JP2001287318A - Recycled plastic product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a product without being affected by colors of the original plastic materials, in recovering and reutilizing plastic materials having various hues widely used in household electric products, car parts, industrial members or the like from a viewpoint of the protection of global environment. SOLUTION: A recycled plastic product is provided by decorating the surface of a molded article, which is formed from a recovered plastic material, by a colored film with a thickness of 50-600 μm comprising an ultraviolet absorber- containing acrylic resin. The acrylic resin film used herein is colored to a degree capable of concealing the color of the substrate recovered resin and may have a single-layer or multilayer structure. By mixing a physical property modifying and enhancing agent with the recovered plastic material, more effective recycling becomes possible.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recycled plastic product obtained by decorating a molded product made of recovered plastic with an acrylic resin film.

[0002]

2. Description of the Related Art As a method of recycling collected plastic products, pellets are often re-pelletized and used for outdoor piles and the like. The reason for this is that, for plastics collected from home appliances, automobile parts, and industrial parts, although the type of resin used in them can be determined, they are colored in various colors, and stains and fading due to use are also observed. Therefore, the color tone when reused is inevitably forced to be a dark color, generally black.

[0003] On the other hand, acrylic resin films are excellent in transparency, so they are widely used for decorating the surface of molded articles while being transparent, or subjected to printing or coloring. Examples of the molded article covered with the acrylic resin film include molded articles made of polycarbonate resin, acrylonitrile-butadiene-styrene (ABS) resin, polystyrene (PS) resin, polypropylene (PP) resin, and the like. . In general, acrylic resin is excellent in weather resistance, for example, JP-B-47-19119
JP (= US 3,594,264), JP-A-55-59929 (= GB
2,028,228) and JP-A-4-270652 have proposed a method of coating the surface of a polycarbonate resin sheet or the like. Such acrylic resin films include:
Adhesiveness with the resin molded article to be coated is required, and it is also required to maintain the transparency of the acrylic resin while being colored.

[0004]

SUMMARY OF THE INVENTION Accordingly, the present inventors
From the standpoint of global environmental protection, plastics such as ABS resin, PS resin, olefin resin, acrylic resin, etc., which are widely used in home appliances, automotive parts or industrial parts and have a wide variety of colors, are used. As a result of intensive studies on reuse, the surface of the collected plastic molded parts is decorated with a specific acrylic resin film, so that the acrylic resin is not affected by the colors of the various collected members. The present inventors have found that a surface-decorated product having a deep coloration can be obtained while maintaining the transparency of the film, and have led to the present invention.

[0005]

That is, according to the present invention, the surface of a molded article made of recovered plastic is made to have a thickness of 50 to 600 μm made of an acrylic resin containing an ultraviolet absorbent.
And a recycled plastic product decorated with a colored film.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The recycled plastic constituting the recycled plastic product of the present invention may be any thermoplastic resin recovered from used home electric appliances, automobile parts, industrial parts, etc., and there is no particular limitation. . For example, polystyrene, high impact polystyrene (HIPS),
Styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile- (ethylene-propylene rubber) -styrene (AES) resin,
Acrylonitrile-acrylic rubber-styrene (AA
S) Resin, styrene resin such as acrylonitrile-chlorinated polyethylene-styrene (ACS) resin, ester resin such as polycarbonate, polybutylene terephthalate, polyethylene terephthalate, modified polyphenylene ether resin, acrylic such as polymethyl methacrylate Resins, polyolefin resins, and the like. Usually, it is molded using a crushed product of these collected plastics.

