JP2001261980A - Resin molded product having designability, method for producing the same and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having high designability and capable of exhibiting an iris suitable for building materials or sanitary articles and to provide a method for producing the resin molded product. SOLUTION: This resin molded product having the designability comprises (a) particles exhibiting an iris and (c) a substrate resin. The resin molded product has 0.001-50% occupancy of surface area of the particles (a) on a significant surface of the resin molded product and 50-99.999% occupancy of the total surface area of the surface area of parts which are achromatic and the surface area of parts which are chromatic and have <=2 Munsell lightness of the substrate resin (c) on the significant surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin molded product having a design property, its production method and use.

[0002]

2. Description of the Related Art Natural opals that exhibit an iris have excellent design properties, but are expensive. The structure of natural opal is
Since it was found that the silica fine particles had a structure in which the silica fine particles were regularly arranged three-dimensionally, techniques for artificially producing particles exhibiting an iris have been studied for many years.

[0003] Japanese Patent Publication No. Sho 48-44652, Japanese Patent Publication No. Sho 48-
No. 46653 and Japanese Patent Publication No. 53-31173 specify the difference in the refractive index between the suspending medium and the polymer beads, the degree of swelling of the polymer beads in the suspending medium, the effective volume fraction of the polymer beads and the center-to-center distance, and the like. It is disclosed that the iris-expressing particles can be produced by performing the method.

[0004] However, this method requires monodispersed polymer beads and requires a long time for the arrangement of the polymer beads, so that the particles are also expensive. Therefore, the particles that express the iris are not widely used.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin molded product having a design even if the content of particles expressing the iris is small.

[0006]

Means for Solving the Problems The present inventor has found that a resin composition having a design property can be obtained under specific conditions by using a combination of particles exhibiting iris and a base resin.

[0007] The gist of the present invention is a resin molded product comprising particles (a) exhibiting an iris and a base resin (c), and the occupancy of the surface area of the particles (a) on the significant surface of the resin molded product. Is 0.001 to 50%, and the occupation ratio of the surface area of the achromatic portion (c) and the chromatic color and the surface area of Munsell brightness 2 or less in the significant surface is 50 to 99. 0.999% in a resin molded product having a design property.

[0008] Further, the gist of the present invention resides in a method for manufacturing the above-mentioned resin molded article, and a building material and a sanitary article comprising the above-mentioned resin molded article.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The resin molded article of the present invention comprises particles (a) exhibiting iris and a base resin (c). In the present invention, the significant surface means a surface of the resin molded product which is visible to a human in a normal use state of the resin molded product. For example, when used as a flooring material, the significant surface is the upper surface side of the floor.

[0010] Examples of the particles (a) expressing the iris include natural products and artificial products.

[0011] Natural products include opal.

The artificial substance, that is, the particle (a) which expresses an artificially produced iris has an average particle diameter of 0.15 to 1.5 μm.
Particles having a structure in which m transparent spherical particles (a1) are regularly three-dimensionally arranged in a medium (a2) so as to satisfy the Bragg reflection condition of visible light. If the average particle size is too small or too large, the expression of the iris decreases, which is not preferable. The average particle diameter of the spherical particles (a1) is preferably uniform, and 80% or more of the whole particles are ±± of the average particle diameter.
The particle diameter is preferably within 10%. The spherical particles (a1) need to be transparent in order to develop an iris.

The spherical particles (a1) include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate;
Acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and amyl acrylate, styrene, methyl styrene,
Spherical particles of a crosslinked polymer comprising at least one polymerizable monomer unit selected from styrene derivatives such as ethylstyrene, chlorostyrene, and dichlorostyrene, and a polyfunctional polymerizable monomer unit copolymerizable therewith. a1) is preferred. Spherical particles (a1) of a crosslinked polymer composed of at least one polymerizable monomer unit selected from methacrylates, styrene and styrene derivatives and a polyfunctional polymerizable monomer unit copolymerizable therewith are more preferred.

As the copolymerizable polyfunctional polymerizable monomer, divinylbenzene, ethylene glycol dimethacrylate and the like are preferable.

