ES2350097T3 - PROCEDURE FOR REUSING A CRUSHED SYNTHETIC RESIN PRODUCT. - Google Patents

Abstract

A process for producing colored particles of regenerated resin comprising the steps of: preparing a molten product comprising a mixture of white pigment, a colored pigment and a sprayed thermoplastic resin product devoid of coating film for regeneration that is selected from the group consisting of a powdered thermoplastic product containing a black pigment, a mixture of a powdered thermoplastic product containing a black pigment and a powdered thermoplastic product containing a colored pigment, and a powdered thermoplastic product containing two or more different colored pigments; and convert the molten product into solid particles.

Description

[Field of the invention]

The present invention is about a process for regenerating a synthetic resin product that is colored with a black or colored pigment. In more detail, the invention relates to a technology for converting a sprayed synthetic resin product, which is colored with black or colored pigment, which is obtainable, for example, from car parts or household appliances.

[Prior art]

Lately, it is desired to regenerate or recycle synthetic resin products represented by auto parts or household appliances parts to avoid environmental damage. Consequently, many industrial companies have studied procedures to efficiently regenerate these synthetic resin products. Since most synthetic resin products comprise a thermoplastic resin, the best known method of recovering synthetic resin product comprises the steps of spraying the synthetic product to prepare a sprayed product, heating the sprayed product to obtain a molten product and convert the molten product into solid particles.

The synthetic resin products mentioned above are generally referred to as waste plastic materials. GB 1 195 458 A1 discloses the use of polyester or waste nylon in the preparation of a mother mixture containing a pigment. US 4 820 469 A discloses a process for processing thermoplastics by subjecting the material to a mixture of high intensity and casting, and a colored film of waste polymer can also be used. Most plastic waste materials are colored with a black pigment to present a black or gray surface, or with colored pigments, such as a red pigment, a blue pigment and a yellow pigment, to present a colored surface. In most cases, the colored products have different colorations or a stained staining

or partial. In some cases, the coloration of the colored synthetic resin products used over a certain period is discolored and varies from the original coloration. Consequently, when the pulverized synthetic resin product melts and becomes recovered resin particles, the resulting resin particles necessarily have black or gray surfaces. Therefore, the resin material so produced that has a black or gray surface can only be reused for the manufacture of black or gray resin articles.

EP 1 500 673 A1, which is a document within the meaning of Article 54 (3) EPC 1973, deals with a process for producing resin particles recovered from a thermoplastic resin product provided with a coating film, as a car bumper without removing the coating film, mixing a powdered thermoplastic resin product containing a small amount of hardened resin particles and a black or colored pigment with one or more photoprotective pigments, such as a white pigment, a black pigment and a colored pigment, converting the mixture into a molten product and converting the molten product into solid particles.

[Disclosure of the invention]

The inventors of the present invention have discovered that a sprayed thermoplastic resin product that is selected from the group consisting of a sprayed thermoplastic product containing a black pigment, a mixture of a sprayed thermoplastic product containing a black pigment and a sprayed thermoplastic product that It contains a colored pigment, and a sprayed thermoplastic product that contains two or more different colored pigments can be converted into recovered resin particles having the desired coloration by the steps of mixing the sprayed product with a white photoprotective pigment and a colored pigment having a hue to adjust the color of the recovered resin, melt the mixture and convert the molten mixture into solid particles. The invention has been based entirely on the aforementioned discovery.

Accordingly, the present invention resides in a process for producing recovered resin particles comprising the steps of preparing a molten product comprising a mixture of white pigment, a colored pigment and a sprayed thermoplastic resin product devoid of coating film for its recovery selected from the group consisting of a powdered thermoplastic product containing a black pigment, a mixture of a powdered thermoplastic product containing a black pigment and a powdered thermoplastic product containing a colored pigment, and a powdered thermoplastic product containing two or More different colored pigments and convert the molten product into solid particles.

Preferably, the step of preparing a molten product involved in the present invention is carried out by mixing the pulverized resin product to be recovered with a white pigment and a colored pigment, and then melting the mixture by heating. However, the step can be carried out by preheating and melting the pulverized resin product to be recovered and then adding the white pigment and the colored pigment to the molten product during the heating process, or a product cooled afterwards. of finishing the heating process of the molten product. The resulting mixture is heated and subsequently melted. The molten product can be converted into solid particles by producing particles of the molten product and cooling them, or by cooling the molten product as such and then spraying the cooled product.

[Detailed Description of the Invention] Preferred embodiments of the invention are described below.

(one)

A black pigment is incorporated into the mixture at the stage of preparing a molten product.

(2)

An inorganic filler material is incorporated into the mixture at the stage of preparing a molten product.

(3)

A thermoplastic resin is incorporated into the mixture at the stage of preparing a molten product.

(4)

A thermoplastic resin and an elastomer are incorporated into the mixture at the stage of preparing a molten product.

(5)

The sprayed thermoplastic resin product to be recovered is a bumper or interior finish taken from a sprayed car lacking coating film.