As an acrylic resin used as a film for coating a molded article made of such recovered plastic, for example, polyalkyl methacrylate, a copolymer of alkyl methacrylate and alkyl acrylate, and the like are suitable. is there. The copolymer is, for example, 50-99% by weight of alkyl methacrylate and 50-1% of alkyl acrylate.
% By weight copolymers are preferred. Further, other monomers may be contained as a copolymer component as long as the object of the present invention is not impaired. Here, as the alkyl methacrylate, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate and the like can be mentioned, but methyl methacrylate is particularly preferable. As the alkyl acrylate, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate,
Examples thereof include butyl acrylate, isobutyl acrylate, hexyl acrylate, and octyl acrylate. The alkyl in the alkyl acrylate has 1 to 1 carbon atoms.
It may be about 0, but particularly preferably has 2 or more carbon atoms. As such an acrylic resin, general-purpose commercial products can be used. In addition, although what is called impact-resistant acrylic resin is contained in this, what does not contain impact-resistant acrylic resin as a surface layer is preferable from a viewpoint of weather resistance and chemical resistance. On the other hand, from the viewpoint of the flexibility of the film, it is preferable to use an impact-resistant acrylic resin for the colored layer of the colored single-layer film or the multilayer film.

The acrylic resin used in the present invention preferably has a glass transition temperature in the range of 40 to 110 ° C. and a weight average molecular weight in the range of 70,000 to 700,000. The glass transition temperature is measured using a differential scanning calorimeter under a nitrogen atmosphere at a heating rate of 10 ° C./min. The weight average molecular weight is measured by gel permeation chromatography (GPC). If the glass transition temperature is too low, a film having a required surface hardness tends not to be obtained. On the other hand, if the weight average molecular weight is too small, the melt viscosity of the polymer will be too low, and the moldability when processing into a film will be poor, and sufficient thickness accuracy will not be obtained. On the other hand, if the weight average molecular weight is too large, the melt viscosity of the polymer is too high, and the moldability when processing into a film is deteriorated, and a gel-like foreign matter is generated in the obtained film, which tends to cause a problem. There is a tendency. Generally, the glass transition temperature of an acrylic resin is generally in the range of 30 to 110 ° C.,
The acrylic resin applied to the present invention is, among general acrylic resins, a glass transition temperature of 40 to 1 which is slightly higher.
What is in the range of 10 ° C. may be appropriately selected. The glass transition temperature of the acrylic resin is preferably 60 ° C. or higher and 106 ° C. or lower. Since the glass transition temperature of the acrylic resin is determined by the composition of the monomer, the monomer composition may be selected so that the glass transition temperature falls within the range described here.

As the acrylic resin, a polymer or a copolymer may be used alone or as a mixture of two or more polymers or copolymers. In particular, in order to increase the surface hardness of the film, it is advantageous to use a mixture containing at least one polymer or copolymer having a weight average molecular weight in the range of 70,000 to 200,000. Furthermore, in order to have both moldability improvement and surface hardness improvement such as preventing the occurrence of irregularities during thermoforming after film formation,
A component having a weight average molecular weight in the range of 70,000 to 200,000 and a component having a weight average molecular weight in the range of 150,000 to 700,000,
Advantageously, each is a mixture comprising at least one type. In this case, the weight average molecular weight of the latter component is 15
In the range of 10,000 to 700,000, the weight average molecular weight of the former component is made larger. When observing the molecular weight distribution measured by GPC in a chart, such a mixture exhibits a form with an expanded base or a form with a shoulder.
The components having a weight-average molecular weight of 70,000 to 200,000 suitably have a glass transition temperature in the range of 90 to 110 ° C, and the components having a weight-average molecular weight of 150,000 to 700,000 have a glass transition temperature of Suitably, it is in the range of 40-80 ° C.

It is also effective to use a composition containing an impact-resistant acrylic resin which is a single-layer or multilayer acrylic rubber particle. In particular, an acrylic polymer having a multilayer structure including a rubber elastic layer is advantageous, and it includes at least two layers,
Preferably, it is an acrylic polymer having a multilayer structure of three layers. Examples of the acrylic polymer having such a multilayer structure include, for example, a copolymer of an alkyl acrylate having 4 to 8 carbon atoms of an alkyl and a polyfunctional monomer, and if necessary, another monofunctional monomer. An acrylic polymer having a two-layer structure having a rubber elastic body as an inner layer and a hard polymer containing methyl methacrylate as a main component as an outer layer, and a hard polymer containing methyl methacrylate as a main component as an innermost layer, Has 4 carbon atoms
Hard polymer mainly composed of methyl methacrylate as a rubber elastic body composed of a copolymer of alkyl acrylates and polyfunctional monomers, and other monofunctional monomers as required, as an intermediate layer Is an outermost layer, and an acrylic polymer having a three-layer structure is preferred. Of these, the latter three-layer structure is preferable. Acrylic polymer having a multilayer structure is described in, for example,
It can be produced by a method described in, for example, US Pat. No. 27576 (= US 3,793,402). The polyfunctional monomer used here is
Compounds having at least two polymerizable carbon-carbon double bonds in the molecule, such as alkenyl esters of unsaturated carboxylic acids such as allyl (meth) acrylate and methallyl (meth) acrylate, and diallyl maleate And dicarboxylic acid diesters of glycols such as alkylene glycol di (meth) acrylate.

