JP2005290207A - Reinforced thermoplastic resin composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a regenerated reinforced resin composition and a method for producing the same, having scarce reduction of mechanical strength and change in molding properties compared to that of a virgin material. <P>SOLUTION: The invention relates to the reinforced thermoplastic resin composition comprising (A) 5-90 wt.% of vinyl based copolymer which is a raw material, (B) 0.5-60 wt.% of modified vinyl based copolymer, (C) 5-40 wt.% of fibrous reinforcing material which is a raw material and (D) 5-50 wt.% of crushed molded articles obtained by crushing a molded article comprising (d4) 95-50 wt.% of vinyl based copolymer comprising (d1) an aromatic vinyl based monomer, (d2) a vinyl cyanide based monomer, and (d3) at least a kind of monomers selected from other copolymerizable monomers and (d5) 5-50 wt.% of fibrous reinforcing material, wherein the sum of each component (A), (B), (C) and (D) is 100 wt.%. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to recycling of a reinforced thermoplastic resin, and more particularly to a reinforced thermoplastic resin composition in which a decrease in mechanical strength and a change in moldability are extremely small and a method for producing the same.

  Reinforced styrenic resin reinforced with glass fiber has mechanical balance such as impact resistance and rigidity, excellent molding processability, excellent dimensional stability of the resulting molded product, and is inexpensive. It is used in a wide range of fields as structural parts and mechanical parts for household electrical equipment, OA equipment and automobiles.

  In recent years, recycling of thermoplastic resins has been demanded due to environmental problems, but styrenic resins reinforced with fibrous reinforcements cause damage to the fibrous reinforcements during the molding and recycling process, so unmolded materials Compared to (virgin material), the recycled material has a problem that the mechanical strength is lowered and it cannot be used under the same conditions as a product using an unmolded material.

  In addition, because the recycled material has improved fluidity compared to the unmolded material due to the damage of the fibrous reinforcing material, it is necessary to reset the molding conditions separately when molding the recycled material. There was also a problem of damaging the mold.

  Furthermore, in the case of recycled materials using molded articles collected after being actually used in the market, dust and oily dirt components are attached, so the mechanical properties are particularly deteriorated. There is a problem that the use of the recycled resin is restricted because an odor derived from the dirt component is generated at the time of processing and use of the molded product.

  As a technique for improving the strength of recycled resin, for example, Patent Document 1 describes a compound of a mixture of raw materials, resin additives, and recovered molded product pulverized products. Recycling methods have been proposed that are less in number and excellent in supply characteristics and moldability of the molding machine.

As a technique for improving the strength of glass fiber reinforced styrene resin, for example, Patent Document 2 and Patent Document 3 describe a resin composition comprising a styrene resin modified with the introduction of a functional group and glass fiber. In addition, resin compositions with improved mechanical properties and heat resistance have been proposed.
Japanese Patent Laying-Open No. 2001-026719 (Claim 1) JP-A-6-73253 JP-A-6-136212

  However, when the recycling method described in Patent Document 1 is applied to a styrene resin reinforced with glass fiber, since the styrene resin has a relatively high melt viscosity, the glass fiber is greatly damaged in the molding process. There was a problem that the physical properties could not be sufficiently lowered and the recycling rate could not be increased. Further, there is no mention at all that the molding conditions need to be set individually in accordance with the change in fluidity. Furthermore, especially in the case of a market-collected product collected after a certain period of time in the market, this may occur due to a decrease in mechanical properties due to dirt components adhering to the molded product, or during molding and use of the molded product. The actual situation is that there is a problem of odor and it cannot be used in the same manner as virgin materials.

  On the other hand, the resin compositions described in Patent Document 2 and Patent Document 3 are for the purpose of improving mechanical strength. By adding and blending the specific modified vinyl copolymer of the present invention, a recycled material is obtained. However, there is no mention of an effect that can be used in exactly the same way as an unmolded material and that an unnecessary molded product can be effectively used.

  The present invention has been achieved as a result of studying the solution of the above-described problems in the prior art as a subject, that is, by adding a specific modified vinyl copolymer, mechanically compared to an unmolded material. The present invention provides a reinforced reinforced resin composition having a very low strength reduction and a change in moldability and a method for producing the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved efficiently by adding a specific modified vinyl copolymer to the recycled material, and have reached the present invention. .

