JP2005226003A - Thermoplastic elastic body composition and its utilization - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastic body composition which satisfies the functions of flexibility, slip preventing nature, moldability/processability, heat resistance, durability and the like without the need for addition of a large quantity of a softener and which is suited for recycling because of being excellent in compatibility with a resin base material such as an ABS resin and capable of being subjected to regeneration treatment after the use as a product without segregating it from a resin molding as a substrate. <P>SOLUTION: The thermoplastic elastic body composition contains 100 pts. wt. of an addition polymerization type thermoplastic block elastic body (A) consisting of a polystyrene block and a hydrogenated or non-hydrogenated polyisoprene and/or polybutadiene block, 20-200 pts. wt. of a polyurethane elastomer (B), 20-100 pts. wt. of a rubber-containing graft copolymer (C) formed by polymerizing a vinyl cyanide monomer and an aromatic vinyl monomer on a rubbery polymer, and 0-50 pts. wt. of an oil (D). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a thermoplastic elastic composition and use thereof. Specifically, it does not require the addition of a large amount of softening agent, satisfies functions such as flexibility, anti-slip properties, molding processability, heat resistance and durability, and is compatible with resin base materials such as ABS resins. A thermoplastic elastomer composition suitable for recycling, which is excellent and can be recycled without being separated from the resin molded product of the substrate after use as a product, and a thermoplastic formed by molding this thermoplastic elastomer composition Elastic molded product, resin molded product with elastic body formed by joining this thermoplastic elastic molded product to resin molded product, recycling method of resin molded product with elastic body, and regenerative heat obtained from resin molded product with elastic body The present invention relates to a plastic resin composition and a recycled thermoplastic resin molded article.

  As a molding material for casings of information equipment and general office equipment, ABS resin or alloy material of ABS resin and polycarbonate, thermoplastic polyester resin, nylon resin or the like is used. And the leg rubber | gum is adhere | attached or welded to the bottom part of such a housing | casing for the purpose of anti-vibration and a slip prevention. In addition, a soft gasket is inserted into the fitting portion of the housing for the purpose of dust prevention and the like.

  By the way, from the viewpoints of resource utilization, waste reduction, and environmental protection, material recycling of plastic products is not limited to these cases, and is an effective means for production in many fields such as information equipment, office equipment, and home appliances. Inspected products extracted during sampling inspections, defective products generated in production processes, returned goods after being shipped as products, and waste products that have finished their role in the market are collected, recycled, and recycled. It is hoped that.

  However, since the above-mentioned leg rubber and gasket are not compatible with ABS resin, which is a molding material of the thermoplastic elastic composition, when recycling the casing to which the leg rubber or gasket is attached in this way. In this case, it is necessary to dismantle and separate these in advance, which is one of the causes of increasing the recycling cost. In particular, since the rubber material is cross-linked, if it is mixed even in a small amount, it will be scattered in the form of black spots in the recycled material, and the appearance of the recycled product will be impaired.

  In general, soft PVC or thermoplastic elastomer is used as a substitute for rubber. However, soft PVC has problems such as deterioration of the casing due to migration of plasticizer and poor thermal stability and is not suitable for recycling. The plastic elastomer has problems such as poor weldability with the casing, compatibility with the ABS resin material, molding processability, and slip resistance.

  For this reason, there is a need for a thermoplastic elastic material that is excellent in vibration proofing, anti-slip effect, molding processability, durability, good compatibility with resin materials, particularly ABS resin materials, and easy to recycle. Yes.

  On the other hand, in recent years, a thermoplastic elastic body has been developed that enhances heat-fusibility with an ABS resin substrate during two-color molding and coextrusion with an ABS resin. Since this technique inevitably increases the compatibility with the ABS-based resin, it is considered that this technique also addresses the above problems.

  For example, JP-A-6-65467 discloses an elastic composition comprising a styrene / isoprene elastomer and a polyester, polyamide, and polyurethane elastomer, and JP-A-6-107898 discloses a styrene / polybutadiene elastomer and a polyurethane system. An elastomer composition comprising an elastomer, Japanese Patent Application Laid-Open No. 9-3323 discloses an elastic composition composed of a styrene / polybutadiene elastomer and a polyamide elastomer, and Japanese Patent Application Laid-Open No. 9-3324 discloses a styrene / isoprene elastomer and a polyamide system. An elastic composition comprising an elastomer is described.