The medium (a2) in which the spherical particles (a1) are regularly arranged is preferably a transparent resin having a different refractive index from the spherical particles (a1). Examples of the monomer unit constituting the resin include those exemplified as the polymerizable monomer unit and the polyfunctional polymerizable monomer unit constituting the above-mentioned crosslinked polymer for the spherical particles (a1). The medium (a2) is preferably a crosslinked resin.

The transparent spherical particles (a1) which are regularly arranged three-dimensionally in the medium (a2) and which exhibit an iris satisfying the Bragg reflection condition of visible light include the following particles (a):
The particles disclosed in JP-B-53-31173 are exemplified.

The base resin (c) constituting the resin molded article of the present invention
Examples include methacrylic resin, styrene resin, unsaturated polyester resin, ABS resin, vinyl ester resin, epoxy resin and the like. The base resin may contain a filler. In this case, it is preferable to further add 10 to 400 parts by weight of at least one filler selected from aluminum hydroxide, calcium carbonate, silica, barium sulfate, talc, mica and the like to 100 parts by weight of the base resin. The filler may be uniformly mixed in the base resin. Filler-containing particles obtained by pulverizing a resin containing a filler may be blended in the base resin.

The occupation ratio of the surface area of the particles (a) on the significant surface of the resin molded product of the present invention is 0.001 to 50%.
When the occupation ratio of the surface area is smaller than 0.001%, the expression of the iris is reduced, and the design property is reduced. It is preferably at least 0.01%, more preferably at least 0.1%, even more preferably at least 1%. If the occupation ratio of the surface area is more than 50%, it is economically disadvantageous. 45
% Or less, more preferably 35% or less.

When the occupation ratio of the surface area of the particles (a) in the resin molded article is the same, although the size of the particles (a) is larger and the number is smaller than that of the particles (a) having a smaller size and a larger number. It is more preferable to improve the design.

The shape of the particles (a) itself is preferably a three-dimensional shape. The shape of the particles (a) on the significant surface of the resin molded article may be any shape. In order to exhibit an iris and impart a design property to the resin molded product, the resin molded product is preferably not a long and thin linear shape but an irregular shape other than a polygonal or linear shape. Moreover, it may be circular. Particle (a)
The length or the diameter of the long side is preferably from 0.01 to 10 mm, more preferably from 1 to 5 mm. The length of the short side is preferably 0.005 mm or more, and more preferably 0.5 mm or more. If the side or the diameter is too short, the expression of the iris decreases, which is not preferable. If the length is too long, the particles (a) become expensive, which is not preferable.

The occupation ratio of the surface area of the achromatic portion of the base resin (c) on the significant surface of the resin molded article and the surface area of the chromatic color and the surface area of Munsell brightness 2 or less is 50 to 99. 0.999%. More preferably, it is at least 65%. If it is 50% or more, the iris in which the particles (a) appear can be effectively enhanced even if the occupancy of the particles (a) in the significant plane is low. It is preferable that the occupation ratio of the surface area of a portion having a chromatic color and a Munsell brightness larger than 2 is low.

Either the occupancy of the surface area of the achromatic portion on the significant surface alone is 50% or more, or the occupancy of the surface area of the chromatic color and the Munsell brightness of 2 or less on the significant surface alone is 50%. It is preferable that it is above.

In a significant aspect, it is preferable that the particles (a) be present in a large amount in the periphery of the base resin (c) where the particles are achromatic, or where the particles are chromatic and have a Munsell brightness of 2 or less. .

It is preferable that a transparent resin layer having a thickness of 3 μm to 15 mm is further provided on at least a part of the significant surface of the resin molded product of the present invention, since a sense of depth is exhibited on the significant surface having design.
More preferably, the thickness is 10 μm to 10 mm.
An acrylic resin layer etc. are mentioned as a transparent resin layer.

[0025] The resin molded article of the present invention is produced by a method in which the particles (a) are pressure-bonded to the resin at a temperature not lower than the softening temperature of the resin or the resin containing the filler formed into a predetermined shape and integrated. Can be. The shape of the particles (a) is preferably a three-dimensional shape. The length of the long side is 0.01-10m
m, more preferably 1 to 5 mm. The length of the short side is preferably 0.005 mm or more, and more preferably 0.5 mm or more.