(6)

The powdered thermoplastic resin product to be recovered comprises a thermoplastic resin selected from the group consisting of polyolefin, polyester, polystyrene, ABS resin and polyamide.

(7)

The powdered thermoplastic resin product to be recovered contains an elastomer.

(8)

Colored particles of recovered resin produced by the process of the invention mentioned above.

(9)

A process for manufacturing a colored resin article comprising the steps of melting the resin particles recovered from the previous point (8) under heating and of molding the molten resin.

The process of the invention for recovering a sprayed synthetic resin product is characterized in that a combination of a white photoprotective pigment and a colored pigment and, optionally, a thermoplastic resin, an elastomer and a filler material are added to the sprayed synthetic resin product .

In the process of the invention, 0-99% by weight of a thermoplastic resin, 0-40% by weight of an elastomer and 0-50% by weight of a filler material at 1-100% by weight of the product are added sprayed (the total amount of the sprayed product, polyolefin, elastomer and / or filler material reaches 100% by weight). To 100 parts by weight of the powdered product are added 0.01-20 parts by weight, preferably 0.05-15 parts by weight, more preferably 0.15-12 parts by weight, more preferably 0.2-12 parts by weight , and more preferably still 0.25-10 parts by weight, both of the white pigment and the colored pigment.

In the invention, the addition of a component selected from a thermoplastic resin, an elastomer and a filler material is preferred, because it improves the physical properties such as the mechanical performance of a resin article manufactured with the recovery method of the invention.

Examples of powdered synthetic resin products to be recovered in the invention include wastes from pulverized resin materials produced in resin molding and resin treatment, used instrument panels, interior and exterior parts, such as bumpers, and parts. of plastic materials of used cars, used appliances, parts of industrial materials and construction materials. Preferably, the process of the invention is used to recover pulverized resinous parts of used cars, such as instrument panels, bumpers and plastic parts, household appliances, industrial materials and materials used for the construction of houses. The hardened resin films (coating films) of the powdered synthetic resin products to be recovered are previously removed.

The sprayed synthetic resin product to be recovered in the invention may be a waste of a sprayed resin product that is obtained from a mixture of a thermoplastic resin product from which a hardened resin coating film has been removed ( Resinous film prepared by hardening a resin layer of a hardenable resin, such as acrylic resin, urethane resin, unsaturated polyester resin, alkyd melanin resin or acrylic melanin resin through the use of heat, light (including ultraviolet rays)) by physical or chemical treatment, water, a solvent, a hardening catalyst and the like.

Examples of the thermoplastic resin materials used in the recovery process of the sprayed resin product are olefinic resins, polycarbonate resins, polyurethane resins, styrene resins, ABS resins (acrylonitrilebutadiene-styrene resins), polyester resins such as terephthalate of polybutylene and polyethylene terephthalate, polyphenyl ether resins such as modified polyphenylene ether and polyphenylene sulfide, polyacrylic resins such as poly (methyl methacrylate), polyamides such as nylon-6, nylon-66, nylon-12 and nylon-6.12, and polysulfones. The sprayed synthetic resin product may be a sprayed product comprising a thermoplastic resin and an elastomer. The powdered synthetic resin product may be in the form of granules.

Representative examples of synthetic resin products to be recovered include bumpers recovered from automobiles. There is no specific limitation with respect to the recovered bumpers. However, it is preferred that the bumper comprises a crystalline propylene resin, an elastomer and a pigment. For example, it is specifically preferred that the recovered bumper comprises 40-90% by weight of a crystalline propylene resin, 10-60% by weight of an elastomer and 0-20% by weight of other resinous materials.

The recovered bumper may contain pigments such as carbon black and titanium dioxide. A recovered bumper containing both carbon black and titanium dioxide is recovered favorably according to the invention. Preferably, the recovered bumper comprises 100 parts by weight of plastic components (resinous component + elastomeric component) and not more than 2 parts by weight, preferably not more than 1.5 parts by weight, more preferably not more than 1 part by weight, and more preferably not more than 0.6 parts by weight of carbon black. Preferably, the recovered bumper comprises no more than 1.5 parts by weight (based on 100 parts by weight of the plastic components), more preferably no more than 1 part by weight, more preferably no more than 0.5 parts by weight , and more preferably still not more than 0.3 parts by weight, of a pigment that is not carbon black. In addition, the recovered bumper may contain no more than 50 parts by weight (based on 100 parts by weight of the plastic components), preferably no more than 40 parts by weight, more preferably no more than 30 parts by weight, and more preferably not more than 20 parts by weight, of a filler material such as talcum powder. Preferably, the recovered bumper comprises a thermoplastic resin having a melt flow index (MFR, measured according to ASTM D1238, at a temperature of 230 ° C and a weight of 2.16 kg) of 1-100 g / 10 min. , more preferably 3-70 g / 10 min, and more preferably even 5-50 g / 10 min.