  That is, the present invention relates to an aromatic vinyl monomer (a1) 5 to 90% by weight, a vinyl cyanide monomer (a2) 1 to 50% by weight, and other copolymerizable vinyl monomers ( a3) Raw material vinyl copolymer obtained by polymerizing 0 to 90% by weight (A) 5 to 90 parts by weight Aromatic vinyl monomer (b1) 5 to 90% by weight, vinyl cyanide monomer ( b2) 1 to 50% by weight, monomer (b3) selected from unsaturated carboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic anhydride, 0.1 to 30% by weight, and other vinyl-based copolymers The modified vinyl copolymer (B) obtained by polymerizing the monomer (b4) 0 to 90% by weight and the raw fiber reinforcing material (C) 5 to 40% by weight and the fragrance Group vinyl monomer (d1), vinyl cyanide monomer (d2), copolymerizable 95 to 50% by weight of a vinyl copolymer (d4) obtained by polymerizing at least one monomer selected from other vinyl monomers (d3), and a fibrous reinforcing material (d5) 5 to 5%. Reinforced thermoplastic resin composition containing 5-50% by weight of a molded product crushed product (D) obtained by crushing a molded product comprising 50% by weight (however, the total content of each component (A) + ( B) + (C) + (D) = 100% by weight).

  In the reinforced thermoplastic resin composition of the present invention, the raw vinyl copolymer (A) and the vinyl copolymer (d4) are both vinyl resins mainly composed of acrylonitrile / styrene copolymer. The raw material fibrous reinforcing material (C) and the fibrous reinforcing material (d5) are both at least one selected from an aminosilane compound, an epoxysilane compound, a urethane resin, an epoxy resin, and an acrylic resin. Surface-treated glass fiber, monomer (b3) selected from unsaturated carboxylic acid, unsaturated dicarboxylic acid and unsaturated dicarboxylic anhydride used in the modified vinyl copolymer (B) Is acrylic acid or methacrylic acid, and the molded product crushed product (D) is a crushed product of air conditioner fan parts recovered from the market. DOO are both described as preferable conditions.

  The method for producing a reinforced thermoplastic resin composition of the present invention includes the step of washing the molded product crushed product (D) with water and then melt-kneading it with the other components (A) to (C). (D) Melting and kneading with an extruder equipped with a vacuum degassing mechanism (vent) in a state where the component contains 1% by weight or more of water, the molded product crushed product (D), and the (A) to (A) C) Resin pellets obtained by melt-kneading a part of the component and resin pellets obtained by melt-kneading the remainder of the components (A) to (C) are pellet-blended at a predetermined ratio, whereby the above reinforced thermoplastic resin. It is a manufacturing method to obtain.

  The fiber-reinforced thermoplastic resin composition obtained by the present invention has the same mechanical strength and moldability as that of an unmolded material, regardless of recycled material, and has an odor during molding processing or use of a molded product. It solves the problem and enables a wide range of uses in fields that could not be used before. Taking advantage of these excellent features, it is possible to provide materials that satisfy recycling requirements for environmental problems.

  Below, the reinforced thermoplastic resin composition of this invention is demonstrated in detail.

  The reinforced thermoplastic resin composition of the present invention comprises a raw material vinyl copolymer (hereinafter referred to as component (A)), a modified vinyl copolymer (hereinafter referred to as component (B)), and a raw fiber reinforcing material (hereinafter referred to as component (A)). (Referred to as component (C)) and a crushed product (hereinafter referred to as component (D)).

  Below, the reinforced thermoplastic resin composition of this invention is demonstrated in detail.

  The reinforced thermoplastic resin composition of the present invention comprises a raw material vinyl copolymer (A), a modified vinyl copolymer (B), a raw fiber reinforcing material (C), and a crushed product (D). Is done.

  In the present invention, the component (A) is an aromatic vinyl monomer (a1) 5 to 90% by weight, a vinyl cyanide monomer (a2) 1 to 50% by weight, and other copolymerizable vinyl monomers. It is a vinyl copolymer composed of 0 to 90% by weight of monomer (a3). Content in the reinforced thermoplastic resin composition of this invention is 5-90 weight%, Preferably it is 20-80 weight%.

  Specific examples of the aromatic vinyl monomer (a1) constituting the component (A) include styrene, α-methylstyrene, orthomethylstyrene, paramethylstyrene, para-t-butylstyrene, and halogenated styrene. 1 type or 2 types or more can be used. Of these, styrene and α-methylstyrene are preferable, and styrene is particularly preferable.

  The content of the aromatic vinyl monomer (a1) in the component (A) needs to be 5 to 90% by weight, and preferably 15 to 80% by weight.

  Specific examples of the vinyl cyanide monomer (a2) constituting the component (A) include acrylonitrile and methacrylonitrile, and one or more of these can be used. Among these, acrylonitrile is preferable in terms of impact resistance.

  The content of the vinyl cyanide monomer (a2) in the component (A) needs to be 1 to 50% by weight, preferably 3 to 40% by weight.

  As the other copolymerizable vinyl monomer (a3) used as necessary for the component (A), an acrylate ester, a methacrylate ester having an alkyl group having 1 to 6 carbon atoms or a substituted alkyl group, Mention may be made of maleimide compounds and unsaturated amide compounds. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, T-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate and 2-chloroethyl (meth) acrylate, N-methylmaleimide, N-cyclohexyl Maleimide, N-phenylmaleimide, acrylamide and the like can be mentioned. These may be used alone or in combination of two or more.

