved by the Invention] As described above, the sheet formed from the vinyl chloride resin plastisol has a soft feeling even when vacuum-formed and is suitable for interior materials such as automobiles, but has been conventionally used. The average degree of polymerization of vinyl chloride resin plastisols for vacuum forming
More than 1400, especially those with an average degree of polymerization of about 2000 have been often used, but sheets formed from plastisol of these high degree of polymerization vinyl chloride resins have the problem that the sheet shrinks greatly after vacuum forming. The secondary shrinkage of the vacuum-formed product, especially when the vacuum-formed product is fitted into another molded product as an interior part of an automobile or the like, or is set in another mold and polyurethane is injection-molded. As a result, there is a big problem that it becomes difficult to set in the injection mold. The present invention has been made against such a background of the prior art, and provides a vinyl chloride resin sheet for vacuum forming, which has extremely little secondary shrinkage after vacuum forming. Means for Solving the Problems That is, the present invention provides (1) a vinyl chloride resin layer having a PVC / ABS resin sheet surface with an uneven pattern of a release paper made of a vinyl chloride resin plastisol composition formed thereon. A vinyl chloride-based resin laminated sheet for vacuum forming, which is composed of more than one layer. (2) A vinyl chloride resin film layer is formed on the surface of the PVC / ABS resin sheet, on which an uneven pattern of a release paper made of a vinyl chloride resin plastisol composition is formed, and a thermoplastic synthetic resin layer is formed on the film layer. A vinyl chloride resin laminated sheet for vacuum forming, in which a skin layer is formed. (3) The vinyl chloride resin sheet for vacuum forming according to claim 2, wherein the coating layer is a non-foamed layer. (4) The vinyl chloride resin sheet for vacuum forming according to claim 2, wherein the coating layer is a foam layer. (5) The vinyl chloride resin sheet for vacuum forming according to any one of claims 2 to 4, wherein the thermoplastic synthetic resin forming the skin layer is formed of polyurethane or a vinyl chloride resin plastisol composition. Is the gist. Examples of the vinyl chloride resin used in the present invention include vinyl chloride alone or vinyl chloride and other vinyl monomers such as vinyl acetate, ethylene, propylene, maleic acid ester, methyl methacrylate, methacrylic acid ester, acrylic acid ester, and higher polymers. Examples thereof include polymers or copolymers obtained by emulsion polymerization or microsuspension polymerization with vinyl ether and the like. These may be used alone or in combination of two or more. Liquid plasticizers that can be used to form plastisols from vinyl chloride-based resins include, for example, phthalic acid di-2-ethylhexyl ester (DOP), phthalic acid diisononyl ester (DINP), phthalic acid butylbenzyl ester (BBP), phthalic acid. General phthalate ester plasticizers such as acid diisodecyl ester (DIDP) and phthalic acid diundecyl ester (DUP), adipic acid dioctyl ester (DOA), sebacic acid dioctyl ester (D
OS), general fatty acid ester plasticizers represented by azelaic acid dioctyl ester (DOZ), trimellitic acid ester plasticizers represented by trimellitic acid trioctyl ester (TOTM), tricresyl phosphate (TCP) ), Triaryl phosphate-based plasticizers such as trixylyl phosphate (TXP),
Epoxy plasticizers such as epoxidized soybean oil,
Polymeric plasticizers such as polyester plasticizers represented by polypropylene adipate and general plasticizers such as chlorinated paraffin can be used, but these plasticizers may be used alone or in combination of two or more. You may use together. These plasticizers are suitable for various intended applications.