  However, these use an expensive elastomer as a main component in order to obtain heat-fusibility with a base material, and there is a problem that the price of the product becomes high. Furthermore, although the weldability with the substrate is excellent, the compatibility is insufficient. Therefore, when it is recycled, there is a problem that the dispersibility is poor and the appearance is poor, and the use for other purposes is limited.

  JP-A-8-34900 and JP-A-9-324100 describe composite molding resin compositions in which a polyolefin resin and an oil as a softening agent are added to a styrene elastomer. Since the base material is an olefin resin, compatibility with the ABS resin cannot be obtained.

JP 2001-247742 A discloses a heat-fusible resin composition in which a rubber-containing graft copolymer, a softener, and a polyurethane / polyester elastomer are blended with a styrene elastomer. This product requires the addition of a large amount of a softening agent in order to obtain an appropriate flexibility, which causes problems such as a decrease in molding processability and heat resistance.
JP-A-6-65467 JP-A-6-107898 Japanese Patent Laid-Open No. 9-3323 JP-A-9-3324 JP-A-8-34900 JP-A-9-234100 JP 2001-247742 A

  The present invention solves the above-mentioned conventional problems, satisfies functions such as flexibility, anti-slip properties, molding processability, heat resistance, durability, and the like, without requiring a large amount of softening agent, and further, ABS resin, etc. An object of the present invention is to provide a thermoplastic elastomer composition suitable for recycling, which is excellent in compatibility with a resin base material and can be regenerated without being separated from a resin molded product of a substrate after being used as a product. To do.

  The present invention also provides a thermoplastic elastic molded product formed by molding the thermoplastic elastic composition, a resin molded product with an elastic body formed by joining the thermoplastic elastic molded product to a resin molded product, and the resin with an elastic body. It aims at providing the recycling method of a molded article, the reproduction | regeneration thermoplastic resin composition obtained from this resin molded article with an elastic body, and the reproduction | regeneration thermoplastic resin molding.

  The thermoplastic elastic composition of the present invention comprises an addition polymerization type thermoplastic block elastic body (A) 100 parts by weight comprising a polystyrene block, a hydrogenated or non-hydrogenated polyisoprene and / or polybutadiene block, and a polyurethane system. 20 to 200 parts by weight of an elastomer (B) and 20 to 100 parts by weight of a rubber-containing graft copolymer (C) obtained by polymerizing a vinyl cyanide monomer and an aromatic vinyl monomer to a rubber polymer. It is characterized by containing.

  By blending the above components (A) to (C) in a specific formulation, functions such as flexibility, anti-slip properties, molding processability, heat resistance and durability are satisfied without the need to add a large amount of softener. Furthermore, a thermoplastic elastomer composition suitable for recycling, which is excellent in compatibility with a resin base material such as an ABS resin and can be recycled without being separated from a resin molded product of a substrate after being used as a product. Can be obtained.

  In particular, the addition polymerization type thermoplastic block elastic body (A) and the polyurethane elastomer (B) have specific hardness, and the rubber-containing graft copolymer (C) has a specific rubber amount, graft ratio and vinyl unit. By using a monomer composition ratio and a molecular weight, the above-described effects can be obtained with certainty.

  In the present invention, the addition polymerization type thermoplastic block elastic body (A) is composed of two or three blocks of a polystyrene block and a hydrogenated or non-hydrogenated polyisoprene block, or a polystyrene block and a hydrogenated or non-hydrogenated block. Those consisting of an attached polybutadiene block are preferred, and their hardness (Shore A) is preferably 80 or less.

  The polyurethane elastomer (B) has a diisocyanate, a hard segment composed of a short-chain glycol, and a soft segment composed of a long-chain polyol, and the long-chain polyol is a polyether-based and / or polyester-based polyol. The hardness (Shore A) is preferably 80 or less.

  Examples of the rubber component of the rubber-containing graft copolymer (C) include one or more rubber components selected from the group consisting of polybutadiene rubber, acrylic rubber, olefin rubber, and silicon rubber, The rubber component content is preferably 40 to 80% by weight.

  The weight ratio of the vinyl cyanide monomer and aromatic vinyl monomer polymerized to the rubber-containing graft copolymer (C) is vinyl cyanide monomer / aromatic vinyl monomer = 15/85. It is preferred that the graft ratio is 40 to 60 and the graft ratio is 15 to 85%.

  The thermoplastic elastic composition of the present invention may further contain 50 parts by weight or less of oil (D) as necessary, and as oil (D), process oil, softener for mineral oil rubber , One or more selected from the group consisting of aromatic oils, paraffinic oils and naphthenic oils.