Further, the particles (a) are mixed with a granular resin, a granular resin containing a filler, or a filler and a granular resin,
It can be manufactured by a method of molding by at least one method selected from injection molding, extrusion molding and press molding while melting the resin. The granular resin is melted and molded to become a base resin. The term “granular” refers to powder, flake, pellet, and the like.

Further, it can be produced by a method in which a mixture obtained by mixing the particles (a) and a polymerizable raw material, or a filler-containing mixture further containing a filler is polymerized and cured. The resin molded article of the present invention can also be laminated on the surface of an article by applying the mixture or the filler-containing mixture to an article such as plastic, glass, or metal and polymerizing and curing the applied mixture. Examples of the polymerizable raw material include a monomer that becomes a base resin by polymerization, and a syrup composed of a monomer and a polymer of the monomer.

Further, a dispersion in which the particles (a) are dispersed in a volatile liquid is applied to at least a part of the significant surface of the base resin (c) or the base resin (c) containing a filler, and the volatile liquid is evaporated. It can be manufactured by a method of volatilizing an ionic liquid. The dispersion liquid is applied to the inner surface of the molding die, and after the volatile liquid is volatilized, the base resin (c) or the base resin (c) containing a filler is filled in the mold in a molten state. It can be manufactured by a method of cooling and releasing. The dispersion liquid is applied to the inner surface of the mold, and after the volatile liquid is volatilized, a polymerizable raw material or a polymerizable raw material containing a filler is filled and solidified by polymerization. it can.
Examples of the volatile liquid include toluene, xylene, and ethyl acetate.

Further, the mixture for coating film obtained by mixing the particles (a) and the polymerizable raw material for coating film is applied to at least a part of the significant surface of the base resin (c) or the base resin (c) containing the filler. It can also be manufactured by a method of applying and polymerizing and curing the mixture for a coating film. After applying the mixture for coating film to the inner surface of the mold in the form of a thin film, the inside of this mold is filled with the base resin (c) or the base resin (c) containing a filler in a molten state to form a coating. The mixture can be produced by a method of polymerizing, solidifying and releasing the mixture. After applying the mixture for coating film in the form of a thin film on the inner surface of the mold, the polymerizable raw material or the polymerizable raw material containing a filler is filled, and the mixture for coating film and the polymerizable raw material are polymerized and solidified, and released. It can be manufactured by a method.
As the polymerizable raw material for a coating film, a material which is polymerized to a transparent coating film such as methyl methacrylate is preferable.

When a transparent coating film containing the particles (a) is present on at least a part of the significant surface of the base resin (c), the visible surface occupancy of the particles (a) on the significant surface is 0.1%.
It is preferably 001 to 50%. The surface area of the achromatic portion and the chromatic color of both the base resin (c) having no transparent coating film and the base resin (c) having a transparent coating film on the significant surface and Munsell The occupancy of the surface area including the surface area of the portion having the brightness of 2 or less is 50 to 9
It is preferably 9.999%.

The particles (a) constituting the resin molded product of the present invention are particles obtained by pulverizing the resin molded product produced by the above-mentioned method, wherein the particles (a) exhibiting an iris are used. The contained pulverized particles (hereinafter referred to as “coarse particles (b)”) can also be used. The coarse particles (b) and the particles (a) can be used in combination. The coarse particles (b) preferably have a three-dimensional shape. The length of the long side is preferably 0.02 to 20 mm, and more preferably 1 to 5 mm.
The length of the short side is preferably 0.01 mm or more,
More preferably, it is 0.5 mm or more.

When the coarse particles (b) are used, the base resin constituting the resin molded product before pulverization is preferably transparent. When a resin molded product is produced using the coarse particles (b) and the polymerizable raw material, the base resin constituting the resin molded product before pulverization is preferably a resin that does not dissolve in the polymerizable raw material.