The sprayed synthetic resin product generally comprises particles having a diameter of not more than 30 mm, preferably 1-30 mm, more preferably 1-25 mm, more preferably 1-20 mm, more preferably even 1-12 mm . The powdered synthetic resin product can be cast and molded in a heated extruder to produce granules. These granules can be used in the invention instead of the pulverized product.

Preferably, the sprayed synthetic resin product containing a black pigment that can be recovered in the invention is a black or gray sprayed product having an L * of not more than 28.00, an a * of -1.00 to 0, 40, and a b * from -1.50 to 0.50. Preferably, the pulverized product has an L * of 20.00 to 37.00, an a * of -1.00 to 0.40, and a b * of -1.50 to 0.60. More preferably, the pulverized product has an L * of 23.00 to 36.00, an a * of -0.70 to 0.10, and a b * of -1.20 to 0.20. More preferably, the pulverized product has an L * of 23.00 to 33.00, an a * of -0.70 to 0.10, and a b * of 1.20 to 0.20. Particularly preferably, the pulverized product has an L * of 23.00 to 28.00, an a * of -0.70 to 0.10, and a b * of -1.20 to 0.20.

It is preferred that the colored particles of recovered resin have chromatic characteristics of L * = 28.00 to 68.00, a * = -8.00 to 7.00 and b * = -12.00 to 20.00.

Examples of white pigments employable for incorporation into the sprayed synthetic resin product include titanium dioxide, lead white and zinc oxide. Most preferred is titanium dioxide.

Any known titanium dioxide pigment can be used without specific limitations. For example, titanium dioxide prepared by the chlorine process or the sulfuric acid process can be used. Titanium dioxide prepared by the chlorine process is preferred. There is no specific limitation with respect to the shape of the particles. Tetragonal titanium dioxide, rutile type or anatase type can be used. Tetragonal or rutile type titanium dioxide is preferred. There is no limitation with respect to the average particle size. It is preferred that the average particle size is within 0.01-0.5 µm, more preferably 0.050.5 µm, more preferably 0.1-0.4 µm, and particularly preferably 0.20, 3 µm, because these particles are satisfactory in dispersibility and ease of handling. There is no limitation regarding the PDO absorption of titanium dioxide. It is preferred that the PDO absorption is within 5-40 cc / 100 g, more preferably 8-30 cc / 100 g, more preferably 10-20 cc / 100 g, and more preferably 12-18 cc / 100 g

Any of the colored pigments can be used in the invention. Examples include inorganic pigments such as oxides, hydroxides, sulphides, chromates, carbonates, sulfates and metal silicates; and organic pigments such as azo compounds, diphenylmethane compounds, triphenylmethane compounds, phthalocyanine compounds, nitro compounds, nitrous compounds, anthraquinone compounds, quinacridone red compounds, benzidine compounds and molten polycyclic compounds. Colored fibers and metal particles are also usable. There is no specific limitation with respect to the dye of the colored pigment. Any of the yellow pigments, blue pigments, red pigments and green pigments can be used. The pigments can be used in combination of two or more.

Examples of the colored pigments employed in the invention include inorganic pigments such as iron oxide red, cadmium red, cadmium yellow, ultramarine blue, cobalt blue, titanium yellow, lead red, lead yellow, Prussian blue, zinc sulphide, chromium yellow, barium yellow, cobalt blue and cobalt green; Organic pigments such as quinacridone red, polyazoic yellow, anthraquinone red, anthraquinone yellow, polyazoic red, lacustrine azo yellow, perylene, phthalocyanine blue, phthalocyanine green, isoindolinone yellow, Watchung red, permanent red, red, garnet toluidine, benzidine yellow, fast sky blue and bright carmine 6B; Colored fibers and shiny metal particles. The pigments can be used in combination of two or more.

There is no specific limitation with respect to the average size of titanium yellow. It is preferred that the average size be within 0.1-1.5 µm, more preferably 0.5-1.3 µm, more preferably 0.7-1.1 µm, and more preferably even 0.8 -1 µm, because the particles are satisfactory in dispersibility and ease of handling. There is no specific limitation regarding the PDO absorption of titanium yellow. It is preferred that the PDO absorption is within 15-40 cc / 100 g, more preferably 20-35 cc / 100 g, and more preferably 20-30 cc / 100 g. There is no specific limitation with respect to the pH of titanium yellow. The pH of 6-10 is preferred, and the pH of 7-9 is the most preferred.

There is no specific limitation with respect to the average size of ultramarine blue. It is preferred that the average size be within 0.1-5 µm, more preferably 0.5-4 µm, more preferably 0.8-3.5 µm, and most preferably 1-3 µm, because the Particles are satisfactory in dispersibility and ease of handling. There is no specific limitation regarding the PDO absorption of ultramarine blue. It is preferred that the PDO absorption is within 20-50 cc / 100 g, more preferably 25-40 cc / 100 g, and more preferably 30-35 cc / 100 g. There is no specific limitation with respect to the pH of ultramarine blue. The pH of 5-11 is preferred, the pH of 5.5-11 is more preferred, and the pH of 7-11 is the most preferred.