  The content of the other copolymerizable vinyl monomer (a3) in the component (A) needs to be 0 to 90% by weight.

  The reduced viscosity (ηsp / c) of the component (A) is not particularly limited, but is preferably in the range of 0.2 to 0.8 dl / g, particularly 03 to 0.7 dl / g. When the reduced viscosity is outside the above range, the impact resistance is lowered, or the melt viscosity is increased and the moldability tends to be deteriorated.

  There is no restriction | limiting in particular in the manufacturing method of (A) component, Any, such as block polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, may be sufficient. There is no particular limitation on the monomer charging method at the time of production, and any of initial batch charging, continuous charging of part or all of the monomer, or split charging of part or all of the monomer is used. May be.

  The component (B) in the present invention is an aromatic vinyl monomer (b1) 5 to 90% by weight, a vinyl cyanide monomer (b2) 1 to 50% by weight, an unsaturated carboxylic acid, an unsaturated dicarboxylic acid. A modified vinyl copolymer comprising 0.1 to 30% by weight of a monomer (b3) selected from acid anhydrides and 0 to 90% by weight of another copolymerizable vinyl monomer (b4) . The content of the reinforced thermoplastic resin composition of the present invention is 0.5 to 60% by weight, preferably 1 to 40% by weight.

  The aromatic vinyl monomer (b1) and the vinyl cyanide monomer (b2) constituting the component (B) are the aromatic vinyl monomers (a1) exemplified in the component (A) and A monomer similar to the vinyl cyanide monomer (a2) can be used, and preferred specific examples thereof are the same as those of (a1) and (a2).

  The content of the aromatic vinyl monomer (b1) in the component (B) needs to be 5 to 90% by weight, and preferably 15 to 80% by weight.

  The content of the vinyl cyanide monomer (b2) in the component (B) needs to be 1 to 50% by weight, preferably 3 to 40% by weight. If it is less than the above range, the impact strength is remarkably lowered, and if it exceeds the above range, the fluidity is lowered.

  Specific examples of the monomer (b4) selected from the unsaturated carboxylic acid, unsaturated dicarboxylic acid and unsaturated dicarboxylic anhydride constituting the component (B) include acrylic acid, methacrylic acid, crotonic acid, maleic acid, Itaconic acid, maleic anhydride and the like can be mentioned, and one or more of these can be used. Of these, acrylic acid and methacrylic acid are preferable in terms of impact resistance.

  The content of the monomer (b3) selected from unsaturated carboxylic acid, unsaturated dicarboxylic acid, and unsaturated dicarboxylic anhydride in the modified vinyl copolymer (B) needs to be 0.1 to 30% by weight. And preferably 1 to 20% by weight. If it is less than the above range, the mechanical strength is lowered, and if it exceeds the above range, the fluidity is lowered.

  The other copolymerizable vinyl monomer (b4) used as necessary for the component (B) is the same as the other copolymerizable vinyl monomer (a3) exemplified in the component (A). Similar monomers can be used, and preferred specific examples are also the same as in (a3).

  Although there is no restriction | limiting in particular in the reduced viscosity ((eta) sp / c) of (B) component, It is preferable to exist in the range of 0.2-0.8 dl / g, especially 03-0.7 dl / g. When the reduced viscosity is outside the above range, the impact resistance is lowered, or the melt viscosity is increased and the moldability tends to be deteriorated.

  There is no restriction | limiting in particular in the manufacturing method of (B) component, Any of block polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. may be sufficient. There is no particular limitation on the monomer charging method at the time of production, and any of initial batch charging, continuous charging of part or all of the monomer, or split charging of part or all of the monomer is used. May be.

  The component (C) in the present invention is a fibrous reinforcing material added to a resin material mainly for the purpose of improving mechanical properties. Specific examples include glass fiber, carbon fiber, alumina fiber, silicon carbide. Examples thereof include fiber, ceramic fiber, asbestos fiber, stone-kow fiber, metal fiber, wollastonite, potassium titanate whisker, and zinc oxide whisker. Among them, glass fiber is preferable.

  Moreover, it is more preferable from the viewpoints of mechanical strength and productivity to use these fibrous reinforcing materials after surface treatment with an aminosilane compound, an epoxysilane compound, a urethane resin, an epoxy resin, an acrylic resin or the like.

  The content of the component (C) in the reinforced recycled thermoplastic resin composition is 5 to 40% by weight, preferably 10 to 30% by weight.

  The component (D) in the present invention refers to a molded product obtained by molding a fiber reinforced thermoplastic resin substantially composed of a vinyl copolymer (d4) and a fibrous reinforcing material (d5) by a known method. Crushed to a size that can be melt kneaded.