The average particle size of the impact-resistant acrylic polymer is as follows:
Usually it is 50 to 500 nm. This average particle size is preferably 100 nm or more, more preferably 250 nm or more, and preferably 400 nm or less, more preferably 3 nm or less.
It is 50 nm or less. If the particle size is too small, the impact resistance of the resulting film tends to be low, while if the particle size is too large, the transparency of the film tends to be low. The impact-resistant acrylic resin composition is
For example, it can be easily manufactured by kneading an acrylic resin and an impact-resistant acrylic resin containing a rubber elastic layer. This composition may also contain other polymer components as long as the object of the present invention is not impaired.

Such an acrylic resin composition is excellent in moldability to a film, for example, extrusion casting by a chill roll, an extrusion molding method in which both sides of the film are brought into contact with the roll surface, and both sides in contact with a metal belt. The film can be easily formed into a film by a belt cooling extrusion method, an inflation extrusion molding method, a solvent casting method, or the like. Furthermore, at the time of general film forming, a method of arranging a screen mesh such as a metal or a sintered ceramic in a passage of a molten resin is used for the purpose of preventing foreign matter from being mixed in.In the case of using a fine mesh, In some cases, clogging may occur immediately, and the production line must be frequently shut down to remove the clogging. In such a case, a rotary screen changer (for example, manufactured by Gnois, Germany) can be used without stopping the production line.
It is possible to produce a film in which a foreign substance of 100 μm or less that inhibits optical performance or printability is not mixed.

Since the film thus obtained has sufficient thickness accuracy, surface smoothness, surface hardness, and excellent moldability, it is necessary to reduce external haze and to prevent printing omission which is a characteristic of printing a pattern. And it is optimally used for the injection molding simultaneous bonding method and the surface coating method. Among them, it is preferable to form the film-like material obtained by melt extrusion molding in a state in which both surfaces are simultaneously in contact with the surface of the metal roll or the surface of the metal belt from the viewpoint of film thickness accuracy and surface smoothness.

The film thus obtained may be used by printing a pattern on one side, or may be provided with an adhesive or antistatic coating on the outermost layer. Further, a film which has been previously subjected to thermoforming such as vacuum forming to give a shape may be used for simultaneous lamination with injection molding. further,
It is also possible to use another resin, for example, a film made of another acrylic resin, a vinyl chloride resin, a transparent ABS resin, a polycarbonate resin, a polyolefin resin, or the like, or a film having a structure backed by a sheet. In particular, composite films combining a colored acrylic resin and a transparent acrylic resin make use of the depth of the colored layer that can be seen through the transparent layer and the characteristics of the weather resistance and surface hardness of the acrylic resin to make bumpers, garnishes, Further, it is effective as a paint substitute for an outer panel of an automobile such as a side molding or a home electric appliance. As a film forming method in this case, a multilayer film forming method by a multilayer extrusion method is most suitable.

In this multilayer film, it is possible to combine films by changing the acrylic resin composition, or as a surface layer of the acrylic resin composition containing a rubber elastic layer, a general-purpose film not containing a rubber elastic body can be used. A surface layer made of an acrylic resin may be provided. If this multilayer film having a transparent layer made of a general-purpose acrylic resin is used, a surface pencil hardness of 2H can be obtained. When a transparent acrylic resin is used as the surface layer, the transparent acrylic resin preferably has a weight average molecular weight in the range of 70,000 to 600,000. More preferable weight average molecular weight is 120,000 or more and 300,000 or less. Further, the transparent acrylic resin preferably has a glass transition temperature of 60 to 110 ° C. A more preferable glass transition temperature is 75 ° C. or higher and 106 ° C. or lower.

The thickness of the film used in the present invention is 50 to 50.
600 μm, preferably 100-600 μm.
m. In order to industrially manufacture the recycled plastic product of the present invention, it is desirable to use a method of continuously supplying a film. Therefore, when the film thickness is 60
If it exceeds 0 μm, it is not preferable because it cannot be wound in a continuous roll form. Further, when a film is continuously supplied, a film thickness of 100 to 300 μm is preferable from the viewpoint of reduction in winding weight and moldability during vacuum forming. In the case of a film thickness exceeding 300 μm, it is advantageous to feed the film into the mold every leaf.

When the product of the present invention is manufactured by the simultaneous lamination method of the injection molding, the resin melt-injected in the mold is, as described above, various kinds of heat recovered from home electric appliances, automobile parts, industrial members and the like. It can be a plastic resin. The use of a resin composition containing an acrylic resin in the range of 10% by weight or less in these melt-injected resins is advantageous in that the adhesion to a film is improved. Injection simultaneous lamination method is disclosed in, for example, Japanese Patent Publication No. 63-6339 (= US 4,545,752),
The method can be carried out according to the method described in JP-A-9-9647, JP-A-7-9484 and the like. That is, open the female mold and the male mold that form the cavity space, insert a film between both molds, close both molds with the film in between, close the mold, and remove the thermoplastic resin melted from the gate. The cavity is injection-filled and cooled and solidified, whereby a film is adhered and integrated on the surface of the injected molded body, and then both dies are opened to obtain a laminated molded product. Conditions such as resin temperature and injection pressure for injection molding are set to appropriate values in consideration of the type of resin to be injected and the like.

In the present invention, the surface of a molded article made of recovered plastic is decorated with a colored film of an acrylic resin containing an ultraviolet absorber. As the ultraviolet absorber, those similar to those added to ordinary acrylic resins can be used. Specifically, benzotriazole-based and benzophenone-based ultraviolet absorbers can be used alone or in combination of two or more. Used in combination. A benzotriazole-based ultraviolet absorber having a large molecular weight is preferable from the viewpoint of reducing volatile components from the film and preventing deterioration of the underlayer. As a suitable benzotriazole-based ultraviolet absorber, for example, 2,2'-methylenebis [6- (2H
-Benzotriazol-2-yl) -4- (1,1,
3,3-tetramethylbutyl) phenol], 2- [2
-Hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole.

When a single-layered colored film is used, an ultraviolet absorber may be present therein, but when a multi-layered film is used, the ultraviolet-absorbing agent is contained in the acrylic resin of the first layer (surface layer). It is preferable to include an agent. By including the ultraviolet absorber in the surface layer as described above, it is possible to suppress the fading of the second and lower layers including the colored layer. The amount of the UV absorber used is usually 0.1 to 2% by weight per acrylic resin constituting the monolayer film, and per acrylic resin constituting the surface layer when forming the multilayer film. It is about.

The acrylic resin composition constituting the film may contain other usual additives. Such additives include, for example, hindered phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, weathering agents such as hindered amine light stabilizers, flame retardants, coloring agents,
Examples include pigments and inorganic fillers.

In the case of a single-layer film, the film itself may have the above-mentioned thickness. However, in the case of a multi-layer film, the thickness of the surface layer is desirably about 50 to 200 μm. If the thickness is less than 50 μm, the transparent depth of the acrylic resin film is likely to be impaired, and ultraviolet rays are likely to be transmitted, so that there is a high possibility that the fading of the second layer including the colored layer cannot be sufficiently suppressed. More preferably, the thickness is 80 μm or more. When the thickness of the surface layer exceeds 200 μm, the impact strength of the film becomes weak. The thickness of the surface layer is preferably 150 μm or less.