As for phthalocyanine blue, any of the known phthalocyanine blue pigments can be used. For example, those produced by the Waller process or by the phthalonitrile process can be used. There is no specific limitation with respect to the form of phthalocyanine blue. Phthalocyanine blue pigments of type α and type β can be used. There is no specific limitation with respect to the average size of the phthalocyanine blue. It is preferred that the average size be within 0.01-2 µm, more preferably 0.05-1.5 µm, more preferably 0.1-0.4 µm, and more preferably even 0.1-1 µm.

As for the phthalocyanine green, any of the known phthalocyanine green pigments can be used. For example, those produced by the Waller process or by the phthalonitrile process can be used. There is no specific limitation with respect to the form of phthalocyanine green. Phthalocyanine green pigments of type α and type β can be used. There is no specific limitation with respect to the average size of the phthalocyanine green. It is preferred that the average size be within 0.01-2 µm, more preferably 0.05-1.5 µm, more preferably 0.1-0.4 µm, and more preferably even 0.1-1 µm. There is no specific limitation with respect to the pH of the phthalocyanine green. The pH of 4-9 is preferred, and the pH of 4-8 is more preferred.

As for the iron oxide red, any of the known iron oxide red pigments can be used. There is no specific limitation with respect to the shape of the iron oxide red. Iron oxide red pigments of the isometric system can be used. There is no specific limitation with respect to the average size of the iron oxide red. It is preferred that the average size be within 0.01-1 µm, more preferably 0.05-0.5 µm, more preferably 0.08-0.4 µm, and more preferably even 0.1-0 , 3 µm. There is no specific limitation regarding the PDO absorption of iron oxide red. It is preferred that the PDO absorption be within 10-50 cc / 100 g, more preferably 12-40 cc / 100 g, and more preferably 15-30 cc / 100 g. There is no specific limitation with respect to the pH of the iron oxide red. The pH of 4-8 is preferred, and the pH of 5-7 is more preferred.

As for quinacridone red, any of the known quinacridone red pigments can be used. There is no specific limitation with respect to the form of quinacridone red. Quinacridone red pigments of type α, type β and type γ can be used. There is no specific limitation with respect to the average size of quinacridone red. It is preferred that the average size be within 0.01-2 µm, more preferably 0.05-1.5 µm, and more preferably 0.1-1 µm.

As for anthraquinone red, any of the known anthraquinone red pigments can be used. There is no specific limitation regarding the form of anthraquinone red. There is no specific limitation with respect to the average anthraquinone red size. It is preferred that the average size be within 0.01-2 µm, more preferably 0.05-1.5 µm, and more preferably 0.1-1 µm. There is no specific limitation with respect to the pH of anthraquinone red. The pH of 4-9 is preferred.

The white pigment and the colored pigment can be added directly or as a mother mixture. The technology of the mother mix that uses a pigment and a resinous component is already known.

Optionally, a black pigment, such as carbon black or iron black, can be added to the sprayed resinous product. The black pigment can impart a high light insulation property to the recovered resin articles. Black pigments can be used in combination of two or more.

As for carbon black, any of the known carbon black pigments can be used without any specific limitation. For example, carbon black, acetylene black, lamp black, channel black or Ketchen black produced by the oven procedure or the channel procedure can be used. Carbon black can undergo oxidation treatment. An oven black produced by the oven process is preferred, because it has a good uniform appearance, good dispersibility and produces blackness and a greater satin of the resulting molded article. There is no specific limitation with respect to the average size of carbon black. It is preferred that the average size be within 0.001-0.3 µm, more preferably 0.005-0.2 µm, more preferably 0.01-0.1 µm, and more preferably even 0.01-0.03 µm, because a carbon black of such average size is excellent in dispersibility and ease of handling and also provides intense blackness and high satin.

The iron black can be an iron black oxide produced by the heating process. There is no specific limitation with respect to the shape of the iron black. Iron black can be used that has a polyhedral shape, such as an octahedral shape or a globular shape. Octahedral iron black is preferred. There is no specific limitation with respect to the average size of the iron black. It is preferred that the average size is within 0.05-0.4 µm, more preferably 0.15-0.35 µm, and more preferably 0.20.205 µm. There is no specific limitation regarding the absorption of PDO from iron black. It is preferred that the PDO absorption is within 10-80 cc / 100 g, more preferably 15-50 cc / 100 g, more preferably 20-40 cc / 100 g, and more preferably even 25-30 cc / 100 g There is no specific limitation with respect to the pH of the iron black red. The pH of 9-11 is preferred, and the pH of 9-10 is more preferred.

Optionally, a filler material can be added to the pulverized resin product, and the addition of a filler material is preferred to improve the physical properties of the articles resulting from recovered resin. Loading materials can be used in combination of two or more.