  The vinyl copolymer (d4) constituting the component (D) is an aromatic vinyl monomer (d1), a vinyl cyanide monomer (d2), and an unsaturated carboxylic acid alkyl ester monomer. It is a copolymer obtained by polymerizing at least one monomer selected from the body (d3), and each of the monomers (d1) to (d3) includes the raw material vinyl copolymer (A). The same monomers as those exemplified in (a1) to (a3) can be used, and preferred specific examples are also the same as those in (a1) to (a3). The content of the vinyl copolymer (d4) in the component (D) needs to be 95 to 50% by weight.

  The fibrous reinforcing material (d5) constituting the component (D) is the same fibrous reinforcing material as the component (C), and preferred specific examples are also the same as those in (C). The content of the fibrous reinforcing material (d5) in the component (D) is 5 to 50% by weight, preferably 5 to 30% by weight.

  Although there is no restriction | limiting in particular in the shaping | molding method of the molded article used for (D) component, Generally, injection molding, extrusion molding, blow molding, vacuum molding, compression molding, etc. are used preferably, and injection molding is especially preferable.

  As the above-mentioned molded products, defective molding products generated in the molding process, unnecessary products such as sprues and runners, and market-collected products that are discarded and collected after the molded products have been used for a certain period in the market are preferably used.

  The resin composition of the molded product used for the component (D) does not have to be one type, and in particular, in the case of a market-recovered product, a molded product having a plurality of resin compositions is mixed. In that case, there is no problem if the average composition after crushing is within the range of the composition of the component (D). Furthermore, if it is 10% by weight or less of the total molded product, a resin molded product other than the vinyl copolymer may be mixed.

  (D) component is obtained by crushing the said molded article into the magnitude | size which can be supplied to an extruder. In this case, the size of the crushed component (D) is preferably such that the major axis dimension of the fragments is 20 mm or less. If the fragments are too large, it is difficult to mix uniformly with other components, and it is difficult to supply them to the melt mixer, which affects the operability and variations in the quality of the recycled material obtained. .

  When using a market recovery molded product as the component (D), it is particularly preferable to remove the deposits by washing with water in advance. The cleaning method is not particularly limited as long as it can remove deposits with water, but it is possible to use a batch type cleaning method in which a molded product is immersed in a water tank and the molded product is taken out after stirring, a belt conveyor or a rotary screen. There is a continuous cleaning method in which water is poured during conveyance of the molded product.

  Moreover, it is also possible to coarsely pulverize before washing for the purpose of improving washing efficiency.

  The content of the component (D) in the reinforced recycled thermoplastic resin composition is 5 to 50% by weight, preferably 5 to 30% by weight.

  When the content of the component (D) exceeds 50% by weight, the mechanical strength of the fiber-reinforced thermoplastic resin is remarkably lowered, and when it is less than 5% by weight, the significance of recycling is lowered, which is not preferable.

  The total content (A) + (B) + (C) + (D) of the components (A) to (D) is 100% by weight.

  Although there is no restriction | limiting in particular as a kind of market collection | recovery molded product which comprises (D) component, The fan component of an air-conditioner is mentioned as a particularly preferable specific example at the point which the resin material currently used is substantially unified.

  The reinforced thermoplastic resin composition of the present invention includes various thermoplastic resins, for example, polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, and nylon, as long as the object of the present invention is not impaired. The performance of the molding resin composition can be further improved by blending polyamide resin such as 6, nylon 6, 6 or the like, modified PPE resin, polycarbonate resin, polyacetal resin, or modified products and elastomers thereof.

  If necessary, the reinforced thermoplastic resin composition of the present invention includes hindered phenol-based, sulfur-containing compound-based, phosphorus-containing organic compound-based antioxidants, phenol-based, acrylate-based thermal stabilizers, etc. , UV absorbers such as benzotriazole, benzophenone, and succinate, light stabilizers such as organic nickel and hindered amine, metal salts of higher fatty acids, lubricants such as higher fatty acid amides, phthalates, phosphates Plasticizers such as brominated compounds, various flame retardants such as brominated compounds, phosphate esters, red phosphorus, flame retardant aids such as antimony trioxide and antimony pentoxide, metal salts of alkyl carboxylic acids and alkyl sulfonic acids, carbon black, Pigments and dyes can be added, and various fillers can be blended.

  Below, the manufacturing method of the reinforced thermoplastic resin composition of this invention is demonstrated in detail.

  The method for melt kneading the fiber reinforced thermoplastic resin composition of the present invention is not particularly limited, and the mixture of raw materials is supplied to a normal melt mixer such as a single or twin screw extruder, Banbury mixer, kneader and mixing roll. As a typical example, a method of melt kneading at a temperature of 200 to 300 ° C. can be given as a typical example. Among them, it is preferable to melt knead and pelletize with a single screw or twin screw extruder. As temperature conditions, it is preferable to set it as 240-290 degreeC in order to suppress the failure | damage of a fibrous reinforcement.