As the acrylic resin and the acrylic rubber, those obtained by mixing these are commercially available, and the commercially available products can be used. Examples of such commercially available products include “Orograss DR” (trade name) manufactured by Athaas Co., Ltd.
"Sumipex HT" (trade name) manufactured by Sumitomo Chemical Co., Ltd. and the like. The amount of the acrylic rubber particles used in the impact-resistant acrylic resin is usually 5 to 50% by weight per acrylic resin.

In the case of forming a multilayer film, the colored layer preferably has a thickness in the range of about 150 to 400 μm.
When the thickness is less than 150 μm, the color scale tends to be remarkable due to the thinness after vacuum forming, and is preferably 200 μm or more. On the other hand, if it exceeds 400 μm, it tends to be more expensive than necessary. For coloring the film, for example, a colorant such as a dye or a pigment may be contained in an acrylic resin constituting the film, and a dye or a pigment is appropriately selected and used according to a desired color. The content of the coloring agent is usually about 1 to 20% by weight in the resin composition constituting the coloring layer.

[0024] Further, by coloring by adding a metal powder, a metallic color can be obtained. As the metal powder, a flat metal powder such as a flat aluminum piece is preferably used. Further, by containing surface-treated mica or the like, it is possible to obtain a pearl color. When metal powder or mica is used, its amount is 1 to 10% by weight in the resin composition constituting the colored film.
It is about. Metal powder, mica and the like may be used in combination with the above-mentioned coloring agents, or may be used alone. When a metal powder or mica is used in combination with a coloring agent, a metallic or pearly and colored acrylic resin film can be obtained. When the metal powder is used alone, a metallic color having a color tone corresponding to the type of metal used is obtained. Specifically, when an aluminum piece is used alone, the color becomes silver metallic.

In the acrylic resin film used in the present invention, an adhesive backing layer may be laminated on the side in contact with a molded product made of recovered plastic. In this case, it is appropriate that the thickness of the adhesive backing layer is 150 μm or more. Since such a backing layer is laminated, the adhesion between the acrylic resin and the recovered polyolefin resin, which is difficult to adhere to the acrylic resin, is increased, and the color of the recovered molding resin can be seen through the acrylic resin film. Can be prevented, or the color sag can be improved. When a backing layer is provided on the multilayer film, a transparent acrylic resin containing an ultraviolet absorber is provided on the surface layer, an opaque colored acrylic resin is provided on the second layer below the backing layer, and a backing layer is provided on the third layer thereunder. Advantageously.

In the present invention, the recovered plastic can be used as it is when the physical properties, such as impact resistance, are satisfied, but can be used as it is. 0.01 to 30% by weight
It is preferable to add and mix at a ratio of More preferably,
The physical property improving enhancer is blended at a ratio of 1 to 30% by weight.
By mixing the physical property improving agent in this way, the number of times of reuse of the collected plastic is significantly increased, and the collected plastic can be repeatedly collected and recycled.

[0027] The physical property improving and strengthening agent referred to herein is a chemical agent added to plastics to improve the physical properties, particularly the strength, of plastic products. Examples of such physical property improving and reinforcing agents include various elastomers, rubbers, and grafts. Polymers. Elastomers include thermoplastic elastomers such as polyester-based elastomers, polyurethane-based elastomers, and polyamide-based elastomers.Rubbers include polybutadiene rubber, butadiene-styrene copolymer rubber, butadiene-acrylonitrile copolymer rubber, and isoprene-based rubber. Diene rubbers such as chloroprene rubber, ethylene-butene copolymer rubber, ethylene-propylene rubber such as ethylene-propylene copolymer rubber and ethylene-propylene-non-conjugated diene copolymer rubber, acrylic ester Rubbers, silicone rubbers, and the like, and the graft polymer includes those obtained by polymerizing a vinyl monomer on these rubbers. Above all, a graft polymer obtained by polymerizing at least an aromatic vinyl monomer on rubber is preferable. in this case,
A graft polymer obtained by polymerizing a vinyl cyanide monomer together with an aromatic vinyl monomer is also advantageous. These physical property improving and strengthening agents are particularly advantageously used when the recovered plastic is the styrene resin described above.

As the rubber constituting the graft polymer which is a physical property improving agent, the above-mentioned rubbers can be used. In particular, diene rubbers such as polybutadiene, butadiene-styrene copolymer rubber, and ethylene- Propylene rubber, ethylene-propylene rubber, as a third component ethylidene norbornene, dicyclopentadiene,
An ethylene-propylene-non-conjugated diene copolymer rubber into which a non-conjugated diene component such as 1,4-hexadiene is introduced is preferable. More specifically, for example, when the ethylene content is 30 to 80% by weight, [ML (1 + 4) 121
° C.] ethylene-propylene-non-conjugated diene copolymer rubber having a Mooney viscosity in the range of 40 to 80,
Particularly preferred examples are given. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, bromostyrene, and the like, and one or more of these may be used. Among these, styrene or α-methylstyrene is particularly preferred.
Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and these can be used alone or in combination as desired.

It is also possible to substitute a part of the aromatic vinyl monomer constituting the graft polymer with another monomer copolymerizable therewith. Such monomers include (meth) acrylate monomers such as methyl methacrylate and methyl acrylate, maleimide monomers such as N-phenylmaleimide and N-cyclohexylmaleimide, acrylic acid And unsaturated carboxylic acids such as methacrylic acid, itaconic acid and fumaric acid, and one or more of these can be used.

The aromatic vinyl monomer and the vinyl cyanide monomer are preferably used in a proportion of 50 to 100% by weight of the former and in a proportion of 0 to 50% by weight of the latter. The composition ratio of the rubber and the monomer (total) is not particularly limited, but it is preferable to use the rubber at a ratio of 10 to 80% by weight and the monomer (total) at a ratio of 90 to 20% by weight.
There is no special restriction on the graft ratio of the graft polymer,
Generally, it is preferably in the range of 10 to 150%, more preferably in the range of 30 to 100%.

Examples of the method of molding the product of the present invention include a simultaneous lamination injection molding method in a mold, a method in which a film formed once by thermoforming or the like is inserted into a mold and then injection molding, and a method of laminating a film during extrusion molding. There is a method of matching. of course,
A product obtained by subjecting the obtained product to secondary processing is also included in the present invention. For example, when a product with a matte surface is preferred, there is a method of transferring a surface such as a metal roll called matting or embossing during the production of a film, and in this case, the temperature of the metal roll to be transferred is, Mat after secondary processing by processing the film at a temperature higher than the secondary processing,
It is possible to prevent grain flow. In addition, as a method for obtaining a product with a matte surface, when the film of the present invention is surface-decorated and bonded, an extruded metal roll, a surface in contact with a film such as a mold used for thermoforming or injection molding, It becomes possible by matting or embossing.

The significance of the present invention is that, as described above, home electric appliances, automobile parts, industrial parts, etc. which have been used at least once for the protection of the global environment can be collected and the resin used therein can be reused. It is in. That is, according to the present invention, by using a resin obtained by pulverizing a product toned in various colors, by decorating the surface with an opaque colored acrylic resin film including a multilayer structure, A product that reuses the recovered plastic is obtained.

[0033]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, percentages and parts representing the content or the used amount are based on weight unless otherwise specified. Also,
The following raw materials were prepared, and these were appropriately used in the examples.

Acrylic resin I: A resin produced by a bulk polymerization method and comprising 99% of methyl methacrylate units and 1% of methyl acrylate units, having a glass transition temperature of 106 ° C. and a weight average molecular weight of 140,000.

Acrylic resin II: A resin produced by a bulk polymerization method, comprising 90% of methyl methacrylate units and 10% of methyl acrylate units, having a glass transition temperature of 95 ° C. and a weight average molecular weight of 120,000.

Acrylic resin III: A resin produced by a suspension polymerization method, comprising 80% of methyl methacrylate units and 20% of butyl acrylate units, having a glass transition temperature of 62 ° C. and a weight average molecular weight of 300,000.

Acrylic polymer A: JP-B-55-27576
Manufactured according to Example 3 of the US Patent Publication (= US 3,793,402)
The innermost layer is a crosslinked polymer polymerized with a small amount of allyl methacrylate in methyl methacrylate, and the intermediate layer is a soft polymer which is mainly composed of butyl acrylate and further polymerized with styrene and a small amount of allyl methacrylate. And a rubber three-layer structure in which the outermost layer comprises a hard polymer obtained by polymerizing methyl methacrylate with a small amount of ethyl acrylate, and has an average particle size of about 300 nm.