The fillers may be organic fillers or inorganic fillers other than pigments. Examples of inorganic fillers include talc, clay, silica, diatomaceous earth, magnesium aluminate, montmorillonite, bentonite, dolomite, dawsonite, silicates, carbon fibers, glasses (including glass fibers), barium ferrite, beryllium oxide , aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, magnesium sulfate, calcium sulfate, barium sulfate, ammonium sulfate, calcium sulphite, calcium silicate, molybdenum sulphite, zinc borate, metaborate Barium, calcium borate, sodium borate, metals such as zinc, copper, iron, lead, aluminum, nickel, chromium, titanium, manganese, tin, platinum, tungsten, gold, magnesium, cobalt and strontium, oxides of these metals, stainless steel, alloy for welding, alloys of metals such as brass, metal ceramic powders such as silicon carbide, silicon nitride, zir conia, aluminum nitride, titanium carbide, metal oxide hairs and fibers. Preferably, the metal oxide fibers and hairs have an L / D ratio of not less than 10, more preferably not less than 15. Preferably, the fibers have a length of 0.1 to 5 mm, more preferably 1 to 5 mm . Preferably, the fiber width is not more than 30 µm, more preferably 1-30 µm, and more preferably even 1-15 µm. In particular, the carbon fiber has a length of 0.1 to 5 mm, more preferably 1 to 5 mm, and a width of not more than 30 µm, more preferably 1-30 µm, and more preferably even 1 -15 µm.

Inorganic filler material is preferred as filler material, and talcum powder is the most preferred.

In the recovery process of the synthetic resin product, additives and dispersants can be used as lubricants, antistatic agents, surfactants, nucleating agents, ultraviolet absorbers, oxidation inhibitors and flame retardants.

Examples of the dispersants include higher fatty acids, higher fatty acid amides, metal soaps, glycerol esters, hydrotalcite, polyethylene wax and polypropylene wax.

Examples of the additives include oxidation inhibitors of the phenol, phosphorus and sulfur type, benzophenone, benzotriazole, ultraviolet ray absorbers such as HALS and phosphorus and halogen type flame retardants.

As described above, a thermoplastic resin and / or an elastomer can be used in the process of the invention to recover the sprayed synthetic resin product. Preferably, the thermoplastic resin and the elastomer to be used are the same or an equivalent of those contained in the resinous product.

Accordingly, examples of thermoplastic resin materials employed in the recovery process of the sprayed resin product are olefinic resins (for example, high density polyethylene, reduced density polyethylene, crystalline polypropylene), polycarbonate resins, polyurethane resins, resins styrene, ABS resins (acrylonitrile-butadiene-styrene resins), polyester resins such as polybutylene terephthalate and polyethylene terephthalate, polyphenyl ether resins such as modified polyphenylene ether and polyphenylene sulfide, polyacrylic resins such as polyacrylic (methyl methacrylate), polyamides such as nylon-6, nylon-66, nylon-12 and nylon-6.12, and polysulfones.

In the process of the invention for producing particles of recovered resin material, the pulverized synthetic resin product is mixed with appropriate amounts of a white pigment and a colored pigment and, optionally, with a thermoplastic resin and an elastomer, and subsequently , the resulting mixture is melted and kneaded. The amounts of these pigments can be determined in consideration of the degree of coloration (such as black or gray) of the sprayed resin product. The kneaded material is then treated to obtain a sample directly or through the recovered resin particles. The sample obtained is subjected to visual observation or observation using a test apparatus to examine the hue or appearance of the color. If desired, certain physical properties are measured to examine whether the amounts of the additives used are appropriate or not. Based on the examination, the preparation of the recovered resin product sample is repeated varying the nature and amounts of the additives to obtain a recovered resin product having the desired coloration.

There is no specific limitation with respect to the procedures and apparatus for mixing the pulverized resin product and the additives. Mixers and / or kneaders called screw extruders (or kneaders), double screw extruders (or kneaders), tandem kneading devices comprising a double screw extruder and an endless screw extruder (or kneader) can be used combined in series, calenders, Banbury mixers, kneading rollers, platographs or Brabender kneaders.

The recovered colored resin particles can be treated by known molding methods, such as extrusion molding, sheet forming molding, injection molding, injection-compression molding, gas injection molding, blow molding of compressed air or vacuum molding, to produce recovered items, such as interior or exterior parts of automobiles, such as bumpers, plastic parts, door finishes, instrument panel finishes, console boxes, car engine cabin parts, such as battery and fan protectors, interior or exterior parts of household appliances, interior or exterior parts of a house, or useable items such as buffer materials or packaging materials. According to the process of the invention, the recovery of plastic materials can produce molded articles provided with a satin surface, embossed articles, articles with colored designs and articles provided with a uniform embossed design.

The following are examples that reflect the invention. In the examples, the brightness and hue of the molded articles (samples) are measured with the following procedures.

Measurement procedures: The relief surface of the sample is subjected to measurements of “luminosity L *”, “hue a *” and “tonality b *” (CIE 1976) by means of a spectrophotometer (light source: D-65, viewing angle: 10 °), available from Kurashiki Spinning Co., Ltd.

[Examples 1-9]

(1) Synthetic resin product to be recovered

A bumper product that had been recovered from a used car (colored with black pigment, from which the coating film was removed) was used and sprayed to produce 5-10 mm chips as plastic waste material.

The powdered bumper had a melt flow index (MFR) of 28.6 g / 10 min (measured according to ASTM D1238, at a temperature of 230 ° C and a weight of 2.16 kg) and comprised approximately 60 parts in weight of crystalline polypropylene, about 30 parts by weight of elastomers (a mixture of EPR and other elastomers), about 10 parts by weight of talc and about 0.5-1 parts by weight of a mixture of pigments containing carbon black, titanium dioxide and other pigments.

(2)

Additive materials

(one)

Polypropylene: crystalline polypropylene (homo, melt flow index (MFR): 30 g / 10 min, slope ratio: 96.0%)

(2)

Elastomer: ethylene-propylene copolymer (Mooney viscosity: ML1 + 4 (100 ° C): 35, ethylene content: 72% by weight)

(3)

Talc endowed with an average diameter of 2.7 µm (laser diffraction procedure)

(4)

Iron oxide black with an average diameter of 0.27 µm, a PDO absorption of 26-30 cc / 100 g and a pH of 9-10

(5)

Carbon black with an average diameter of 0.017 µm (prepared by the oven procedure)

(6)

Titanium dioxide with an average diameter of 0.22 µm, a PDO absorption of 14 cc / 100 g and a pH of 5.5-7.5

(7)

Titanium yellow with an average diameter of 0.91 µm, a PDO absorption of 25cc / 100g and a pH of 7.8

(8)

Ultramarine blue A with an average diameter of 1-3 µm, a PDO absorption of 31-33 cc / 100 g and a pH of 8.5-10.5

(9)

Phthalocyanine blue belonging to type α

(10)

Phthalocyanine green belonging to type α and endowed with a PDO absorption of 39.3 cc / 100g and a pH of 7

(eleven)

Iron oxide red with an average diameter of 0.16 µm, a PDO absorption of 23cc / 100g and a pH of 5-7

(12)

Quinacridone red belonging to type β and endowed with a pH of 8.5-9.5

(13)

Anthraquinone red endowed with a PDO absorption of 54 cc / 100 g and a pH of 5.5-8.5

(14)

Oxidation inhibitor: IRGANOX 1010 (0.05 parts by weight) and IRGAFOS 168 (0.05 parts by weight) were used in all examples

(fifteen)

HALS additive: Sanol LS770 (0.2 parts by weight) was used in all examples

(16)

Dispersant: in all the examples calcium stearate (0.1 parts by weight) was used

(3)

The additives were mixed in a drum mixer (available from Platech Co., Ltd.) in the dry state and kneaded in a double screw extruder (UME 40-48T, available from Ube Industries, Ltd.) under the conditions of L / D = 47.7, barrel temperature: 200 ° C, sieve screen 20 and treatment speed: 60 kg / hr to produce granules.

In each example, the total amount of the plastic waste material, polypropylene, elastomer and talc was set at 100 parts by weight (plastic waste material: 77% by weight; polypropylene: 15% by weight; elastomer: 3% by weight; talcum powder: 5% by weight).

The granules were placed in an injection molding machine (metal mold: square plate (100 mm × 100 mm × 3 mm, with relief) under the following conditions, to produce the sample:

molding temperature: 180 ° C, 190 ° C, 200 ° C, 210 ° C molding pressure: P1-P2-P3-P4 = 108-98-88-78 (MPa) molding rate: V1-V2-V3-V4 = 30-30-20-20 (%)

screw back pressure: free screw rotation: 60% mold temperature: 40 ° C cycle: injection: 10 seconds, and cooling: 20 seconds

5 molding cycle conditions: 10 continuous molding cycles were used for measurements, with samples in the 6th and 10th cycles

The molded products (samples) were subjected to luminosity and hue measurements. Table 1 shows the additive (quantity in terms of parts by weight) and the results of the evaluation.

10 Table 1 [Examples 10-15]

Sample prepared with plastic waste material L *: 25.55, a *: -0.19, b *: -0.52 Hue of the plastic waste material (visual observation): black

Example 1: Pigment [titanium dioxide (0.3), titanium yellow (0.06), phthalocyanine green (0.01)] Resin recovered: L *: 29.05, a *: -0.11, b *: -1,23 Hue of the recovered resin (visual observation): dark blue-gray

Example 2: Pigment [titanium dioxide (2.3), ultramarine blue A (0.07), iron oxide red (0.01)] Resin recovered: L *: 49.05, a *: -0, 51, b *: -2,59 Hue of the recovered resin (visual observation): dark blue-gray

Example 3: Pigment [titanium dioxide (0.78), phthalocyanine blue (0.11), quinacridone red (0.05)] Resin recovered: L *: 31.12, a *: -1.33, b *: -4,89 Hue of the recovered resin (visual observation): dark blue bruised

Example 4: Pigment [titanium dioxide (1.2), phthalocyanine blue (0.035), phthalocyanine green (0.06)] Resin recovered: L *: 34.61, a *: -2.29, b * : -3.34 Hue of the recovered resin (visual observation): dark grayish greenish yellow