  When using a market-recovered molded product for component (D), for the purpose of reducing odor, component (D) is supplied to the extruder in a state of containing 1% or more of water, and reduced in pressure during melt kneading. A more preferable production condition is to remove volatile components by a deaeration mechanism (vent).

  From the viewpoint of productivity, melt (D), resin pellets obtained by melting and kneading a part of the components (A) to (C), and the remainder of components (A) to (C). The kneaded resin pellets are preferably pellet blended at a predetermined ratio.

  The reinforced thermoplastic resin composition obtained as described above is a known method currently used for molding thermoplastic resins such as injection molding, extrusion molding, blow molding, vacuum molding, compression molding, and gas assist molding. Can be molded into an arbitrary shape to obtain a molded product.

  The molded product of the present invention is a structural component such as a household electrical appliance, an OA device, and an automobile, taking advantage of the excellent dimensional stability and molding processability of the obtained molded product, and electrical insulation and low cost. Used as a mechanical component in a wide range of fields.

  Specifically, the molded product of the present invention is an air conditioner fan for indoor units in air conditioner parts for home use and business use, etc., and electric / electronic represented by propeller fans for outdoor units, liquid crystal display parts, computer related parts, etc. Parts, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, typewriter parts, word processor parts, etc. Home / office electrical product parts represented by, pachinko, slot machine, game / entertainment product parts represented by game machines, office computer related parts, telephone related parts, facsimile related parts, copier related parts, writer, type Represented by lighters It is useful for various applications such as machine parts, microscopes, cameras, optical equipment such as cameras, precision machine parts, toiletries, toys, chemical plants, aircraft parts, etc. On the other hand, it can be suitably used by taking advantage of small changes in mechanical strength and fluidity and low odor.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this does not restrict | limit this invention with this. In Examples and Comparative Examples, “parts” or “%” are all weight ratios unless otherwise specified. First, a method for evaluating the characteristics and the like of the reinforced thermoplastic resin will be described below.

(1) Tensile strength The pellets of the thermoplastic resin composition dried for 3 hours in a hot air dryer at 80 ° C. are filled into a Toshiba Machine Co., Ltd. IS50A molding machine set at a cylinder temperature of 250 ° C., and a test piece is formed by injection molding. Got. Measured according to ASTM D638.

(2) Flexural modulus The pellets of the thermoplastic resin composition dried for 3 hours in an 80 ° C. hot air dryer were filled into an IS50A molding machine manufactured by Toshiba Machine Co., Ltd. set at a cylinder temperature of 250 ° C. and tested by injection molding. I got a piece. Measurement was performed in accordance with ASTM D790 (12.7 mm (W) × 127 mm (L) × 6.4 mm (t), 23 ° C.).

(3) Izod impact strength The pellets of the thermoplastic resin composition dried for 3 hours in an 80 ° C. hot air dryer were filled in an IS50A molding machine manufactured by Toshiba Corporation set at a cylinder temperature of 250 ° C., and a test piece was formed by injection molding. Got. Measured according to ASTM D256 (12.7 mm notched, 23 ° C.).

(4) Fluidity The pellets of the thermoplastic resin composition dried for 3 hours in a hot air dryer at 80 ° C. were filled into a Toshiba IS50A molding machine set at a cylinder temperature of 250 ° C., and 10 mm at an injection pressure of 70 MPa. A spiral shaped product of (W) × 2 mm (t) was injection molded, and the spiral flow length was measured.

(5) Creep strain A test piece similar to the above-described tensile strength measurement was subjected to a tensile load of 35 MPa in a 60 ° C. atmosphere, and the amount of creep strain after 300 hours from the start of the test was measured.

(6) Odor level The pellets of the thermoplastic resin composition dried for 3 hours in an 80 ° C. hot air dryer were filled into an IS50A molding machine manufactured by Toshiba Machine Co., Ltd. set at a cylinder temperature of 250 ° C., and the screw retracted position was 80 mm. The operation of purging after metering was repeated three times until a mass was obtained to obtain a massive molten resin.
Immediately from the position of 50 cm, 1 m and 2 m, the obtained molten resin was subjected to the following 5 odor differences from the virgin material (AC-1 described in Reference Example 5) containing no recycled material. It was scoring at the stage, and the average of the scores of 5 people was taken as the odor level.
1: Feels no odor difference from virgin material even at 50cm.
2: The odor difference is slightly felt at the position of 50 cm, but the odor difference is not felt at the position of 1 m.
3: Feel the odor difference at the 50 cm position, but do not feel the odor difference at the 1 m position.
The odor difference is felt at the position of 4: 1 m, but the odor difference is not felt at the position of 2 m.
I feel a difference in odor from the virgin material even at 5: 2 m.