Acrylic polymer B: Japanese Patent Publication No. 55-27
No. 576 (= US Pat. No. 3,793,402), except that the innermost layer is manufactured without forming a crosslinked polymer layer, and the inner layer is mainly composed of butyl acrylate, and further contains styrene and a small amount of allyl methacrylate. Soft rubber elastic body polymerized using, the outer layer consists of a hard polymer polymerized using a small amount of ethyl acrylate in methyl methacrylate,
A spherical two-layer structure having an average particle size of about 300 nm.

Ultraviolet absorber: "Adecastab" manufactured by Asahi Denka Kogyo Co., Ltd., which is a benzotriazole-based compound having a large molecular weight.
LA-31 "(chemical name: 2,2'-methylenebis [6- (2
H-benzotriazol-2-yl) -4- (1,1,
3,3-tetramethylbutyl) phenol]).

Physical property improving reinforcing agent A: ethylene content 41
%, An iodine value of 15, a Mooney viscosity of 60, and 50 parts of ethylene-propylene-dicyclopentadiene rubber, 35 parts of styrene and 15 parts of acrylonitrile, which are graft-polymerized by a suspension polymerization method so as to have a graft ratio of 40%.

Physical property improving reinforcing agent B: ethylene content 41
%, An iodine value of 15, a Mooney viscosity of 60, and 50 parts of ethylene-propylene-dicyclopentadiene rubber, and 50 parts of styrene, which are graft-polymerized to a graft ratio of 40% by a suspension polymerization method.

Strengthening agent C for physical properties: 95% gel content,
A polymer obtained by graft-polymerizing 50 parts of polybutadiene rubber having an average particle diameter of 0.3 μm, 35 parts of styrene, and 15 parts of acrylonitrile so as to have a graft ratio of 45% by an emulsion polymerization method.

The resin composition is produced by kneading the raw materials in a tumbler-type mixer, and using a twin-screw extruder rotating in the same direction to melt and knead the mixture while keeping the resin temperature at 255 ° C. to form a pellet. Was performed.

Example 1 78% of acrylic resin I and 18 of acrylic polymer A
% And the inorganic red pigment were kneaded at a ratio of 4%, and supplied to a single screw extruder manufactured by Toshiba Machine Co., Ltd. having a barrel diameter of 65 mmφ. On the other hand, 99% of acrylic resin II and ultraviolet absorber (ADK STAB LA-31)
Was kneaded at a rate of 1%, and the mixture was supplied to a single screw extruder manufactured by Hitachi Zosen Corporation having a barrel diameter of 45 mmφ. Extruded through a two-layer multi-manifold type film die (lip clearance 0.5 mm, 600 mm width) connected to both extruders at a set temperature of 250 ° C., and formed by completely contacting both sides with a cooling polishing roll to form a total thickness A multilayer film having a thickness of 0.3 mm (red layer 0.2 mm, transparent layer 0.1 mm) was obtained.

This film was warmed by a far-infrared heater in an injection mold at a temperature of 50 ° C., vacuum-molded, and then, on the back surface (red layer side), the exterior was cream-colored and AB
A resin composition obtained by kneading a pulverized material obtained by regenerating and pulverizing plastic collected from a vacuum cleaner made of S resin was injected with an injection pressure of 1.1
90mm × 150mm at 50kg / cm ² and resin temperature 230 ℃
It was injection molded to a thickness of 3 mm. As a result, a red injection-molded product which was not affected by the color of the recovered plastic was obtained.

The obtained molded product was placed as a test piece with the multilayer film side facing up, and a 12.2 mm diameter piece was placed on top of it.
A 7 mmφ hammer is installed, the hammer falls naturally, and the minimum energy required to break the test piece (unit:
J) was measured to determine the surface impact strength. As a result, 50J
Surface impact strength was obtained.

Examples 2 to 4 In Example 1, 100% of ABS-based recovered plastic was used.
In place of the product, a resin composition obtained by kneading 98% of a ground material obtained by regenerating and grinding the same ABS-based recovered plastic and 2% of a physical property improving agent A, a physical property improving agent B or a physical property improving agent C at a ratio of 2% is used. Other than that, the same operation was performed to obtain a red injection molded product which was not affected by the color tone of the recovered plastic. For each molded product, the surface impact strength was measured in the same manner as in Example 1, and the result was used in Example 1.
The results are shown in Table 1 together with the results. From these results, the effect of the property improving enhancer A, the property improving agent B or the property improving agent C was confirmed.

[0048]

[Table 1]

Example 5 30% of acrylic resin II and 48 of acrylic resin III
%, An acrylic polymer B of 18%, and an average particle size of 30.
Toshiba Machine having a barrel diameter of 65 mmφ was obtained by kneading resin composition pellets obtained by kneading flat aluminum powder (manufactured by Toyo Aluminum Co., Ltd.) having an average thickness of 5 μm and an average thickness of 5 μm at a ratio of 4%.
The extruder is fed to a single screw extruder, extruded through a 250 ° C film die (lip clearance 0.5 mm, 600 mm width) connected to the extruder, and both sides are completely contacted with a cooling polishing roll. Then, a silver metallic color film having a total thickness of 0.3 mm was obtained.

This film was heated in a 50 ° C. injection mold with a far-infrared heater, vacuum-formed, and then, on the back surface thereof, plastic recovered from a HIPS resin television having a black exterior was used. The resin composition obtained by kneading the regenerated pulverized material was injected at an injection pressure of 1,150 kg / cm ² ,
Injection molding was performed at a resin temperature of 230 ° C. to a thickness of 90 mm × 150 mm × 3 mm. As a result, an injection molded product having a silver metallic color which was not affected by the color tone of the recovered plastic was obtained. When the surface impact strength of this molded product was measured in the same manner as in Example 1, a value of 30 J was obtained.

Example 6 In Example 5, HIPS-based recovered plastic 100 was used.
%, Instead of using a resin composition in which 98% of the same HIPS-based recovered plastic was regenerated and pulverized, and 2% of the physical property improving agent A were used. An injection molded product of silver metallic color which is not affected by the color tone of the recovered plastic was obtained. When the surface impact strength of this molded product was measured in the same manner as in Example 1, a value of 40 J was obtained, and the effect of the physical property improving and strengthening agent A was confirmed.

[0052]

The recycled plastic product according to the present invention has the effect of protecting the global environment by collecting and using plastics that have been used at least once, and the surface is decorated with an acrylic resin-based film. It can be reproduced as a product with excellent transparency, transparency, and color depth. Then, if a physical property improving enhancer is added to the recovered resin, it can be regenerated as a product excellent in physical properties.

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Claims (8)

[Claims] 1. The surface of a molded article made of recovered plastic,
A recycled plastic product characterized by being decorated with a colored film made of an acrylic resin containing an ultraviolet absorber and having a thickness of 50 to 600 μm. 2. The product according to claim 1, wherein the recovered plastic is a crushed product of a home appliance, an automobile part, or an industrial member. 3. The product according to claim 1, wherein the colored film is a multilayer film having a surface layer made of a transparent acrylic resin containing an ultraviolet absorber. 4. A molded article of a colored film having a transparent acrylic resin containing an ultraviolet absorber as a surface layer, an opaque colored acrylic resin as a second layer therebelow, and an adhesive backing layer formed of recovered plastic. The product according to claim 3, wherein the product is a multilayer film that serves as a third layer in contact with. 5. The colored film is formed by simultaneously contacting both surfaces of a film obtained by melt extrusion molding with a metal roll surface or a metal belt surface. Products described in. 6. The product according to any one of claims 1 to 5, wherein the recovered plastic is a compound in which a physical property improving and strengthening agent is added and mixed at a ratio of 0.01 to 30% by weight. 7. The product according to claim 6, wherein the physical property improving and strengthening agent is a graft polymer obtained by polymerizing at least an aromatic vinyl monomer on rubber. 8. The product according to claim 7, wherein the physical property improving reinforcing agent is a graft polymer obtained by polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer on rubber.