JP3839011B2 - Vinyl chloride resin film for vacuum forming and vacuum forming method - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a vinyl chloride resin film containing short glass fibers for vacuum forming and a vacuum forming method using such a film, and more particularly, easy bonding processing along a substrate having a cubic surface by vacuum forming. In addition, the vacuum molded product thus obtained has no shrinkage of the film after processing, and the surface film has excellent scratch resistance and abrasion resistance, and such a vinyl chloride resin film. The present invention relates to a vacuum forming method using a film.

  In recent years, decorative materials obtained by bonding a film made of a vinyl chloride resin to a three-dimensional base material having a curved cubic surface, such as MDF, a steel plate, an inorganic plate, etc. by vacuum forming, for example, building materials, furniture, It has been widely used for household electrical appliances and vehicle interior materials. Since the vinyl chloride resin is flexible, it can be suitably used for such vacuum forming, but on the other hand, there is a problem that the scratch resistance and wear resistance of the surface are not sufficient.

  On the other hand, various vinyl chloride resin films containing various fillers are already known. For example, Japanese Utility Model Publication No. 60-33005 discloses an intermediate layer made of a resin layer in which short glass fibers are dispersed together with a colorant between a translucent or opaque base layer and a surface layer made of a transparent or translucent resin layer. And a decorative material formed by laminating a pattern layer between the intermediate layer and the surface layer. Such a decorative material is intended to give a high design to the appearance and does not take into consideration the scratch resistance or wear resistance of the surface layer. Not suitable for use as a plate.

  There is already known a surface protective sheet having improved surface slipperiness by providing an adhesive layer on one side of a soft or semi-rigid vinyl chloride resin sheet containing a finely divided inorganic filler such as silica or zeolite ( Patent Document 1). However, this resin sheet is also insufficient in scratch resistance and wear resistance.

In addition, a resin film in which short glass fibers are dispersed, an internal plasticized resin film, and an adhesive layer are laminated in this order, providing excellent scratch resistance and wear resistance, as well as conformability to a cubic surface. Excellent interior decoration materials are also known (see Patent Document 2). However, there is no description that the film is used for vacuum forming.
JP-A-56-69158 Japanese Patent Laid-Open No. 6-79835

  The present invention has been made in order to solve the above-described problems in vacuum forming using a conventional vinyl chloride resin film, and can easily perform bonding processing along a substrate having a cubic surface by vacuum forming. In addition, in the vacuum molded product thus obtained, there is no shrinkage of the film, and the vinyl chloride resin film which gives the molded product a surface excellent in scratch resistance and wear resistance, and such a film An object of the present invention is to provide a method for producing a vacuum-formed product using the above.

  The vinyl chloride resin film for vacuum forming according to the present invention is a glass short having a plasticizer of 0 to 35 parts by weight, a particle size of 6 to 12 μm, and an average length of 0.2 to 1.0 mm with respect to 100 parts by weight of polyvinyl chloride. It contains 0.5 to 30 parts by weight of fiber and has a Crashberg softening temperature of 45 ° C. or higher.

  In addition, the vacuum forming method according to the present invention is a vacuum forming method in which a vinyl chloride resin film is bonded to a substrate having a cubic curved surface via an adhesive by vacuum forming. A film containing 0 to 35 parts by weight of an agent, 0.5 to 30 parts by weight of short glass fibers having a particle size of 6 to 12 μm and an average length of 0.2 to 1.0 mm, and a Crashberg softening temperature of 45 ° C. or higher It is characterized by being bonded to a substrate at 60 to 90 ° C.

  As described above, the vinyl chloride resin film for vacuum forming according to the present invention contains short glass fibers at a predetermined ratio with respect to polyvinyl chloride and has a predetermined Crashberg softening temperature. In the obtained molded product, the surface layer has excellent scratch resistance and wear resistance, and the film does not shrink and peel off from the molded product.

  Furthermore, according to the present invention, the vinyl chloride resin film can be made substantially transparent. In such a case, this film is used as a surface layer, and a film having a pigment or a pattern is used as a support layer. It is possible to manufacture vacuum-formed products with high design properties.

  The polyvinyl chloride used in the present invention is not particularly limited, and those for ordinary calendar molding are used. If necessary, in order to improve the processability of polyvinyl chloride or improve the properties of the resin, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, chloride Vinyl- (meth) acrylic acid ester copolymer, polyurethane-vinyl chloride copolymer, methyl methacrylate (copolymer) resin, etc. may be used in combination with polyvinyl chloride usually in the range of 10% by weight or less. . For example, methyl methacrylate (copolymer) resin is useful as a modifier.

  The vinyl chloride resin film for vacuum forming according to the present invention is blended uniformly with such a polyvinyl chloride by adding a stabilizer, a plasticizer, and other additives in addition to short glass fibers as necessary. Can be obtained by preparing a compound, ie a compound, and calendering it. The plasticizer may be a conventional plasticizer conventionally used for the production of vinyl chloride resin calendered products. Therefore, for example, in addition to phthalic diesters such as diethylhexyl phthalate (DPO), linear dibasic acids Diesters, phosphate esters, epoxidized soybean oil, polyester plasticizers and the like are also used. The amount of such a plasticizer depends on the required properties for the film to be obtained, but is usually in the range of 0 to 35 parts by weight, preferably 10 to 30 parts by weight with respect to 100 parts by weight of polyvinyl chloride. It is a range.

  The vinyl chloride resin film for vacuum molding according to the present invention closely follows a substrate having a cubic surface under vacuum molding conditions, the film does not shrink in the resulting molded product, and the surface of the molded product is resistant to damage. Usually, short glass fibers having a particle diameter of 6 to 12 μm and an average length of 0.2 to 1.0 mm are used with respect to 100 parts by weight of polyvinyl chloride so as to be excellent in scratch resistance and wear resistance. , 0.5 to 30 parts by weight, preferably 3 to 30 parts by weight, and most preferably 10 to 30 parts by weight.

  Such a vinyl chloride resin film for vacuum forming is obtained by blending short glass fibers having a particle diameter of 6 to 12 μm and an average length of 2 to 12 mm into the polyvinyl chloride described above, and, if necessary, a stabilizer, a plasticizer, Other additives are added, and the mixture is uniformly mixed and kneaded to prepare a compound, that is, a compound, which can be obtained by calendering. As the short glass fibers, those in which 200 to 300 fibers are generally converged by a silane coupling agent that is a converging agent, that is, chopped strands are preferably used. Such short glass fibers are kneaded with polyvinyl chloride and calendered, so that they are separated and crushed into individual short fibers having an average length of 0.2 to 1.0 mm and uniformly dispersed in the film. The

  When the blended amount of short glass fibers is less than 0.5 parts by weight with respect to 100 parts by weight of polyvinyl chloride, the obtained film cannot obtain the intended scratch resistance and wear resistance, When the amount exceeds 30 parts by weight, film production by calendar molding becomes difficult, which is not preferable.

  Furthermore, a stabilizer is normally mix | blended with a formulation. As the stabilizer, metal soaps such as barium, cadmium and zinc are usually preferably used. The stabilizer is usually used in a range of 0.5 to 10 parts by weight, preferably in a range of 1 to 5 parts by weight with respect to 100 parts by weight of polyvinyl chloride.

  In addition to the above, when preparing the formulation, within the range that does not impair the desired properties of the resulting film, ordinary lubricants, colorants such as pigments, antioxidants, ultraviolet absorbers, flame retardants, antistatic agents, etc. May be blended.

  In the present invention, the vinyl chloride resin film has a Crashberg (Crashberg) softening temperature in the range of 45 to 75 ° C, preferably 48 to 60 ° C. When the crusberg (crashberg) softening temperature of the film is lower than 45 ° C., the obtained molded article has a large shrinkage of the film, and depending on the environmental conditions, the film may be peeled off from the substrate and may shrink. . On the other hand, when the flexible temperature is too high, the film is less likely to follow the substrate during vacuum forming, and is usually 75 ° C. or lower.

  The crushberg temperature of the vinyl chloride resin film can be adjusted to the target range depending on the type and amount of the additive. For example, by increasing the amount of plasticizer or liquid stabilizer added to polyvinyl chloride, the crashberg temperature of the resulting film can be lowered, while an acrylic heat resistance improver or a resin with a high softening point can be used. It can be raised by mixing, and by adding an inorganic filler such as calcium carbonate or glass fiber, the Crashberg temperature can be raised somewhat. The unplasticized vinyl chloride resin film usually has a crushberg temperature of about 75 ° C.

  The vinyl chloride resin film for vacuum forming according to the present invention includes short glass fibers and a vinyl chloride resin film that forms a surface layer of a vacuum formed product, and does not include short glass fibers, and supports the film of the surface layer. Further, it may be a multilayer film composed of a reinforcing support layer. In the case of such a multilayer film, the film forming the surface layer must have a Crashberg softening temperature of 20 ° C. or higher, and the film forming the support layer must have a Crashberg softening temperature of 48 ° C. or higher. Thereby, the same vacuum formability as in the case of the single layer film can be ensured. In particular, according to the present invention, the crushberg softening temperature of the film forming the surface layer is preferably in the range of 20 to 50 ° C., and the crushberg softening temperature of the film forming the support layer is preferably in the range of 48 to 65 ° C. .

  Thus, by using a vinyl chloride resin film for vacuum forming as a multi-layer and using one having a low Crashberg softening temperature on one side, the composition has good thermal stability and excellent calendar moldability in its manufacture. At the same time, the obtained film has advantages such as excellent weather resistance and further excellent cold resistance.

  When the vinyl chloride resin film for vacuum forming according to the present invention is a multilayer film, the film forming the surface layer and the film forming the support layer are usually laminated and bonded together by thermal fusion or using an appropriate adhesive. It can be obtained by laminating and bonding. Although it does not specifically limit as an adhesive agent, For example, a ultraviolet curable urethane acrylate resin adhesive agent can be used suitably. In addition, the film forming the support layer may contain a normal lubricant, a colorant, an antioxidant, an ultraviolet absorber, a flame retardant, an antistatic agent, and the like, if necessary.

  Further, according to the present invention, when the vinyl chloride resin film for vacuum forming is a multilayer film, various patterns and characters may be printed on the surface of the film forming the support layer. The surface of the film forming the substrate may be embossed, and the surface layer may be bonded and laminated thereon, or the film forming the support layer may be appropriately colored with a pigment.

  Further, whether the vacuum forming film according to the present invention is a single layer or a multilayer, for example, an acrylic pressure-sensitive adhesive layer or a hot-melt adhesive layer may be provided as the lowermost layer in advance.

  The vinyl chloride resin film for vacuum forming according to the present invention is excellent in scratch resistance and wear resistance because the short glass fibers are almost uniformly dispersed from the front surface to the back surface. Even so, it retains scratch resistance. Furthermore, when the film according to the present invention has a composition that does not hinder its transparency, so-called clear composition, the short glass fibers are transparent, so the film is also excellent in transparency, and usually has a light transmittance of 75% or more. According to a preferred embodiment, it has 80% or more. As described above, since the vinyl chloride resin film for vacuum forming according to the present invention is substantially transparent, as described above, a layer having a pigment or a design pattern is used as a support layer to form a high design property. Can be manufactured.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1
Eight parts by weight of ethylhexyl phthalate and chopped strands of short glass fibers having a particle diameter of 6 μm and a length of 8 mm (Glaslon chopped strand 06 manufactured by Asahi Fiber Glass Co., Ltd.) per 100 parts by weight of polyvinyl chloride (average polymerization degree 800) -IE-830A) 3 parts by weight, and further, a cadmium-barium stabilizer and a methyl methacrylate-butadiene-styrene copolymer resin (MBS resin) manufactured by Kaneka Chemical Industry Co., Ltd. An appropriate amount of “Kane Ace B-11A” and a pigment were added, mixed and kneaded with a Henschel mixer to form a compound, and then formed into a 0.2 mm thick film by calendar molding. The film thus obtained had a Crashberg softening temperature of 50 ° C., and the average length of the short glass fibers in the film was 0.51 mm. The Crashberg softening temperature of the film was measured according to JIS K-6734.

This film was bonded to a substrate by vacuum forming to produce a molded product. As a base material, MDF (vertical 15 cm, horizontal 30 cm, height 1.8 cm) having a vertical cross-sectional shape, a vertical cross-section having a substantially rectangular shape, and a flat bottom surface is used at the upper four corners. A urethane two-component water-based adhesive was applied to a surface having a cubic curved surface, and the film was bonded to the surface by vacuum forming to obtain a molded product. The vacuum forming conditions were a press pressure of 3.0 kg / cm ² , a press temperature (silicone rubber temperature) of 65 ° C., a press time of 150 seconds, and a preheating of 15 seconds. Table 1 shows the scratch resistance, wear resistance, and vacuum forming suitability of the molded product thus obtained.

  The scratch resistance was evaluated by a pencil scratch test method of JIS K-5400, and the wear resistance was evaluated by a Taber type wear test method using a wear wheel CS-17 under a load of 1 kg. The suitability for vacuum forming refers to the suitability of the molded product to follow the cubic curved surface and the shrinkage of the film when the molded product is left at 60 ° C. for 48 hours (the shrinkage of the film from the lower end of the substrate is defined as the four corners of the substrate). And took 1/4 of that). Moreover, as needed, the transparency calculated | required the light transmittance according to JISK-7105.

Examples 2-5
A film having a thickness of 0.2 mm was obtained in the same manner as in Example 1 except that short glass fibers were used in an amount shown in Table 1 with respect to 100 parts by weight of polyvinyl chloride. Table 1 shows the Crashberg softening temperature, the average length of short glass fibers in the film, the scratch resistance, the wear resistance and the vacuum forming suitability of the surface of the obtained molded product.

Example 6
100 parts by weight of polyvinyl chloride (average polymerization degree 800), 20 parts by weight of ethylhexyl phthalate, chopped strands of short glass fibers having a particle diameter of 6 μm and a length of 8 mm (Glaslon chopped strands 06 made by Asahi Fiber Glass Co., Ltd.) IE-830A) 5 parts by weight, and further, as a cadmium-barium stabilizer and an impact-resistant agent, methyl methacrylate-butadiene-styrene copolymer resin (MBS resin) “Kane Ace” manufactured by Kaneka Chemical Industry Co., Ltd. An appropriate amount of “B-11A” was added to form a clear composition, mixed and kneaded with a Henschel mixer to form a compound, and then formed into a 0.2 mm thick film by calendering. The surface layer film thus obtained had a Crashberg softening temperature of 28 ° C., and the average length of the short glass fibers in the film was 0.54 mm. The light transmittance of this film was 83%.

  Separately, to 100 parts by weight of polyvinyl chloride (average polymerization degree 800), 8 parts by weight of ethylhexyl phthalate, cadmium-barium stabilizer, the same impact agent and pigment as described above are added, and they are mixed and kneaded in a Henschel mixer. After being compounded, a 0.2 mm thick film was formed by calendering. The film for the support layer thus obtained had a Crashberg softening temperature of 51 ° C. The film for the surface layer and the film for the support layer were bonded and laminated by heat fusion to obtain a vacuum forming film, and a vacuum formed product was produced in the same manner as in Example 1. Table 1 shows the scratch resistance, abrasion resistance and vacuum forming suitability of the surface of the obtained molded product.

Relatively 1
The film for the support layer of Example 6 was used as a vacuum forming film. Table 1 shows the scratch resistance, abrasion resistance and vacuum forming suitability of the surface of the obtained molded product.

Claims (2)

Crashberg contains 100 to 35 parts by weight of polyvinyl chloride, 10 to 35 parts by weight of plasticizer, 0.5 to 30 parts by weight of short glass fibers having a particle size of 6 to 12 μm and an average length of 0.2 to 1.0 mm. It contains 10 to 35 parts by weight of a plasticizer with respect to 100 parts by weight of polyvinyl chloride and a film forming a surface layer in which the softening temperature is in the range of 20 to 50 ° C., and the crash Berg softening temperature is in the range of 48 to 65 ° C. A vinyl chloride resin film for vacuum forming comprising a film forming a certain support layer, and comprising a multilayer film having a crushberg softening temperature of the surface layer lower than a crushberg softening temperature of the film forming the support layer . In a vacuum forming method in which a vinyl chloride resin film is bonded to a substrate having a cubic curved surface via an adhesive by vacuum forming, 10 to 35 parts by weight of a plasticizer and a particle size of 6 with respect to 100 parts by weight of polyvinyl chloride. A film forming a surface layer containing 0.5 to 30 parts by weight of short glass fibers having an average length of 0.2 to 1.0 mm and a crushberg softening temperature in the range of 20 to 50 ° C., and polyvinyl chloride relative to 100 parts by weight, include a plasticizer 10-35 parts by weight, crash Berg flexible temperature Ri Do and a film constituting the support layer in the range of 48 to 65 ° C., crash Berg flexibility temperature of the surface layer is above A vacuum forming method characterized in that a multilayer film having a lower temperature than the Crashberg softening temperature of a film forming a support layer is bonded to a substrate at a temperature of 60 to 90 ° C.