Example 5: Pigment [titanium dioxide (1.26), titanium yellow (1.08), iron oxide red (0.08)] Resin recovered: L *: 45.30, a *: 1.01 , b *: 5.68 Hue of the recovered resin (visual observation): greyish yellow

Example 6: Pigment [titanium dioxide (1.92), titanium yellow (1), iron oxide red (0.087)] Resin recovered: L *: 57.58, a *: 2.43, b *: 9.00 Hue of the recovered resin (visual observation): light yellowish reddish gray

Example 7:

Pigment [titanium dioxide (0.37), titanium yellow (0.06), phthalocyanine green (0.02), iron black (0.5)] Resin recovered: L *: 28.63, a * : -0.08, b *: -1.21 Hue of the recovered resin (visual observation): bluish dark gray

Example 8:

Pigment [titanium dioxide (0.58), titanium yellow (0.19), phthalocyanine green (0.02), carbon black (0.2)] Resin recovered: L *: 29.44, a * : 0.05, b *: -0.98 Hue of the recovered resin (visual observation): dark blue-gray

Example 9:

Pigment [titanium dioxide (1.1), titanium yellow (0.9), iron oxide red (0.155), carbon black (0.05)] Resin recovered: L *: 39.31, a * : 1.57, b *: 3.55 Hue of the recovered resin (visual observation): greyish reddish yellow

(1) Synthetic resin product to be recovered

A waste polyethylene resin material produced for industrial uses was used as waste plastic material and colored with a black pigment.

5 (2) The 100 parts by weight of the waste polyethylene resin material and the additives were mixed in a drum mixer (available from Platech Co., Ltd.) in the dry state and kneaded in a double screw extruder ( UME 40-48T, available from Ube Industries, Ltd.) under the conditions of L / D = 47.7, barrel temperature: 100 ° C, die head: 180 ° C, sieve screen 100 and treatment speed: 35 kg / hr to produce granules.

10 The granules were placed on a hot plate and molded (pressing pressure: 40 t, separator: 100 mm × 100 mm × 1 mm, heating temperature: 230 ° C, pressure: 100 kg / cm2, cooling temperature: 20 ° C, cooling period: 2 min) to produce the sample. The samples were subjected to brightness and hue measurements. Table 2 shows

15 the additive (quantity in terms of parts by weight) and the results of the evaluation.

Table 2

Sample prepared with plastic waste material L *: 25.52, a *: 0.31, b *: 0.33 Hue of the plastic waste material (visual observation): black

Example 10: Pigment [titanium dioxide (2.55), titanium yellow (0.64), phthalocyanine green (0.09)] Resin recovered: L *: 52.21, a *: 1.16, b *: 2.36 Hue of the recovered resin (visual observation): medium yellowish reddish gray

Example 11: Pigment [titanium dioxide (0.75), phthalocyanine blue (0.24), quinacridone red (0.09), carbon black (0.05)] Resin recovered: L *: 28.21 , a *: -1.01, b *: -4.57 Hue of the recovered resin (visual observation): intense blue

Example 12: Pigment [titanium dioxide (1.45), phthalocyanine blue (0.03), phthalocyanine green (0.12), carbon black (0.05)] Recovered resin: L *: 35.24 , a *: -3.35, b *: -3.42 Hue of the recovered resin (visual observation): grayish-blue-green

Example 13: Pigment [titanium dioxide (1.20), titanium yellow (0.12), iron oxide red (0.39), carbon black (0.05)] Resin recovered: L *: 35 , 22, a *: 2.45, b *: 0.08 Hue of the recovered resin (visual observation): grayish red

Example 14: Pigment [titanium dioxide (0.65), titanium yellow (0.55), iron oxide red (0.12), carbon black (0.05)] Recovered resin: L *: 31 , 86, a *: 0.81, b *: 0.82 Hue of the recovered resin (visual observation): dark grayish purple

Example 15: Pigment [titanium dioxide (2.10), titanium yellow (0.98), iron oxide red (0.05)] Resin recovered: L *: 61.68, a *: 1.90 , b *: 11,26 Hue of the recovered resin (visual observation): reddish yellowish light gray

[Examples 16-21]

(one)

Synthetic resin product to be recovered

A waste polyamide resin material produced for industrial uses containing 20% by weight of carbon fibers was used as waste plastic material and colored with a black pigment.

(2)

The 100 parts by weight of the waste polyamide resin material and the additives (shown in Table 3) were mixed in a drum mixer (available in Platech

Co., Ltd.) in the dry state and kneaded in a double screw extruder (UME 40-48T, available from Ube Industries, Ltd.) under the conditions of L / D = 47.7, barrel temperature: 260 ° C, and treatment speed: 40 kg / hr to produce granules.

The granules were placed in an injection molding machine (metal mold: 5 square plate (100 mm × 100 mm × 3 mm, with surface drawing) under the following

Conditions, to produce the sample: molding temperature: 270 ° C, 280 ° C, 280 ° C, 280 ° C molding pressure: P1-P2-P3-P4 = 108-98-88-78 (MPa) molding rate: V1-V2-V3-V4 = 30-30-20-20 (%)

10 screw back pressure: free screw rotation: 60% mold temperature: 80 ° C cycle: injection: 10 seconds, and cooling: 20 seconds molding cycle conditions: 10 molding cycles were used for measurements

15 continuous, with samples in the 6th and 10th cycles. The samples were subjected to luminosity and hue measurements. Table 3 shows the additive (quantity in terms of parts by weight) and the results of the evaluation.

Table 3

Sample prepared with plastic waste material L *: 24.98, a *: 0.13, b *: 0.28 Hue of the plastic waste material (visual observation): black

Example 16: Pigment [titanium dioxide (2.75), titanium yellow (0.71), phthalocyanine green (0.11)] Resin recovered: L *: 51.97, a *: 1.21, b *: 2.55 Hue of the recovered resin (visual observation): reddish yellowish medium gray

Example 17: Pigment [titanium dioxide (0.92), phthalocyanine blue (0.28), carbon black (0.05)] Resin recovered: L *: 28.18, a *: -1.06, b *: -4,46 Hue of the recovered resin (visual observation): intense blue

Example 18: Pigment [titanium dioxide (1.55), phthalocyanine blue (0.05), phthalocyanine green (0.15), carbon black (0.05)] Resin recovered: L *: 35.11 , a *: -3,22, b *: -3,48 Hue of the recovered resin (visual observation): grayish-blue-green

Example 19:

Pigment [titanium dioxide (1.4), titanium yellow (0.15), iron oxide red (0.42), carbon black (0.05)] Resin recovered: L *: 35.47, a *: 2.51, b *: 0.14 Hue of the recovered resin (visual observation): grayish red

Example 20:

Pigment [titanium dioxide (0.82), titanium yellow (0.71), iron oxide red (0.14), carbon black (0.05)] Resin recovered: L *: 32.03, a *: 0.85, b *: 0.84 Hue of the recovered resin (visual observation): dark grayish purple

Example 21:

Pigment [titanium dioxide (2.35), titanium yellow (1.07), iron oxide red (0.06)] Resin recovered: L *: 61.36, a *: 1.93, b * : 10.85 Hue of the recovered resin (visual observation): light yellowish reddish gray

[Use in industry]

According to the present invention, plastic waste products can be effectively recovered which comprise as a main component a thermoplastic resin, such as polypropylene resin.

The process of the invention for the recovery of waste plastic material allows to prepare colored resin products (other than black resin products) using a combination of a white photoprotective pigment and an optionally selected colored pigment. If desired, the recovered resin product may have a color other than the color of the initial plastic waste material. Consequently, the

The procedure is particularly advantageous for recycling waste plastic material.

Claims (11)

 Claims

one.

A process for producing colored particles of regenerated resin that

It comprises the steps of: preparing a molten product comprising a mixture of white pigment, a colored pigment and a sprayed thermoplastic resin product devoid of coating film for regeneration which is selected from the group consisting of a sprayed thermoplastic product containing a pigment black, a mixture of a powdered thermoplastic product containing a black pigment and a powdered thermoplastic product containing a colored pigment, and a powdered thermoplastic product containing two or more different colored pigments; and convert the molten product into solid particles.

2.

The process for producing colored particles of recovered resin as defined in claim 1 wherein the step of preparing a molten product comprises a step of mixing the product to be regenerated with the white pigment and the colored pigment, and a step subsequent heating and melting of the resulting mixture.

3.

The process for producing colored particles of regenerated resin as defined in claim 1 wherein the step of preparing a molten product comprises incorporating a black pigment.

Four.

The process for producing colored particles of regenerated resin as defined in claim 1 wherein an inorganic filler material is incorporated into the mixture produced in the step of preparing a molten product.

5.

The process for producing colored particles of regenerated resin as defined in claim 1 wherein a thermoplastic resin is incorporated in the mixture produced in the step of preparing a molten product.

6.

The process for producing colored particles of regenerated resin as defined in claim 1 wherein a thermoplastic resin and an elastomer are incorporated into the mixture produced in the step of preparing a molten product.

7.

The process for producing colored particles of regenerated resin as defined in claim 1 wherein the sprayed thermoplastic resin product to be regenerated is a bumper or the interior finish taken from a sprayed car devoid of coating film thereon.

8.

The process for producing colored particles of regenerated resin as defined in claim 1 wherein the powdered thermoplastic resin product to be

regenerating comprises a thermoplastic resin selected from the group consisting of polyolefin, polyester, polystyrene, ABS resin and polyamide.

9.

The process for producing colored particles of regenerated resin as defined

in claim 1 wherein the pulverized thermoplastic resin product to be regenerated contains an elastomer.

10.

Colored particles of regenerated resin produced by the method of claim 1.

eleven.

A process for manufacturing a resin article prepared by melting the particles

colored of regenerated resin of claim 10 under heating and molding of the molten particles.