It is added in an appropriate amount to the vinyl chloride resin. Generally, the amount added is about 30 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, but the present invention is not limited thereto. As the PVC-based resin used for forming the PVC / ABS-based resin sheet used in the present invention, all the vinyl chloride-based resin compositions forming the vinyl chloride-based resin layer described above can be used. However, the vinyl chloride resin is obtained by suspension polymerization. As the ABS resin, an acrylonitrile-butadiene-styrene copolymer is generally used, but a copolymer using another acrylic monomer instead of acrylonitrile, such as a methylmethacrylate-butadiene-styrene copolymer. Or a copolymer using acrylic rubber in place of butadiene, a copolymer using other diene-based monomers in place of butadiene, a copolymer using other styrene-based monomers in place of styrene, etc. It can be used and is not limited to ordinary ABS copolymers. PVC / ABS-based resin sheet is a blend of vinyl chloride-based resin and ABS-based resin, and if necessary, additives such as plasticizer and stabilizer that are generally used as additives for vinyl chloride-based resin are added. It is obtained by adding and sheeting by a vinyl chloride resin sheet forming method such as calendering. The thickness of the PVC / ABS resin sheet is 0.05 to 1 mm, preferably 0.15 to 0.7 mm. Incidentally, NBR or an acrylic processing aid may be added as an additive. Further, the vinyl chloride resin of the present invention, as a stabilizer,
For example, metal stearate such as lead stearate, barium stearate, zinc stearate, cadmium stearate, calcium stearate, tin-based stabilizer such as dibutyltin dilaurate, dibutyltin malate, organotin mercaptide, organotin sulfonamide, tribasic Lead sulfate, tribasic lead phosphite, tribasic lead maleate and the like are used, and these stabilizers can be used alone or in combination of two or more, and the stabilizer is not particularly limited. The amount of the stabilizer added is 0.5 to 10 parts by weight, preferably about 1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. A foaming agent can be added to the vinyl chloride resin to obtain a foamed sheet. In the case of foaming, for example, azodicarbonamide, which is a foaming agent for vinyl chloride resin, dinitrosopentatetramine, oxybisbenzenehydrazide, or the like can be used for foaming, and a foaming accelerator or, if necessary, A foaming inhibitor may be added. Further, a foamed sheet can be obtained by mechanically foaming the vinyl chloride resin plastisol for obtaining the vacuum molding vinyl chloride resin sheet of the present invention. In this case, it is preferable to use an organic surfactant such as sodium alkylbenzene sulfonate or potassium alkylbenzene sulfonate or silcorn oil such as polydimethylsiloxane or polymethylphenylsiloxane as the foam stabilizer. The amount of foam stabilizer added is vinyl chloride resin Plastisol 10
It is 0.1 to 5 parts by weight with respect to 0 parts by weight. In addition to the above, if necessary, antimony trioxide, flame retardant such as trialkoxyalkyl phosphate, calcium carbonate, talc, hydrotalcite, magnesium carbonate, in addition to fillers such as aluminum hydroxide, processing aids, Pigments, ultraviolet absorbers, antistatic agents, antiaging agents and the like can also be added. In the present invention, it is sufficient that the surface of the PVC / ABS resin sheet has at least one vinyl chloride resin layer on which the uneven pattern of the release paper made of the plastisol composition of the vinyl chloride resin is formed. The vinyl chloride resin layer may be a single layer or multiple layers. In the case of multiple layers, a vinyl chloride resin layer having a low average degree of polymerization and a vinyl chloride resin layer having a high average degree of polymerization may be used in combination.
The vinyl chloride resin layer having a low average degree of polymerization may be exposed on the front surface side to form a skin layer, or may be located on the back surface side to form a coating layer. When the skin layer is formed of a vinyl chloride resin layer having a high average degree of polymerization, one or more film layers of a vinyl chloride resin sheet obtained from a plastisol composition of a vinyl chloride resin having a low average degree of polymerization are formed. It may be a polyvinyl chloride resin sheet for vacuum forming having a multilayer structure. In this case, the coating layer may be a non-foamed layer, a foamed layer, or a combination of a foamed layer and a non-foamed layer. The one in which the skin layer is formed of a plastisol composition of a vinyl chloride resin having a high average degree of polymerization is preferable because the surface of the vacuum molded product obtained by vacuum molding does not disappear and the gloss is extremely small. [Operation] In the present invention, the polyvinyl chloride-based resin sheet for vacuum forming has at least one vinyl chloride-based resin layer made of the vinyl chloride-based resin plastisol composition on the surface of the PVC / ABS-based resin sheet. After the vacuum forming, the sheet formed of the plastisol composition containing the vinyl chloride resin as the main component is formed of only the vinyl chloride resin.
It is suitable for an inner panel, a safety pad, a lid, a console box, an assist grip, etc. used for vehicles such as automobiles and interiors of vehicles such as ships without causing subsequent contraction. [Examples] Hereinafter, examples of the present invention will be specifically described, but the present invention is not limited to these examples. Example 1 The vinyl chloride resin plastisol of the formulation example 1 shown in Table 1 was kneaded for 20 minutes with a liquor machine and then applied to a release paper having a leather diaphragm-like uneven pattern so as to have a thickness of 0.5 mm, and this was applied at 200 ° C. In 2
It was heated and gelated for a minute to obtain a vinyl chloride resin sheet. The obtained vinyl chloride resin sheet had the uneven pattern formed on the release paper clearly transferred, and had a good leather-like appearance. The vinyl chloride resin sheet was laminated on a PVC / ABS resin sheet which was kneaded at 185 ° C. with the composition shown below and dispensed with a calender to a thickness of 0.6 mm to obtain a vinyl chloride resin laminated sheet for vacuum forming. When this vinyl chloride resin laminated sheet for vacuum forming was heated by a far infrared heater and vacuum formed at a surface temperature of 160 ° C., a good vacuum formed product was obtained. The shrinkage rate (secondary shrinkage rate) of the obtained vacuum-formed product was measured. The results are shown in Table 2.