(Reference Example 1) Production Method A-1 of Vinyl Copolymer (A): A monomer mixture consisting of 70% by weight of styrene and 30% by weight of acrylonitrile is bulk polymerized,
A pellet-shaped copolymer was obtained. The intrinsic viscosity [η] of the copolymer was 0.53 dl / g.

(Reference Example 2) Production Method B-1 of Modified Vinyl Copolymer (B): Suspension polymerization of 70% by weight of styrene, 25% by weight of acrylonitrile, and 5% by weight of methacrylic acid to produce a bead-like modified vinyl copolymer. A polymer was obtained. The intrinsic viscosity [η] of the copolymer was 0.60 dl / g.

(Reference Example 3) Fibrous reinforcement (C)
C-1: Nippon Electric Glass Co., Ltd. chopped strand ECS03T-351 (average fiber diameter 13 μm) was used.

(Reference Example 4) Molded product pulverized product (D)
D-1: After blending the above A-1, 80% by weight and C-1, 20% by weight, the mixture was melt-kneaded with a 40 mmφ single-screw extruder having a cylinder setting temperature of 250 ° C., pelletized, and then cylinder temperature An IS50A molding machine manufactured by Toshiba Machine Co., Ltd. set to 250 ° C. was filled, and a tensile test piece compliant with ASTM D638 was obtained by injection molding.

The tensile test piece was crushed with a crusher so that the major axis dimension was 10 mm or less. The moisture content of the crushed product was 0.1 wt%.
D-2: The air conditioner fan parts collected after use in the market were roughly crushed with a crusher so that the major axis dimension was 100 mm or less, and the crushed product was stirred and washed in a water tank.

The washed crushed material was drained with a metal punch for 12 hours, and then crushed with a crusher so that the major axis dimension was 10 mm or less. The resin component of the crushed product was mainly composed of acrylonitrile / styrene copolymer, the ash content was 20.1 wt%, and the ashed product was mainly composed of glass fiber. The moisture content of the crushed product was 2.7 wt%.
D-3: The crushed product D-2 was further air-dried for one week, and the moisture content was dried to 1.1 wt%.
D-4: The air conditioner fan parts collected after use in the market were crushed with a crusher so that the major axis dimension was 10 mm or less without washing with water. The ash content was 20.4 wt%, and the ashed product was mainly composed of glass fiber. The moisture content of the crushed product was 0.3 wt%.

(Reference Example 5) Resin pellet AC-1 composed of vinyl copolymer (A) and fibrous reinforcing material (C): After blending the above A-1, 80% by weight and C-1, 20% by weight The mixture was melt-kneaded with a vented 40 mmφ single-screw extruder having a cylinder set temperature of 250 ° C. to obtain a pellet-shaped resin.
Various characteristics of the obtained pellets were evaluated in the same manner as in Examples as specific examples of unmolded materials that did not contain the crushed molded product (D), and the results are listed in Table 1.

(Reference Example 6) Pellet DBC-1 composed of a pulverized product (D), a modified vinyl copolymer (B), and a fibrous reinforcing material (C): the crushed product D-1, 80 wt%, B-1 , 16 wt%, C-1, 4 wt%, and then melt-kneaded in a vented 40 mmφ single screw extruder with a cylinder set temperature of 250 ° C. to obtain a pellet-shaped recycled resin.
DBC-2: After blending the above crushed product D-2, 80 wt%, B-1, 16 wt%, C-1, 4 wt%, melt kneading in a 40 mmφ single screw extruder with a vent with a cylinder set temperature of 250 ° C A pellet-shaped recycled resin was obtained.
DBC-3: After blending the crushed product D-3, 80 wt%, B-1, 16 wt%, C-1, 4 wt%, melt kneading with a 40 mmφ single screw extruder with a vent with a cylinder set temperature of 250 ° C. A pellet-shaped recycled resin was obtained.
DBC-4: After blending the crushed product D-4, 80 wt%, B-1, 16 wt%, C-1, 4 wt%, melt kneading with a vented 40 mmφ single screw extruder with a cylinder set temperature of 250 ° C. A pellet-shaped recycled resin was obtained.

(Example 1)
40 mmφ single-screw extruder having a cylinder set temperature of 250 ° C. after blending the A-1, B-1, C-1 and the crushed tensile test piece D-1 described in Reference Examples 1 to 4 at the ratio shown in Table 1. And kneaded to obtain a pellet-shaped resin.

  Various characteristics of the obtained pellets were evaluated by the above-described analysis method, and the results are shown in Table 1. The compounding formulation of the present invention is excellent in mechanical properties, fluidity and creep strain, and is equivalent to the unmolded material (Reference Example 5).