  The thermoplastic elastic molded article of the present invention is formed by molding such a thermoplastic elastic composition of the present invention, and is used for parts such as dustproof, vibration-proof and anti-slip parts of equipment (eg, leg rubber). Useful.

  The resin molded product with an elastic body of the present invention is a resin molded product in which the thermoplastic elastic molded product of the present invention is joined and integrated by welding, fitting, adhesion, etc. Can be subjected to a regeneration treatment without the need to remove the thermoplastic elastic molded product.

  The method for recycling a resin-molded article with an elastic body of the present invention is a method of melting and recycling such a resin-molded article with an elastic body of the present invention, wherein a thermoplastic elastic molded article bonded to the resin molded article is recycled. It is characterized by melting as it is without removing.

  That is, the thermoplastic elastomer composition of the present invention does not interfere with the performance of the resin base material of the resin molded product, has good compatibility and dispersibility, and does not mix as foreign matter. It is possible to recycle by melting, kneading, etc. by simply crushing, pulverizing, etc. as necessary, in the joined state, without requiring separation or separation of the thermoplastic elastic molded product made of this thermoplastic elastic body composition. it can.

  The regenerated thermoplastic resin composition of the present invention is obtained by melting the thermoplastic elastic molded product of the resin molded product with an elastic body of the present invention without removing it from the resin molded product, and the regenerated thermoplastic resin of the present invention. The resin molded product is formed by molding this recycled thermoplastic resin composition.

  According to the present invention, functions such as flexibility, anti-slip properties, molding processability, heat resistance, durability, and the like are satisfied without requiring a large amount of softening agent, and further, a resin base material such as an ABS resin is applied. Provided is a thermoplastic elastomer composition suitable for recycling, which is excellent in compatibility and can be recycled without being separated from a resin molded article of a substrate after use as a product.

  According to the thermoplastic elastic body composition of the present invention, in recycling a resin molded product with an elastic body that is joined and integrated with a resin molded product, the resin molded product with an elastic body is peeled off from the resin molded product, etc. Without being disassembled and subsequent separation work, it can be directly subjected to the regeneration process. For this reason, it is possible to greatly reduce the labor, time and cost of recycling.

  Hereinafter, embodiments of the present invention will be described in detail.

  The thermoplastic elastic composition of the present invention comprises an addition polymerization type thermoplastic block elastic body (A) comprising a polystyrene block and a hydrogenated or non-hydrogenated polyisoprene and / or polybutadiene block, and a polyurethane elastomer (B ) And a rubber-containing graft copolymer (C) obtained by polymerizing a vinyl cyanide monomer and an aromatic vinyl monomer into a rubbery polymer, and an oil (D) as necessary. ).

  The addition polymerization type thermoplastic block elastic body (A) has a block structure of polyisoprene and / or polybutadiene as an elastic phase and a block structure of polystyrene as a constraining phase. Among these, the polyisoprene and / or polybutadiene block constituting the elastic phase may be either hydrogenated or non-hydrogenated, but those in which 90% or more of the double bonds are hydrogenated form a good elastic phase. Desirable above.

  The addition polymerization type thermoplastic block elastic body (A) is preferably composed of 2 or 3 blocks of a polystyrene block and a hydrogenated or non-hydrogenated polyisoprene block, and such an addition polymerization type thermoplastic block. If it is an elastic body, it is excellent in the point from which an effect is acquired especially in the characteristic of heat resistance and vibration resistance. Further, the addition polymerization type thermoplastic block elastic body (A) is preferably composed of a polystyrene block and a hydrogenated or non-hydrogenated polybutadiene block. If such an addition polymerization type thermoplastic block elastic body is used, it is flexible. , Excellent compatibility with aromatic polymers, and excellent raw material costs.

  The hardness (Shore A) of such an addition polymerization type thermoplastic block elastic body (A) is preferably 80 or less. If the hardness of the addition-polymerized thermoplastic block elastic body (A) exceeds 80, the desired softness cannot be obtained, and it is necessary to add a large amount of oil as a softening agent. The characteristics such as the property are impaired, and this causes trouble such as bleeding of oil components in the recycled material. In addition, although there is no restriction | limiting in particular about the minimum of the hardness of an addition polymerization type thermoplastic block elastic body (A), Usually, it is about 30.

  In order to realize such hardness, it is preferable that the proportion of the polystyrene block in the addition polymerization type thermoplastic block elastic body (A) is 10 to 40% by weight, and the remainder is a polyisoprene and / or polybutadiene block.

  Commercially available products can be used as the addition polymerization type thermoplastic block elastic body (A). For example, “Septon” manufactured by Kuraray Co., Ltd., “Clayton D, G, IR” manufactured by Kraton Polymer Japan Co., Ltd., JSR ( "JSR DYNARON" manufactured by Co., Ltd. can be used.

  The polyurethane-based elastomer (B) preferably has a hard segment composed of diisocyanate and short-chain glycol and a soft segment composed of long-chain polyol, and the long-chain polyol is composed of polyether-based and / or polyester-based polyol.

  The hardness (Shore A) of the polyurethane elastomer (B) is preferably 80 or less. When the hardness of the polyurethane elastomer (B) exceeds 80, the desired softness cannot be obtained, and the compatibility with the ABS resin material is lowered. In addition, although there is no restriction | limiting in particular about the minimum of the hardness of a polyurethane-type elastomer (B), Usually, it is about 30.

  In order to realize such hardness, the proportion of the long-chain polyol component in the polyurethane elastomer (B) is preferably 25 to 75% by weight.

  As such a polyurethane-based elastomer (B), a commercially available product can be used, and for example, “Kuramylon U” manufactured by Kuraray Co., Ltd., “Miraktolan” manufactured by Nippon Miractolan Co., Ltd., and the like can be used.

  The rubber-containing graft copolymer (C) has a core / shell structure in which a hard polymer is graft-polymerized to a rubbery polymer, which is generally expressed by ABS, ASA, AES, MBS or the like. Examples of the rubbery polymer forming the rubber-containing graft copolymer (C) include conjugated dienes such as polybutadiene, styrene / butadiene copolymer, acrylate ester / butadiene copolymer, and styrene / isoprene copolymer. Examples thereof include rubber, acrylic rubber such as polybutyl acrylate, olefin rubber such as ethylene / propylene copolymer, and silicon rubber such as polyorganosiloxane. These may be used alone or in combination of two or more. Can be used as a mixture. These rubbery polymers can be used from monomers, and the structure of the rubbery polymer may take a core / shell structure. For example, a rubbery polymer having polybutadiene as the core and acrylic acid ester as the shell can be used.

  The gel content of the rubbery polymer is 60 to 100%, preferably 80 to 99.5%. Within this range, the sheet can be formed efficiently and stably, and the impact strength can be maintained even after recycling. Note that various solvents can be used as the measurement method. For example, in the case of polybutadiene, the degree of swelling can be measured using toluene.

  The rubber-containing graft copolymer (C) is preferably composed of a vinyl cyanide monomer and an aromatic vinyl monomer that form a hard polymer in the presence of 40 to 80% by weight of the rubbery polymer. The monomer mixture can be obtained by graft polymerization of 60 to 20% by weight, where the graft ratio ((acetone insoluble matter weight / rubber polymer weight-1) × 100) is 15 to 85%, particularly It is preferable that it is 20 to 70%, especially 30 to 50%. When the graft ratio of the rubber-containing graft copolymer (C) is lower than 15%, the dispersibility of the rubber-like polymer is lowered, the tear strength, the tensile strength, the tensile elongation is lowered, the gloss is lowered, and the surface is roughened ( It becomes easy to produce a rash. On the other hand, when the graft ratio is higher than 85%, the extrusion moldability tends to be lowered, and the slipperiness is affected, so that the anti-slip effect (coefficient of friction) is lowered.

  As the monomer component forming the above hard polymer, for example, acrylonitrile is used for the vinyl cyanide monomer, and for example, styrene or α-methylstyrene is used for the aromatic vinyl monomer. The weight composition ratio of vinyl cyanide monomer / aromatic vinyl monomer is preferably 15/85 to 40/60, particularly 20/80 to 30/70. If the weight composition ratio of the vinyl cyanide monomer / aromatic vinyl monomer is outside this range, the dispersibility and the thermal stability are lowered. The rubber-containing graft copolymer (C) may be copolymerized with another monomer that can be copolymerized with a vinyl cyanide monomer or an aromatic vinyl monomer.

  Examples of other monomers include (meth) acrylic acid esters such as methacrylic acid esters or acrylic acid esters such as methyl methacrylate and methyl acrylate, and maleimide compounds include N-phenylmaleimide and N-cyclohexyl. Maleimide and the like can be mentioned, and examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid and fumaric acid. These can be used individually by 1 type or in mixture of 2 or more types, respectively.