[0033] The resin molded article of the present invention can be used for building materials and sanitary articles. Examples of building materials include table tops, flooring materials, wall materials, partition materials, and the like. Sanitary articles include bathtubs, washbasins, kitchen tops, and the like.

Further, it can be used for displays, interior products, miscellaneous goods and the like.

[0035]

The present invention will be specifically described below with reference to examples. In addition, the design property in an Example was evaluated by visual judgment.

[Example 1] A pulverized opal product having a side of 0.3 to 3 mm (hereinafter referred to as "OM") was used as the particle (a).
Was used. OM is dispersed on the upper surface side of Acrylite # 377 (acrylic resin plate manufactured by Mitsubishi Rayon Co., Ltd.), and both surfaces of the resin plate are sandwiched between two mirror-finished stainless steel plates, and heated at 160 ° C., 2 MPa, and 10 minutes. A resin molded article was manufactured by pressing. The surface area occupancy of the particles (a) on the significant upper surface is 0.30
%, And the surface area occupancy of the portion having a chromatic color and a brightness of 2 or less was 99.70%. Table 1 shows the evaluation results.

[Examples 2 to 14] Resin molded products were manufactured in the same manner as in Example 1 except that the type of the acrylic resin plate and the surface area occupancy of the particles (a) were changed. Table 1 shows the evaluation results.

Examples 15 to 30 Copolymers comprising 97.5% by mass of methyl methacrylate units and 2.5% by mass of divinylbenzene units, having an average particle size of 0.16 μm
Are regularly arranged three-dimensionally in a medium of a copolymer composed of 95% by mass of methyl methacrylate units and 5% by mass of divinylbenzene units.
(A) (hereinafter referred to as “PM”). PM
And a resin molded article was manufactured in the same manner as in Example 1 except that the type of the acrylic resin plate and the surface area occupancy of the particles (a) were changed. Table 2 shows the evaluation results.

Comparative Examples 1 to 6 Resin molded products were produced in the same manner as in Example 15 except that the type of the acrylic resin plate and the surface area occupancy of the particles (a) were changed. Table 3 shows the evaluation results.

Example 31 0.03 parts by mass of PM was dispersed in 100 parts by mass of a polymerizable raw material in which 25% by mass of a crushed product of acrylite # 377 was dissolved in 75% by mass of methyl methacrylate. Further, 0.05 parts by mass of azobisisobutyronitrile as a polymerization initiator was further dissolved to obtain a mixture. The mixture was poured into a cell composed of two glass plates and a gasket made of vinyl chloride, and was molded in a 10 mm thick resin plate over 2 hours in hot water at 60 ° C. and then 2 hours in an air bath at 120 ° C. The product was manufactured. In this resin molded product, the lower surface was regarded as a significant surface. Table 4 shows the evaluation results.

[Examples 32 to 39] A resin molded product was manufactured in the same manner as in Example 31 except that the type of the resin plate to be pulverized and dissolved and the amount of PM dispersed were changed. Table 4 shows the evaluation results.

Example 40 The resin molded product obtained in Example 38 was pulverized with a pulverizer to obtain coarse particles (b-1) having a side of 0.1 to 20 mm. 0.5 part by mass of the coarse particles (b-1) was mixed with 100 parts by mass of a transparent vinyl ester resin and a redox polymerization initiator to obtain a mixture for a coating film. The mixture for a coating film was applied on an unsaturated polyester artificial marble having a Munsell lightness of 1.2 and cured at room temperature. The surface area occupancy of the particles (a) on the significant surface of the obtained resin molded product was 0.3%. A vivid iris was developed and the design was high.

Example 41 The coarse particles (b-1) obtained in Example 40 were further pulverized and classified, and one side was 0.01%.
~ 0.08 mm of coarse particles (b-2) were obtained. One part by mass of the coarse particles (b-2) was mixed with 100 parts by mass of a black acrylic resin having a Munsell brightness of 0.5 (Dianal LR-162 manufactured by Mitsubishi Rayon Co., Ltd.) together with a redox polymerization initiator, and zinced. Painted on steel plate. The surface area occupancy of the particles (a) on the painted significant surface was 0.6%. A vivid iris was developed and the design was high.

Example 42 10 parts by mass of the coarse particles (b-1) obtained in Example 40, 100 parts by mass of Acrypet MD (acrylic resin molding material manufactured by Mitsubishi Rayon Co., Ltd.), and an average as a colorant 3 parts by mass of barium sulfate powder having a particle size of 6 μm were mixed, and a plate-shaped resin molded product having a plate thickness of 3 mm was produced by injection molding.

The ratio of the surface area of the particles (a) on the significant surface is 0.1.
08%, a vivid iris was developed on an achromatic white background, and the design was high.

Example 43 2.5 parts by mass of the coarse particles (b-1) obtained in Example 40 were mixed with 100 parts by weight of a transparent vinyl ester resin and a redox polymerization initiator to prepare a mixture for a coating film. Obtained. An acrylic resin plate (Acrylite PX, 5 mm thick transparent product manufactured by Mitsubishi Rayon Co., Ltd.) was molded into a bathtub shape, and the mixture for a coating film having a thickness of 0.5 was applied from the back surface of the molded product.
mm and polymerized and cured. It contains 20% by mass of glass fiber and 20% by mass of calcium carbonate from above,
Unsaturated polyester resin colored with black paint, thickness 3
mm and cured. The surface area occupancy of the particles (a) on the significant surface of the obtained molded article was 0.03.
%, The Munsell lightness was 1.0.

The iris floated on a black background, and the surface layer had a sense of depth due to the presence of the transparent acrylic resin, and the design was high.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

[0051]

[Table 4]

[0052]

Industrial Applicability The resin molded product of the present invention has a high design even if the content of the particles (a) expressing the iris is small, and is suitable for building materials and sanitary articles.

Continued on the front page F-term (reference) 4F071 AA22 AA33 AA42 AA49 AB26 AE09 AH03 BA01 BB03 BB05 BB06 BC09 4J002 BC021 BC042 BF011 BG052 BG061 BN151 CD001 CF211 DE147 DE237 DG047 DJ006 DJ017 DJ047 FD017PA090109

Claims (11)

[Claims] 1. A resin molded product comprising particles (a) expressing an iris and a base resin (c), wherein the occupation ratio of the surface area of the particles (a) on a significant surface of the resin molded product is 0.001.
And the occupation ratio of the surface area of the achromatic portion of the base resin (c) and the chromatic color and the surface area of the Munsell lightness of 2 or less in the significant surface is 5%.
A resin molded product having a design property of 0 to 99.999%. 2. With respect to 100 parts by mass of the base resin (c),
The resin molded product according to claim 1, further comprising 10 to 400 parts by mass of a filler. 3. The resin molding according to claim 1, wherein a transparent resin layer having a thickness of 3 μm to 15 mm is a laminated body further present on at least a part of the significant surface. Goods. 4. The resin according to claim 1, wherein the particles (a) are pressure-bonded to the resin at a temperature equal to or higher than the softening temperature of the resin formed into a predetermined shape or the resin containing a filler to be integrated. Manufacturing method of molded article. 5. Mixing the particles (a) with a granular resin, a granular resin containing a filler, or a filler and a granular resin,
The method for producing a resin molded product according to claim 1 or 2, wherein the resin is molded by at least one method selected from injection molding, extrusion molding, and press molding while the resin is being melted. 6. The method for producing a resin molded article according to claim 1, wherein a mixture obtained by mixing the particles (a) and the polymerizable raw material or a filler-containing mixture further containing a filler is polymerized and cured. 7. A dispersion in which the particles (a) are dispersed in a volatile liquid is applied to at least a part of the base resin (c) or the base resin (c) containing a filler, and the volatile liquid is applied. The method for producing a resin molded product according to claim 1, wherein the resin molded product is volatilized. 8. A building material comprising the resin molded product according to any one of claims 1 to 3. 9. The building material according to claim 8, wherein the building material is any one selected from a table top, a floor material, a wall material, and a partition material. 10. A sanitary article comprising the resin molded article according to any one of claims 1 to 3. 11. The sanitary article according to claim 10, wherein the sanitary article is any one selected from a bathtub, a sink, and a kitchen top.