(Example 2)
The blending ratio of D-1 in Example 1 was reduced from 20% to 10%, and similarly A-1, B-1, and C-1 were blended in the ratios shown in Table 1, and then melt-kneaded in the same manner as in Example 1. The evaluation results of the pellet-shaped resin are listed in Table 1. The compounding formulation of the present invention is excellent in mechanical properties, fluidity and creep strain, and is equivalent to the unmolded material (Reference Example 5).

(Example 3)
The blending ratio of D-1 in Example 1 was increased from 20% to 45%, and similarly A-1, B-1, and C-1 were blended in the ratios shown in Table 1, and then melt-kneaded in the same manner as in Example 1. The evaluation results of the pellet-shaped resin are listed in Table 1. The compounding formulation of the present invention is excellent in mechanical properties, fluidity and creep strain, and is equivalent to the unmolded material (Reference Example 5).

Example 4
The blending ratio of B-1 in Example 1 was increased from 4% to 32%, and A-1, C-1, and D-1 were blended in the ratios shown in Table 1 and then melt-kneaded in the same manner as in Example 1. The evaluation results of the pellet-shaped resin are listed in Table 1. The compounding formulation of the present invention is excellent in mechanical properties, fluidity and creep strain, and is equivalent to the unmolded material (Reference Example 5).

(Example 5)
D-1 in Example 1 was changed to air-conditioner fan crushed product D-2, and after blending A-1, B-1, and C-1 in the ratio of Table 1 as well, melt-kneaded in the same manner as in Example 1, pellets Table 1 shows the evaluation results of the resin-like resins. The compounding formulation of the present invention is excellent in mechanical properties, fluidity and creep strain, and is equivalent to the unmolded material (Reference Example 5).

(Example 6)
D-1 in Example 1 was changed to an air-conditioner fan crushed product D-3, and after blending A-1, B-1, and C-1 in the ratios shown in Table 1, they were melt-kneaded in the same manner as in Example 1. Table 1 shows the evaluation results of the resin-like resins. The compounding formulation of the present invention is excellent in mechanical properties, fluidity and creep strain, and is equivalent to the unmolded material (Reference Example 5).

(Example 7)
D-1 in Example 1 was changed to air-conditioner fan crushed product D-4, and A-1, B-1, and C-1 were similarly blended in the ratios shown in Table 1, and then melt-kneaded in the same manner as in Example 1. Table 1 shows the evaluation results of the resin-like resins. In the compounding formulation of the present invention, mechanical properties, fluidity and creep strain are slightly lower than those of the unmolded material (Reference Example 5), but various properties are better than those of Comparative Example 5 in which B-1 is not used. It is.

(Example 8)
After pellet blending of AC-1 described in Reference Example 4 and DBC-1 described in Reference Example 5 at the ratio shown in Table 1, various characteristics were evaluated by the above-described analysis method, and the results are shown in Table 1.

  The compounding formulation of the present invention is excellent in mechanical properties, fluidity and creep strain, and is equivalent to the unmolded material (Reference Example 5).

Example 9
DBC-1 in Example 8 was changed to DBC-2. Similarly, AC-1 was pellet-blended at the ratio shown in Table 1, and then various characteristics were evaluated by the analysis method described above. The results are shown in Table 1.

  The compounding formulation of the present invention is excellent in mechanical properties, fluidity and creep strain, and is equivalent to the unmolded material (Reference Example 5).

(Example 10)
The blend ratio of DBC-12 in Example 9 was increased from 25% to 56%. Similarly, after AC-1 was pellet-blended at the ratio shown in Table 1, various characteristics were evaluated by the analysis method described above. It was raised in.

  The compounding formulation of the present invention is excellent in mechanical properties, fluidity and creep strain, and is equivalent to the unmolded material (Reference Example 5).

(Example 11)
DBC-1 in Example 8 was changed to DBC-3. Similarly, AC-1 was pellet-blended at the ratio shown in Table 1, and then various characteristics were evaluated by the analysis method described above. The results are shown in Table 1.
The compounding formulation of the present invention is excellent in mechanical properties, fluidity and creep strain, and is equivalent to the unmolded material (Reference Example 5).

(Example 12)
DBC-1 in Example 8 was changed to DBC-4. Similarly, AC-1 was pellet-blended at the ratio shown in Table 1, and then various characteristics were evaluated by the analysis method described above. The results are shown in Table 1.
In the compounding formulation of the present invention, mechanical properties, fluidity and creep strain are slightly lower than those of the unmolded material (Reference Example 5), but various properties are better than those of Comparative Example 5 in which B-1 is not used. It is.

(Comparative example)
In Comparative Example 1, various properties were evaluated in the same manner as in the Examples for the pelletized resin pellets after blending A-1, C-1 and the pulverized tensile test piece D-1 in the ratios shown in Table 2. Since the modified vinyl copolymer (B) is not included, mechanical properties, fluidity, and creep strain are all deteriorated.