[Shrinkage test]

The obtained vinyl chloride resin laminated sheet for vacuum forming was vacuum formed, and the shrinkage ratio of the 100% stretched part after standing for 24 hours was measured. The smaller the shrinkage ratio, the more preferable. Example 2 A vinyl chloride resin laminated sheet for vacuum forming was obtained in the same manner as in Example 1 except that the vinyl chloride resin plastisol of Formulation Example 2 was used. The same test as in Example 1 was conducted on this vacuum-molded vinyl chloride resin laminated sheet. The results are shown in Table 2. Examples 3 to 5 By using the vinyl chloride resin plastisols of Formulation Examples 1, 2, 3, and 4 and combining Formulation Example 1 and Formulation Example 3, Formulation Example 4 and Formulation Example 2, and Formulation Example 4 and Formulation Example 3 in combination. 0.1m skin layer on release paper
Example 1 except that the coating was applied to give a thickness of m and gelled, and then the coating was applied onto the epidermis layer to give a thickness of 0.4 mm, and two layers were drawn to gel the coating. A vinyl chloride resin laminated sheet for vacuum forming was obtained in the same manner as in. Example 1 of this vinyl chloride resin laminated sheet for vacuum forming
The same test was performed. The results are shown in Table 2. Comparative Examples 1 to 2 The vinyl chloride resin plastisols of Formulation Examples 1, 2, 3 and 4 were used, and a combination of Formulation Example 4 and Formulation Example 3 and Formulation Example 1 and Formulation Example 2 provided a skin layer of 0.1 on the release paper. mm to a thickness of 2 mm, gelled, and coated on the skin layer to a skin layer thickness of 0.4 mm, and then gelled to form a two-layer vacuum-molded vinyl chloride resin laminated sheet. Obtained. The same test as in Example 1 was conducted on this vacuum-molded vinyl chloride resin laminated sheet. The results are shown in Table 2. As is clear from Table 2, the vinyl chloride resin laminated sheet for vacuum forming of the present invention has at least one layer of vinyl chloride resin made of a plastisol composition of vinyl chloride resin on the surface of the PVC / ABS resin sheet. Therefore, it can be seen that the secondary shrinkage after vacuum forming is extremely small. A vinyl chloride resin laminated sheet for vacuum forming having a layer made of a vinyl chloride resin plastisol composition having a low average degree of polymerization (Comparative Example 2) is a vacuum forming made of only a vinyl chloride resin plastisol composition having a high average degree of polymerization. The vinyl chloride resin laminated sheet for vacuum forming (Examples 1 to 5) of the present invention is better than the vinyl chloride resin laminated sheet for vacuum forming (Comparative Example 1) with less secondary shrinkage. It is preferable because it has less secondary shrinkage. (Effects of the invention) The present invention is a polyvinyl chloride-based resin sheet for vacuum forming as described above, which has a PVC / ABS-based resin sheet surface formed with an uneven pattern of release paper made of a vinyl chloride-based resin plastisol composition. Since it has at least one vinyl resin layer, it is possible to prevent secondary shrinkage after vacuum forming like a sheet consisting only of a vinyl chloride resin layer formed of a plastisol composition containing a vinyl chloride resin as a main component. It is possible to obtain a vacuum-formed product that does not wake up and is soft and has a good feel to the touch. It is used for the interior panels, safety pads, lids, console boxes, and assist grips used in the interior of vehicles such as automobiles and vehicles such as ships. And so on. Further, the polyvinyl chloride-based resin sheet for vacuum forming of the present invention is particularly suitable for male drawing vacuum forming, because the coating layer is formed by transferring the uneven pattern of the release paper beforehand. In addition, the uneven pattern on the surface that has been shaped in advance remains as it is, and a fine squeezing pattern or the like can be exposed on the surface.

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Claims (5)

[Claims] 1. A vacuum molding vinyl chloride comprising one or more vinyl chloride resin layers formed on the surface of a PVC / ABS resin sheet with an uneven pattern of a release paper made of a vinyl chloride resin plastisol composition. Series resin sheet. 2. A PVC / ABS resin sheet surface is formed with a vinyl chloride resin film layer on which an uneven pattern of a release paper made of a vinyl chloride resin plastisol composition is formed, and a thermoplastic layer is formed on the film layer. A vinyl chloride resin sheet for vacuum forming, in which a synthetic resin skin layer is formed. 3. The vinyl chloride resin sheet for vacuum forming according to claim 2, wherein the coating layer is a non-foaming layer. 4. The vinyl chloride resin sheet for vacuum forming according to claim 2, wherein the coating layer is a foam layer. 5. The vinyl chloride resin sheet for vacuum forming according to claim 2, wherein the thermoplastic synthetic resin forming the skin layer is formed of polyurethane or a vinyl chloride resin plastisol composition.