JPH0366160B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a decorative material and a method for producing the same, and more particularly, to an automotive interior material, particularly a door side,
The purpose of the present invention is to provide decorative materials that are useful as interior materials for instrument panels, seat covers, etc., exterior materials for furniture, bags such as shopping bags, and other materials, and that have unique shadows and deep color tones. . (Prior art) Various decorative materials have been known in the past, and in particular, colored plastic sheets and three-dimensional molded products are very widely used because they are easy to color and pattern and can be mass-produced. has been done. For example, colored molding of soft vinyl chloride resin,
It is obtained by kneading a coloring agent and a vinyl chloride resin to form a sheet using a calendering method or a coating method, or by casting (powder slush molding) using a colored dry blend powder. In addition, colored sheets, colored films, three-dimensional colored molded products, etc. made of thermoplastic resins other than soft vinyl chloride resins are also widely used, and these colored products are mostly made by melt-kneading pigments and thermoplastic resins. and then molded into the respective shapes. (Problems to be Solved by the Invention) In the conventional colored molding of thermoplastic resins, etc. as described above, the coloring agent and thermoplastic resin are uniformly applied, whether it is a single color or a blended hue using mixed pigments. It is most important to mix and disperse the colorant uniformly, so that if the colorant is dispersed satisfactorily, a molded article with a good uniform tone will be obtained, whereas if the colorant is not sufficiently dispersed, a molded product will be obtained. If this occurs, the colored molded product will generally have uneven coloring or poor color development, resulting in a defective product. For example, if a yellow pigment and a blue pigment are used in a color scheme and sufficient mixing and dispersion is achieved, a sufficiently uniform green color can be obtained.Although such a green color is excellent as a green color, this is simply not the case. It is a green color, flat and monotonous, and is not suitable for cases where a luxurious or subdued color tone, or furthermore, a shaded or deep green color is required. Of course, using conventional coloring techniques, it is possible to color in any tone, but in any case, as a result of the requirement that the blended pigment be uniformly dispersed, the color tone of the colored molded product obtained is flat and uneven. It is monotonous, and it is impossible to create a more luxurious feel, shadow, or deeper color tone. The above facts are the same for powder slush molding methods and other colored molding techniques. On the other hand, there are examples in which colored pellets of several millimeters in size are made of thermoplastic resin, etc., and these colored pellets of multiple hues are fused together to form a mosaic pattern and are used as flooring materials. These flooring materials have large patterns, so they are gorgeous, but as a result of the different colored pellets being clearly observed separately, it is difficult to create a sense of luxury with shadows and depth. Can not. Therefore, there is a demand for decorative materials with shadows and depth that cannot be obtained using the conventional techniques as described above, and with subdued and luxurious colors, for use as interior materials for automobiles, exterior materials for furniture, flooring materials, wall materials, etc. There is. (Means for Solving the Problems) The present inventor completed the present invention as a result of intensive research in order to meet the demands of the prior art as described above. That is, the present invention consists of two inventions, the first of which is a decorative material made by fusing a mixture of two or more types of colored thermoplastic synthetic resin powders with different hues into a desired shape without melt-kneading. A decorative material characterized in that the particle size of the powder is within the range of 50 μm to 350 μm, and the second invention is a decorative material characterized in that the particle size of the powder is within the range of 50 μm to 350 μm. This is a method for producing a decorative material, which is characterized by spreading a powder mixture of two or more of these different hues onto a substrate and fusing them without melt-kneading. Next, to explain the present invention in more detail, according to detailed research by the present inventor, a mixture of two or more types of colored thermoplastic synthetic resin powders having different hues can be fused into a desired shape without melt-kneading. In some cases, the color tone of the resulting molded product changes slightly depending on the particle size of the colored powder, especially when the particle size is within a range that can or may not be discerned with the naked eye.
It has been found that compared to colored molded products of the prior art, the color tone is noticeably darker, deeper, and calmer, and has a very luxurious feel. The thermoplastic resin powder used in the present invention refers to vinyl chloride-based resins such as vinyl chloride homopolymers and copolymers of vinyl chloride and other monomers,
Any conventionally known thermoplastic resin may be used, such as ABS resin, MBS resin, chlorinated polyethylene resin, acrylic resin, polyolefin resin such as polyethylene, polypropylene, polystyrene, polyamide, polyester, polyurethane, polycarbonate, polysulfone, etc. The most preferable ones are those that can absorb liquid plasticizers well, such as vinyl chloride resin, and have good surface adhesion and dyeability of colorants.