  Comparative Example 2 evaluates various properties of pelletized resin pellets after blending A-1, B-1, C-1, and D-1 at the ratios shown in Table 2 in the same manner as in Examples. Since the blending amount of D-1 is out of the range of the present invention, the mechanical properties, fluidity and creep strain are remarkably lowered.

Comparative Examples 3-6 evaluated various characteristics of the pelletized resin pellets after blending A-1, C-1 and air-conditioner fan crushed products D-2-4 at the ratios shown in Table 2, respectively. Is. Since none of them contains the modified vinyl copolymer (B), various properties are deteriorated.

Claims (8)

Aromatic vinyl monomer (a1) 5 to 90% by weight, vinyl cyanide monomer (a2) 1 to 50% by weight, and other copolymerizable vinyl monomers (a3) 0 to 90 5% to 90% by weight of a raw vinyl copolymer (A) obtained by polymerizing% by weight,
Aromatic vinyl monomer (b1) 5 to 90% by weight, vinyl cyanide monomer (b2) 1 to 50% by weight, selected from unsaturated carboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride Modified vinyl copolymer (B) 0 obtained by polymerizing 0.1 to 30% by weight of monomer (b3) and 0 to 90% by weight of other copolymerizable monomer (b4) 5-60% by weight,
Raw fiber reinforcing material (C) 5 to 40% by weight, and
Polymerizing at least one monomer selected from an aromatic vinyl monomer (d1), a vinyl cyanide monomer (d2), and other copolymerizable vinyl monomers (d3); Molded product crushed product (D) 5 to 50% by weight obtained by crushing a molded product comprising 95 to 50% by weight of vinyl copolymer (d4) and 5 to 50% by weight of fibrous reinforcing material (d5) Reinforced thermoplastic resin composition (however, the total content of each component (A) + (B) + (C) + (D) = 100% by weight)).   The raw material vinyl copolymer (A) and the vinyl copolymer (d4) are both vinyl copolymers mainly composed of acrylonitrile / styrene copolymer. The reinforced thermoplastic resin composition as described.   Both the raw material fibrous reinforcing material (C) and the fibrous reinforcing material (d5) are surface-treated with at least one selected from an aminosilane compound, an epoxysilane compound, a urethane resin, an epoxy resin, and an acrylic resin. The reinforced thermoplastic resin composition according to claim 1 or 2, wherein:   The monomer (b3) selected from the unsaturated carboxylic acid, unsaturated dicarboxylic acid, and unsaturated dicarboxylic anhydride used in the modified vinyl copolymer (B) is acrylic acid or methacrylic acid. The reinforced thermoplastic resin composition according to any one of claims 1 to 3.   The reinforced thermoplastic resin composition according to any one of claims 1 to 4, wherein the crushed product (D) is a crushed product of air-conditioner fan parts recovered from the market. Polymerizing at least one monomer selected from an aromatic vinyl monomer (d1), a vinyl cyanide monomer (d2), and other copolymerizable vinyl monomers (d3); The molded product crushed product (D) obtained by crushing a molded product comprising 95 to 50% by weight of the vinyl copolymer (d4) and 5 to 50% by weight of the fibrous reinforcing material (d5) is washed with water. After
Aromatic vinyl monomer (a1) 5 to 90% by weight, vinyl cyanide monomer (a2) 1 to 50% by weight, and other copolymerizable vinyl monomers (a3) 0 to 90 Raw material vinyl copolymer (A) obtained by polymerizing wt%, aromatic vinyl monomer (b1) 5 to 90 wt%, vinyl cyanide monomer (b2) 1 to 50 wt%, A monomer (b3) 0.1 to 30% by weight selected from a saturated carboxylic acid, an unsaturated dicarboxylic acid, and an unsaturated dicarboxylic anhydride and another copolymerizable vinyl monomer (b4) are polymerized. Modified vinyl copolymer (B) and raw fiber reinforcing material (C)
And a method for producing a reinforced thermoplastic resin composition, characterized by melting and kneading.   The reinforced product according to claim 6, wherein the crushed product (D) is melt-kneaded with an extruder equipped with a vacuum degassing mechanism (vent) in a state containing 1% by weight or more of water. A method for producing a thermoplastic resin composition.   Obtained by melt-kneading a part of the molded product crushed product (D), the raw material vinyl copolymer (A), the modified vinyl copolymer (B), and the raw fiber reinforcing material (C). Pellet blending resin pellets and resin pellets obtained by melting and kneading the raw material vinyl copolymer (A), the modified vinyl copolymer (B) and the remainder of the raw fiber reinforcing material (C) component; The method for producing a reinforced thermoplastic resin composition according to claim 6 or 7, characterized in that: