JPH0592430A - Production of injection molded product - Google Patents

Abstract

PURPOSE:To reutilize a composition containing waste material of painted car parts as a raw material as an injection molded product of various uses by markedly improving the impact resistance of said composition. CONSTITUTION:A waste material of painted car parts made of an olefinic resin is ground and 0.5-20 pts.wt. of an olefinic resin (a), 0.25-10 pts.wt. of an olefinic elastomer (b), 0.01-0.5 pts.wt. of a diene polymer (c) having a hydroxyl group at its terminal or hydrogenated matter thereof and 0-4 pts.wt. of talc (d) are compounded with 1 pts.wt. of the ground matter and the resulting composition is subjected to injection molding.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention improves the impact resistance of blended waste materials of olefin resin automobile parts by blending specific components, and reuses the waste materials for injection molding. The present invention relates to a method of manufacturing an injection molded body that enables the above.

[0002]

2. Description of the Related Art Conventionally, materials for automobile parts, which are mainly composed of olefin resin, are mainly composed of ethylene / propylene rubber, propylene polymer and talc. The one to which the agent is added is used. Specifically, JP-A-60
-3420, JP-A-59-49252, JP-A-61
The compositions described in JP-A-276840 and JP-A-63-65223 are known.

[0003]

However, the materials for automobile parts containing these olefin resins as main components are mainly ethylene / propylene rubber, propylene polymer and talc, if necessary a small amount of polyethylene, and different kinds of rubber. The waste material for automobile parts, which is composed of the ones with fillers and fillers added, has some impact resistance in the unpainted ones, but the coated olefin resin automobile parts If pulverized and granulated, and then reused as an injection-molded body, impact resistance will decrease due to poor compatibility between paint resin and olefin resin, and it is difficult to reuse as it is. .. For this reason, the waste material of the coated olefinic resin is blended with the currently used composition for injection molding within a range that does not significantly impair the performance of the product. % Or less, and this is standing as a major obstacle to the reuse of the waste material of the painted olefin resin, which is expected to be discarded in a large amount in the future. Therefore, the present invention will improve the impact resistance of the above-mentioned waste material of automobile parts containing olefinic resin as a main component, and make it possible to reuse a large amount of waste material as various injection molded material. It is what

[0004]

[Means for Solving the Problems]

[Summary of the Invention] The inventors of the present invention have conducted extensive studies in view of the above problems, and as a result, have a olefin resin, an olefin elastomer, and a terminal hydroxyl group in a waste material of an automobile part of the above-mentioned coated olefin resin. By blending a specific blended composition comprising a diene polymer or its hydrogenated product and talc optionally blended in a specific weight ratio, the impact resistance of the composition blended with the waste material is remarkably improved. The present inventors have completed the present invention by obtaining the knowledge that they can be obtained. That is, in the method for producing an injection-molded article of the present invention, the waste material of the coated olefin resin automobile parts is crushed, and 1 part by weight of the crushed product is used as a reference,
Each of the following components (a) to (d) is blended in the following amount ratio and injection-molded. (a) Olefin-based resin 0.5 to 20 parts by weight (b) Olefin-based elastomer 0.25 to 10 parts by weight (c) Diene polymer having terminal hydroxyl group or hydrogenated product thereof 0.01 to 0.5 parts by weight (d) Talc 0 to 4 parts by weight [Detailed description of the invention]

[I] Raw materials (1) Waste materials of painted olefin resin automobile parts (a) Painted olefin resin automobile parts Olefin resin automobile parts Used as raw materials for olefin resin automobile parts As the olefin resin thus obtained, a single weight of α-olefin represented by ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-pentene and the like is used. Coalescing and these α
-A copolymer of olefins and the like can be mentioned. Specific examples of such an olefin resin include polyethylene resins such as so-called low-pressure polyethylene, medium-pressure polyethylene, high-pressure polyethylene, and linear low-density polyethylene, stereoregular polypropylene, stereoregular poly-1-butene, Stereoregular poly-4-methyl-1-
Examples include stereoregular poly-α-olefin resins such as pentene. Of these, stereoregular polypropylene (hereinafter simply referred to as “polypropylene”) is preferably used. Among the polypropylenes, a copolymer of propylene and 40% by weight or less of another α-olefin is preferable, and a copolymer of 35% by weight or less, especially 30% by weight or less of ethylene is preferable. The copolymer may be a random copolymer or a block copolymer, but a block copolymer is particularly preferable.
These olefin resins can be used alone or as a mixture of a plurality of them. Further, an amorphous or low crystalline copolymer of α-olefins such as ethylene, propylene, 1-butene, 1-pentene and 1-hexene, or a non-conjugated diene is further mixed with these α-olefins. It is also possible to use a mixture of an olefinic elastomer such as an amorphous or low crystalline copolymer obtained as described above, a filler such as talc, etc., to the extent that the object of the present invention is not impaired.

Coating As waste materials of the coated olefin resin automobile parts used in the method of the present invention, acrylic resin, alkyd resin, epoxy resin, polyurethane resin, It is a resin for coating such as saturated polyester resin. However, in the method of the present invention, although it is most suitable for the method for recycling the waste material of the coated olefin resin automobile parts, the coating material is not formed on the waste material of the coated olefin resin automobile parts. Waste materials of resin-based automobile parts may be mixed.

Waste materials The painted olefin resin automobile parts used in the method of the present invention include, specifically, automobile bumpers, mat guards, side moldings, wheel caps,
Examples thereof include automobile exterior parts such as spoilers, instrument panels, levers, knobs, and interior parts such as linings.

(B) Crushing The waste material of the above-mentioned olefinic resin-made automobile parts coated with a crusher or the like is usually 20 to 0.1 mm, preferably 5
It is shredded by crushing to a size of about 1 mm.

(2) Compounding composition The compounding composition to be compounded in the waste material of the above-mentioned coated olefin resin automobile parts in the present invention is shown below (a)
To (c), preferably the compounding ingredients (a) to (d). (a) Olefin-based resin component As the olefin-based resin component used in the above-mentioned composition, ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene , A homopolymer of α-olefin represented by 1-pentene and the like, and a copolymer of these α-olefins having a flexural modulus of 500 to 30 measured according to JIS K-7203. Examples of the resin include 000 kg / cm ² , preferably 1,000 to 20,000 kg / cm ² , and particularly preferably 1,500 to 15,000 kg / cm ² . The melt flow rate (MFR) of the olefin resin is not particularly limited, but the ASTM
The value measured according to D-1238 is usually 0.01 to
500 g / 10 minutes, preferably 0.1-200 g / 10
Min, particularly preferably 0.5 to 100 g / 10 min. Specific examples of such an olefin resin include:
Polyethylene resins such as so-called low-pressure polyethylene, medium-pressure polyethylene, high-pressure polyethylene, linear low-density polyethylene, stereoregular polypropylene, stereoregular poly-1-butene, stereoregular poly-4-methyl-1.
A stereoregular poly-α-olefin resin such as pentene can be mentioned, and all of these are industrially available. Of these, stereoregular polypropylene (hereinafter simply referred to as “polypropylene”) is preferably used. Further, among the polypropylene, a copolymer of propylene and 40% by weight or less of another α-olefin is preferable, and particularly 35% by weight or less, especially 3% by weight.
Copolymers with 0% by weight or less of ethylene are preferred. The copolymer may be a random copolymer or a block copolymer, but a block copolymer is particularly preferable. These olefin resin components can be used alone or as a mixture of a plurality of them.

(B) Olefin-based Elastomer Component As the olefin-based elastomer used in the above-mentioned compounded composition, ethylene, propylene, 1-butene, 1-
A copolymer of α-olefins such as pentene and 1-hexene, or a copolymer obtained by further mixing these α-olefins with a non-conjugated diene.
The initial elastic modulus measured according to K-6301 is 400.
It is an amorphous or low crystalline copolymer having a weight of not more than kg / cm ² , preferably not more than 200 kg / cm ² , particularly preferably not more than 100 kg / cm ² . Specific examples of the non-conjugated diene include dicyclopentadiene and 1,4-
Hexadiene, cyclooctadiene, dicyclooctadiene, methylene norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5-methyl-1,4-hexadiene, 7- Methyl-1,6-octadiene etc. can be mentioned. These olefin elastomers have 1
Mooney viscosity (ML _{1 + 4} ) measured at 00 ° C is usually 1
-500, preferably 5-200, particularly preferably 7-
A range of 150 is used. Preferred specific examples of the olefin elastomer include ethylene / propylene copolymer rubber (EPM), ethylene / 1-butene copolymer rubber, ethylene / propylene / 1-butene copolymer rubber, ethylene / propylene / non-conjugated diene copolymer. Examples thereof include rubber (EPDM), ethylene / 1-butene / non-conjugated diene copolymer rubber, ethylene / propylene / 1-butene / non-conjugated diene copolymer rubber.

(C) A diene polymer having a hydroxyl group at the terminal or a hydrogenated compound component thereof A diene polymer having a hydroxyl group at the terminal As the diene polymer having a hydroxyl group at the terminal used in the above-mentioned compounded composition, for example, polyhydroxypolybutadiene is used. Can be mentioned. Specifically, it has at least one hydroxyl group at the terminal and has a molecular weight of 200 to 200,00.
Polymers which are liquid, semi-solid or solid at room temperature of 0, preferably 500 to 100,000, and particularly preferably 800 to 100,000 are included. The average number of hydroxyl groups per molecule is preferably 1.5 to 5.0. The diene polymer having a hydroxyl group at the terminal can be produced from 1,3-diene as a raw material by a known method such as a radical polymerization method or an anionic polymerization method. For example, JP-A-51-7
1391, JP-A-53-123452, JP-A-53.
The method described in each gazette of No.-136053 can be mentioned. When produced by radical polymerization, it can be easily obtained by polymerizing a diene monomer with hydrogen peroxide as a polymerization initiator. Further, when produced by anionic polymerization, the living polymer produced, for example, monoepoxy compound, formaldehyde, acetaldehyde, acetone, or halogenoalkyne oxide,
Obtained by reacting a polyepoxide. The living polymer referred to herein is a polymer obtained by polymerizing a conjugated diene with an anionic polymerization catalyst, for example, an alkali metal or organic alkali metal compound, according to a well-known method, and at least one of both ends thereof. One having an alkali metal bonded structure. At least one type of conjugated diene monomer is used as a raw material monomer for these polymers. As the conjugated diene monomer, 1,3-butadiene, 1,3-
Pentadiene, isoprene, chloroprene, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-
Butadiene etc. are mentioned.

Water of a diene polymer having a hydroxyl group at the terminal
Further, the hydrogenated product of the diene polymer having a hydroxyl group at the terminal is a diene polymer having a hydroxyl group at the terminal,
It can be produced by hydrogenation in a usual manner. Specific examples thereof include the methods described in JP-A-51-71391, JP-A-53-123452, and JP-A-53-136053. Regarding the degree of hydrogenation, a double bond contained in the polymer may be wholly or partially hydrogenated. These diene polymers having a hydroxyl group at the terminal and their additives can be used either alone or as a mixture of a plurality of them.

(D) Talc component In the above-mentioned compounded composition, in order to improve the physical properties such as the flexural modulus of the injection-molded product which is the final product, the talc component, which is optionally compounded, is a commercially available talc, particularly a talc component. It is preferable to use the one produced by dry-classifying the talc and then dry-classifying it, having an average particle size of 5 μm or less (preferably 0.5 to 3 μm) and a specific surface area of 3.5 m ² / g or more (preferably 3.5 to ⁶ m ² / g)
It is more preferable to use the one of The average particle size can be determined by the particle size value at a cumulative amount of 50% by weight read from a particle size cumulative distribution curve measured using a liquid layer sedimentation type light transmission method (for example, CP type manufactured by Shimadzu Corporation). .. Further, the specific surface area can be determined by a measurement value by an air permeation method (for example, SS-100 type constant pressure ventilation type specific surface area measuring device manufactured by Shimadzu Corporation). If the average particle size exceeds the above range, the impact resistance tends to decrease, and if the specific surface area is less than the above range, the bending elastic modulus tends to decrease, so that it is preferable to use those within the above range.