Thermoplastic resins that have excellent heat fusion properties at relatively low temperatures, such as polyvinyl chloride and vinyl chloride-based resins such as copolymers of vinyl chloride and comonomers such as ethylene and vinyl acetate. The above-mentioned thermoplastic resins are used in the form of colored powders in the present invention, but these colored powders may be those obtained by pulverizing colored thermoplastic resins to a desired particle size using a freeze-pulverization method or the like. It may be a colored powder resin obtained by an emulsion polymerization method or a suspension polymerization method, and is not particularly limited. However, the most preferred is a vinyl chloride resin powder obtained by a suspension polymerization method.
The vinyl chloride resin powder obtained by such a suspension polymerization method is a porous powder, and this powder has very good absorbency of liquid plasticizer, and when a liquid plasticizer is added and mixed, the plasticizer is absorbed into the inside of the powder through the pores of the powder, resulting in a powder that has a moist texture rather than a wet or fluidized state, and is a powder that is smooth and easy to handle. If the mixture is mixed at a temperature of 50 to 80 PHR, the absorption of the plasticizer will be further promoted, and even if a large amount of plasticizer, 50 to 80 PHR, is added, the powder after mixing will have a smooth and dry feel. Such powders are commonly referred to as dry blend powders. By adding colorants such as pigments and dyes at the same time during the plasticizer absorption process, the colorant is uniformly adsorbed or adhered to the powder surface by the action of the plasticizer, resulting in a very good result. A colored dry blend powder is obtained. A particularly preferred embodiment is a method of using what is called a toner, in which a colorant is uniformly dispersed in a liquid plasticizer, and a colored dry blend powder that is most uniformly colored can be most easily obtained. The colored synthetic resin powder can be obtained arbitrarily by the method described above, with a particle size ranging from a few μm to several 100 μm, but those preferably used in the present invention have a particle size in the range of 50 μm to 350 μm. By using colored synthetic resin powder having such a particle size, it is possible to obtain the decorative material of the present invention, which has shadows and depth, and has a calm and luxurious feel. When the particle size is less than 50 μm, there is not much difference in shadow or depth compared to conventional uniform coloring, and when the particle size exceeds 350 μm,
This is undesirable because individual particles become visible to the naked eye, which results in shadows and depth, making it impossible to obtain a decorative material with a calm and luxurious feel. The decorative material of the present invention is obtained by fusing the colored thermoplastic synthetic resin powder as described above into a predetermined shape without melt-kneading, and the colored thermoplastic synthetic resin powder mixture is coated on any substrate. Since it is heated and melted and molded while it is in a spread state,
The melting characteristics of the thermoplastic resin itself under heating are important. Therefore, from a process standpoint, it is preferable to use a thermoplastic resin with a relatively low molecular weight and a low softening point, but even if it is a relatively high molecular weight thermoplastic resin, it is heated above its softening point and the colored resin powders are sufficiently bonded together. There is no particular limitation as long as the temperature is such that it can be fused to. For example, in the case of vinyl chloride resins, if their particle size, plasticity content, thickness of spreading on the substrate, etc. are the same, the lower the degree of polymerization, the lower the temperature. , and when the vinyl chloride resin is a copolymer of vinyl chloride and other monomers,
The melting temperature also changes depending on the monomer components of the copolymer; for example, a vinyl chloride-ethylene copolymer has a lower softening point than a vinyl chloride straight polymer and a vinyl chloride-vinyl acetate copolymer with the same degree of polymerization. have. Therefore, in the present invention, it is preferable to use a thermoplastic resin having a low softening temperature. For example, in the case of a vinyl chloride resin, one having a degree of polymerization of 2500 or less, more preferably 1500 or less is suitable. However, if the strength of the decorative material or a variety of other high properties are required, thermoplastic resin powders such as higher molecular weight vinyl chloride resin, ABS resin, MBS resin, etc. can also be used. When using thermoplastic resins with a high softening point, relatively low molecular weight vinyl chloride resin or vinyl chloride-ethylene copolymer powder is added to these thermoplastic resins to fuse the entire mixture. Preferably, the temperature is lowered. In such cases, thermoplastic resin powder with a relatively low softening point is
It acts like an adhesive to the thermoplastic resin powder, which has a high softening point, and is integrated as a whole. The colored thermoplastic synthetic resin powders used in the present invention are as described above, and these colored thermoplastic synthetic resin powders contain, in addition to the thermoplastic resin and colorant as essential components, other additives as necessary. For example, plasticizers, stabilizers, fillers, etc. can naturally be included, and they may be added when the thermoplastic resin is powdered or when the thermoplastic resin powder is colored, and are not particularly limited. . For example, if the thermoplastic resin is a soft vinyl chloride resin, the vinyl chloride resin powder, plasticizer, colorant, stabilizer, filler, etc. may be mixed at high speed in a Henschel mixer. Uniformly colored vinyl chloride resin powder can be easily obtained. In particular, the Henschel mixer has rotating blades set at the bottom of the stirring tank, and the high speed rotation of the blades allows each component to be uniformly dispersed and mixed.
It is suitable for the purpose of the present invention, and it is effective to attach a baffle plate or the like to further improve the stirring and mixing efficiency. In addition, absorption of the plasticizer, that is, dry blending, is promoted by heating, and therefore it is preferable to use a double jacket type stirring tank and heat the mixture while heating the mixture by passing a heat medium through the jacket. For example, 5-10 at a temperature of 50-80℃
A uniformly colored dry blend powder can be obtained by mixing and stirring for several minutes. In the present invention, colored thermoplastic synthetic resin powders of various hues are prepared as described above, and two or more of these colors are uniformly mixed and molded into a desired shape. The colored synthetic resin powder may be mixed in any color as long as it is two or more colors, and is determined by the desired color tone and purpose of the final decorative material, and the number of colors to be mixed is not particularly limited. . The mixing ratio is also determined depending on the hue and tone required for the final molded product.For example, in the case of mixing two colors, the mixing ratio is generally 1:1, but The ratio is, for example, 5 to
95: Can be selected in a wide range such as 95 to 5. The same applies to the case of mixing three or more colors. The colored synthetic resin powders may be mixed by any mixing method as long as the powders are not melted and kneaded together. However, when using a Henschel mixer, for example, in a double jacket to prevent the powders from fusing together. It is preferable to carry out the process at a relatively low temperature while running cold water. The mixed colored thermoplastic synthetic resin powder obtained as described above is molded according to the present invention, but these moldings may be performed by any method as long as the mixture is fused without being melted and kneaded. For example, preferred methods for obtaining sheet-like decorative materials include the following methods. (1) Substrates that are integrated with decorative materials formed by themselves, such as paper linings, woven fabrics, non-woven fabrics, wood boards,
A method in which the material is spread onto a substrate such as a metal plate or glass plate using a doctor roll or doctor blade coating machine to the desired thickness and surface shape, and then heated and fused into a sheet. (2) A method in which the above method is carried out on a temporary substrate (carrier) such as a release paper that is not integrated with the decorative material but is peeled off after molding, and then the substrate is peeled off. The sheet-like material of the present invention can be prepared by spreading the mixed colored thermoplastic synthetic resin powder as described above on the substrate as described above and fusing the mixed powder layer, or by peeling off the substrate as necessary. A decorative material is obtained, but the spreading thickness may be any thickness and is not particularly limited. However, the bulk height of the spread powder layer is significantly reduced by fusion, so if the spread thickness is too thin, pinholes may occur when the powders fuse together due to heating, or so-called insect bites may occur. In some cases, some parts may occur. Therefore, when obtaining a complete film-like or sheet-like decorative material without pinholes, etc., pinholes are likely to occur when the spread thickness is within 1.2 times the maximum particle size of the powder. The spread thickness of the powder is preferably 1.2 times or more the maximum particle size of the powder. There is no particular upper limit to the spreading thickness, but the thickness of the decorative material formed is generally 50 μm.
Since the thickness is approximately 5 mm, a spread thickness corresponding to this thickness is generally used. Fusion of the powder layer spread as described above is performed by heating the powder layer to a temperature that melts or softens the powder layer and fuses the powders together to form a sheet. The method is not particularly limited and may be carried out by any method such as continuous heating using a hot air heating furnace, surface heating using an infrared heater, or pressure heating using a press or hot roll. It is very easy to form a sheet by such heat fusion, and a sheet material with a smooth surface can be obtained. However, if the powder mixture is a mixture of thermoplastic resin powders with different softening points and the melting temperature is low, the surface may become uneven and have a fine uneven shape or a yuzu skin shape. The uneven shape can also be used as it is as a surface decoration. If such an uneven surface shape is not required, heat treatment at a temperature higher than the softening point of the powder with a higher softening point in the mixed powder will prevent unevenness from occurring, and even if it does occur, it will not occur. It is also possible to smoothen the surface by, for example, pressing with a hot roll or the like afterwards. Moreover, instead of such surface smoothing, an intentional uneven shape may be imparted to the surface by heating and pressing with an embossing roll or the like. The temperature used for fusing the powder spread layer cannot be unconditionally defined because it varies depending on the type of thermoplastic resin powder used, degree of polymerization, spread thickness, etc., but it is generally 120 to 250°C. It is carried out at a temperature of about Furthermore, the present invention is not limited to film-like or sheet-like shapes, but also provides three-dimensional decorative materials, such as interior materials for automobiles such as door sides and instrument panels. be able to. That is, on a cavity surface such as a mold surface having a releasable surface that gives a desired surface shape,
The above powder mixture is adhered or spread to a predetermined thickness, the mold surface is heated in advance or the powder mixture is fused and integrated in the same manner as above by heating in advance, and then peeled off from the mold surface. This makes it possible to provide the three-dimensional decorative material of the present invention having a desired surface shape. (Operation/Effect) According to the present invention as described above, two or more types of colored thermoplastic synthetic resin powders having a specific particle size and different hues are mixed, and the mixture is fused and molded without melt-kneading. By doing so, it is possible to provide a decorative material that is rich in shade and depth, and has a calm and luxurious feel, which was hitherto unknown. In other words, conventional decorative materials that are uniformly colored exhibit a flat and monotonous visual appearance without giving any special visual appearance under any conditions, whereas the decorative materials of the present invention appear to be similar to conventional decorative materials at first glance. However, due to changes in surrounding conditions such as viewing angle, type of light source (for example, fluorescent lamps, daylight, incandescent lamps, or when they coexist), and the angle of incidence of these lights, Each of them gives a slightly changing shadow and a sense of depth, making it a highly luxurious decorative material that has never existed before. In addition, when compared with conventional decorative materials such as flooring materials in which colored pellets of several millimeters are fused together, these conventional decorative materials exhibit a mosaic-like visual appearance, but are different from the conventional uniformly colored materials described above. On the other hand, the decorative material of the present invention does not give such a mosaic-like appearance, but exhibits a visual impression with very deep shadows and depth, giving a completely different aesthetic sense. The unique decorative effect of the decorative material of the present invention is due to the fact that the colored thermoplastic synthetic resin powder, which has a particle size that is invisible to the human eye, is fused without melting and kneading. In other words, there are countless subtle color differences, such as a high color density at the interface where the colored powder is fused and a lower color density in other parts, and these combine to create a unique product. This is thought to be because it is recognized by human vision as a color tone. Therefore, the decorative material of the present invention can be used as an interior material for automobiles,
It is extremely useful as flooring and wall materials for rooms such as homes, hotels, and stores, as well as exterior materials for furniture, clothing, bags, bags, and other materials. Next, the present invention will be explained in more detail with reference to Examples. In addition, parts and percentages in the text are based on weight unless otherwise specified. Examples 1 to 10 Vinyl chloride resin (degree of polymerization P≒1000) *1 100 parts DOP 70 parts Stabilizer (Ba-Zn stabilizer) 3 parts Pigment (toner) Appropriate amount *1; S- manufactured by Kureha Chemical Co., Ltd. 901, 42 mesh (350μm) pass 100% 200 mesh (74μm)
Pass 10% or less The above mixture is stirred at high speed (1400 rpm) for 6 minutes using a Henschel mixer running hot water at 70°C, then switched to cold water and rotated at low speed (400 rpm).
The mixture was cooled to 30° C. to obtain colored dry blend powders having six different hues shown in Table 1 below.

[Table] These colored dry blend powders are mixed in the combinations shown in Table 2 below at a weight ratio of 1:1 or 1:1:1 to form a mixed colored powder, and then spread on a 0.12 mm thick flame retardant paper with a thickness of 0.6 mm. A total thickness of 0.48 ~ 200℃, heated at 200℃ for 2 minutes to melt, and lined with flame retardant paper.
A decorative sheet of the present invention having a thickness of 0.52 mm was obtained. On the other hand, using the same mixed colored powder as above,
After kneading for 10 minutes using a 9 inch φ x 20 inch L test roll at 165°C, the mixture was rolled into a sheet with a thickness of 0.2 mm to obtain a sheet for comparison. Although the spread molten sheet of the present invention and the kneaded and rolled sheet of the comparative example have similar color tones when viewed at a distance or from a distance, it can be seen that there is a considerable difference in color representation and Munsell value. These results are shown in Table 2 below.

【table】

【table】

【table】

[Table] From the above table, it is found that Examples (Comparative Examples) 1, 2, and 6 show a significant difference in color difference between Examples and Comparative Examples, and the decorative sheets of Examples have the same colorant composition. Nevertheless, it is clear that the sample has significant shadows and deeper color tone than the comparative example. In terms of color difference, the value is not as large as the previous three, but it has a unique visual effect.
5, 7, 8 and 10, all of which are mixed with a difference of 1.0 or more in brightness (V) and chroma (C), and as colored sheets are shown in Table 2. However, in terms of microstructure, particles with high brightness and chroma are dispersed as they are without being kneaded, which gives rise to unique visual and coloring effects. Ru. For example, in Example 3, the colored sheet appears to have a Munsell value of 4.4OY0.18/3.16, but in terms of microstructure, it looks like colored powder A.
9.29BG0.11/1.79 as base color and coloring powder D
8.00YR2.24/3.04 shows fine dispersion, and this D particle is relaxed or emphasized depending on the condition of the light, visual perception, and light source difference, giving the unique shading and depth of the colored sheet. On the other hand, colored sheets of comparative examples prepared from compositions having exactly the same combinations as those of Examples 1, 2, and 6 and Examples 3, 5, 7, 8, and 10 had the Munsell values shown in Table 2, respectively. However, these sheets were merely sheets having coloring according to the Munsell value, and did not exhibit any specificity or unique coloring effect. As described above, since the decorative material of the present invention has the above-mentioned characteristics, it is suitable as an elegant decorative material for automobile interior materials, indoor interior materials, accessories for Japanese clothing, sandals, etc. . Furthermore, according to the method of the present invention, a decorative material having the above-mentioned unique decorative effect can be provided very simply and easily.

Claims (1)

[Scope of Claims] 1. A decorative material obtained by fusing a mixture of two or more colored thermoplastic resin powders with different hues into a desired shape without melt-kneading, wherein the powder has a particle size of 50 μm to 350 μm. Decorative materials characterized by: 2. The decorative material according to claim 1, wherein the colored thermoplastic synthetic resin powder is a colored dry blend powder of vinyl chloride resin. 3. The decorative material according to claim 1, which has a planar shape. 4. The decorative material according to claim 1, which has a three-dimensional shape. 5. Prepare multiple colors of colored thermoplastic synthetic resin powder with a particle size of 50 μm to 350 μm, and use two different colors of these powders.
1. A method for producing a decorative material, which comprises spreading a powder mixture of at least one kind on a substrate and fusing it without melting and kneading. 6. The method for producing a decorative material according to claim 5, wherein the colored thermoplastic synthetic resin powder is a dry blend powder of vinyl chloride resin. 7. The method for producing a decorative material according to claim 5, wherein the substrate is a non-peelable sheet of paper, cloth, nonwoven fabric, wood, metal, etc. 8. The method for producing a decorative material according to claim 5, wherein the substrate is a releasable carrier such as release paper. 9. The method for producing a decorative material according to claim 5, wherein the substrate is of a removable type.