(E) Additional components In addition to the above-mentioned components (a) to (d), additional components may be added to the above-mentioned compounded composition, if necessary, within a range that does not significantly impair the effects of the present invention. .. As the additional component, an additive usually added to the olefin resin, for example, a processability stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a neutralizing agent, a fluidity improving agent, a metal corrosion inhibitor, etc. In addition to antistatic agents, lubricants, pigments and pigment dispersants, etc., fillers other than talc, for example, whiskers such as fibrous potassium titanate, fibrous magnesium oxalphate, fibrous aluminum borate and carbon fibers, glass fibers, etc. Can also be added if necessary.

(3) Amount ratio The amount of each of the above-mentioned components used in the present invention is usually the waste material 1 of the coated olefin resin automobile parts.
The above components (a) to (d) are blended in the following amount ratios by weight. (a) Olefin-based resin: 0.5 to 20 parts by weight, preferably 1.0 to 5 parts by weight, particularly preferably 1.5 to 3 parts by weight, (b) olefin-based elastomer: 0.25 to 10 parts by weight. , Preferably 0.5 to 2.5 parts by weight, particularly preferably 0.8 to 1.5 parts by weight, (c) 0.01 to 0.5 parts by weight of a diene polymer having a hydroxyl group at the terminal or a hydrogenated product thereof. Part, preferably 0.0
5 to 0.3 parts by weight, particularly preferably 0.1 to 0.2 parts by weight (d) Talc: 0 to 4 parts by weight, preferably 0.1 to 1 part by weight, particularly preferably 0.25 to 0. 5 parts by weight, when the amount of the olefin resin is less than the above range and the amount of the olefin elastomer is less than the above range, the impact resistance is impaired because the amount of the waste material is excessively large, which is unsuitable. Become. When the amount of the olefin resin is less than the above range and the amount of the olefin elastomer is more than the above range, the resulting composition has poor mechanical properties as a resin, that is, it is too soft, which is not preferable. .. Further, if the amount of the olefin resin is in the above range and the amount of the olefin elastomer is less than the above range, the impact resistance becomes poor. If the amount of the olefin resin exceeds the above range and the amount of the olefin elastomer exceeds the above range, the amount of the waste material blended is too small, which is not preferable from the original purpose of effective utilization of the waste material. Further, if the blending amount of talc exceeds the above range, impact resistance is impaired, which is not suitable. Further, if the amount of the diene polymer having a hydroxyl group at the terminal or the hydrogenated product thereof is less than the above range, the effect of improving the impact resistance becomes poor and it becomes unsuitable. Further, even if the amount exceeds the above range, no further effect is expected, and the amount of the expensive polymer added is increased, and the cost of the obtained resin composition is increased, which is not preferable.

[II] Blending The waste material of the above coated olefin resin automobile parts and the above blended composition are blended by mixing both. Kneading is performed in order to perform particularly sufficient mixing. The kneading is carried out by using an ordinary kneading machine such as an extruder, a Banbury mixer, a super mixer, a roll, a Brabender plastograph or a kneader. It is preferable to knead using an extruder, especially a twin-screw extruder. The kneading is performed at 180 to 250 ° C., preferably 19
It is carried out at a temperature of 0 to 230 ° C.

[III] Molding (1) Molding Method Molding is performed by injection molding using an injection molding machine. When the other molding is performed, the flowability is high, so that there is a problem in the moldability. (2) Molding conditions The injection molding is 180 to 250 ° C., preferably 190 to 2
It is carried out at a temperature of 30 ° C. and a discharge pressure of 400 to 2,000 kg / cm ² , preferably 500 to 1,500 kg / cm ² .

[IV] Injection-Molded Product (1) Physical Properties The injection-molded product obtained by the method of the present invention has a paint resin mixed therein, and the compatibility of the paint-based resin with the olefin resin. Is good, the impact resistance is 5 to 50
kg · cm / cm ² , preferably 8 to 15 kg · cm /
Izod impact strength of cm ² , 60-90 kg · cm,
Preferably, the falling weight impact strength is 75 to 85 kg · cm, 5,
000 to 25,000 kg / cm ² , preferably 8.0
Bending elastic modulus of 00 to 17,000 kg / cm ² , 300
% Or more, preferably 500% or more, mechanical properties such as elongation at break, and MFR of 5 to 30 g / 10 minutes, preferably 10 to 20 g / 10 minutes, 0.9 to 1.1 g /
It has physical properties such as a density of cm ³ , preferably 0.95 to 1.05 g / cm ³ .

(2) Usage The injection-molded article obtained by producing a large amount of waste automobile parts as a raw material can be reused as an injection-molded article for various purposes. .. Specifically, automobile exterior parts such as automobile bumpers, mat guards, side moldings, wheel caps, spoilers, instrument panels, levers,
Examples thereof include automobile interior parts such as knobs and linings, electric pots such as pots, vacuum cleaners, washing machines, refrigerators, lighting equipment, audio equipment, and daily sundries such as color boxes and storage cases.

[0020]

EXAMPLES The method for producing the injection-molded article of the present invention will be specifically described below with reference to experimental examples thereof. [I] Evaluation method Evaluation of physical properties in Examples and Comparative Examples is shown below (1) to
It was evaluated by the method of (6). (1) MFR: Compliant with ASTM-D1238, 2.1.
It measured at 230 degreeC using a 6 kg load. (2) Density: Measured at a temperature of 23 ° C. according to ASTM-D1505. (3) Flexural modulus: 23 according to ASTM-D790
It was measured at a temperature of ° C. (4) Tensile elongation at break: Measured at a temperature of 23 ° C. according to ASTM-D638. (5) Izod impact strength: Measured at a temperature of 23 ° C. according to ASTM-D256. (6) Drop weight impact strength: A dart, which is a load sensor, is dropped onto a test piece (120 mm x 80 mm, thickness 2 mm) installed on a support (hole diameter 40 mm) (2 m x 4 kg).
f), the deformation and fracture behavior of the test piece under an impact load was measured, and the impact energy absorbed up to the crack initiation point in the obtained impact pattern was calculated and used as the impact strength of the material.

[II] Experimental Examples Examples 1 to 18 and Comparative Examples 1 to 8 Ethylene content of 8.2% by weight, Flexural modulus of 10,000
0 kg / cm ² , and an MFR of 33 g / 10 min ethylene-propylene block copolymer (hereinafter simply referred to as “EPP”).
Is abbreviated. ), Mooney viscosity at 100 ° C (M
L _{1 + 4} ) is 70 and the density is 0.86 g / cm ² ethylene / propylene copolymer rubber (hereinafter simply abbreviated as “EPM”), hydroxyl group-containing diene polymer having a hydroxyl value of 88 (KOHmg / g) (hereinafter Simply referred to as "diene polymer"), iodine value 1.5 g / 100 g and hydroxyl value 87.
8 (KOHmg / g) diene polymer hydrogenated material and mechanically crushed waste material of painted automobile bumper were blended in the ratios shown in Table 1 and Table 3 and further mixed in a Kawada super mixer. And mixed for 5 minutes, and then kneaded and granulated at a temperature of 210 ° C. by an FCM twin-screw kneader manufactured by Kobe Seisakusho to obtain a composition for injection molding. In order to confirm the physical properties of this injection molding composition, various test pieces were prepared at an injection molding machine with a mold clamping force of 100 tons at a molding temperature of 220 ° C., and the performance was evaluated according to the above-described evaluation method. The evaluation results are shown in Table 1.

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

[Table 3]

[0025]

According to the method for producing an injection-molded article of the present invention as described above, a specific compounding composition is blended in a specific weight ratio using waste material of a large amount of painted automobile parts as a raw material. As a result, the impact resistance of the composition obtained by blending the waste material can be remarkably improved. Therefore, it can be reused as an injection-molded article for various applications such as automobile exterior parts, automobile interior parts, electric products, and sundries. You can

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number in the agency FI Technical indication B29K 105: 16 105: 26 (72) Inventor Hiroyuki Tsuruda 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Yuka Co., Ltd. Yokkaichi Research Institute

Claims (1)

[Claims] 1. A waste material of a coated olefin-based resin automobile part is crushed, and based on 1 part by weight of the crushed product, the following:
A method for producing an injection-molded article, which comprises blending the components (a) to (d) in the following quantitative ratios and injection-molding the mixture. (a) Olefin-based resin 0.5 to 20 parts by weight (b) Olefin-based elastomer 0.25 to 10 parts by weight (c) Diene polymer having terminal hydroxyl group or hydrogenated product thereof 0.01 to 0.5 parts by weight (d) Talc 0-4 parts by weight