  The rubber-containing graft copolymer (C) preferably has a weight average molecular weight of 30,000 to 300,000, particularly preferably 60,000 to 250,000, in the acetone-soluble component. When the molecular weight of the rubber-containing graft copolymer (C) is out of this range, the properties are deteriorated. For example, when the molecular weight is large, dispersibility and extrusion processability are inferior, and the appearance of the extruded sheet is deteriorated. Conversely, when the molecular weight is small, the tensile strength cannot be obtained.

  The average particle size of the rubbery polymer of the rubber-containing graft copolymer (C) is usually 0.05 to 2.0 μm, preferably 0.2 to 0.8 μm. About the measuring method of the average particle diameter of a rubber-like polymer, if it is before graft polymerization, it can measure by an optical method and there exists the method of measuring turbidity in the simplest method. Moreover, after graft polymerization, it can measure using a transmission electron microscope (TEM), after dye | staining a rubbery polymer with a dyeing agent.

  In the thermoplastic elastic composition of the present invention, the oil (D) as a softening agent used as necessary may be one generally used as a softening agent for a thermoplastic elastic composition. One or more of softening agents for mineral oil rubbers, aromatic oils, paraffin oils, naphthenic oils and the like can be used. “Diana process oil” manufactured by Idemitsu Kosan Co., Ltd. is known as a commercially available oil.

  In the present invention, 20 to 200 parts by weight of the polyurethane elastomer (B) and 20 to 100 parts by weight of the rubber-containing graft copolymer (C) with respect to 100 parts by weight of the addition polymerization thermoplastic block elastic body (A). And, if necessary, 50 parts by weight or less of oil (D).

  In this blending, the components (A) and (B) alone are difficult to disperse when recycled, so that they tend to be poor in appearance and blisters as foreign matters, and the weldability tends to decrease. Only with the component (A) and the component (C), the hardness is high, the elongation is low, and the weldability tends to be lowered. Only the component (B) and the component (C) have high hardness, low elongation, and light resistance. By including the component (A), the component (B), and the component (C) in the above composition, the flexibility, anti-slip property, and moldability can be obtained without requiring the addition of a large amount of the softening agent that is the object of the present invention. , Satisfying functions such as heat resistance and durability, and excellent compatibility with resin base materials such as ABS resin, and can be recycled without being separated from the resin molded product of the substrate after use as a product A thermoplastic elastic composition suitable for recycling can be realized.

  In addition, when adding oil (D), the addition amount has the preferable range of 50 weight part or less with respect to 100 weight part of addition polymerization type thermoplastic block elastic bodies, More preferably, it is 20 weight part or less. When the amount of oil (D) added is increased, bleeding occurs during the molding process, and problems such as contamination of the roll of the extrusion molding machine and the mold of the injection molding machine are likely to occur. In addition, problems such as transition troubles, bleeding, thermal deformation, etc. are likely to occur after the product is manufactured.

  Various additives can be further blended in the thermoplastic elastic composition of the present invention. In this case, various additives include known antioxidants, UV absorbers, lubricants, plasticizers, mold release agents, antistatic agents, colorants (pigments, dyes, etc.), carbon fibers and glass fibers, talc and watts. Fillers such as lastite, calcium carbonate and silica, flame retardants (halogen flame retardants, phosphorus flame retardants, antimony compounds, etc.), anti-drip agents, antibacterial agents, anti-fungal agents, silicone oils, coupling agents, etc. 1 type or 2 types or more are mentioned.

  The thermoplastic elastomer composition of the present invention can be prepared by mixing the components (A) to (C) and the component (D) blended as necessary and a predetermined amount of additives. The pelletizing method is not particularly limited, but for example, a melt kneading method using a twin screw extruder, a Banbury mixer, a heating roll or the like is preferable.

  The thermoplastic elastomer composition of the present invention thus obtained can be molded into various molded articles by injection molding, sheet extrusion molding, profile extrusion molding, blow molding, calendar molding, and the like.

  The thermoplastic elastic molded product formed by molding the thermoplastic elastic composition of the present invention exhibits excellent performance such as dustproof, vibration-proof, anti-slip, etc. Electrical and electronic equipment and electronic equipment parts, especially OA equipment such as computers, printers, copiers, etc., as well as lid parts of mobile information devices such as mobile computers, desktop holders, mobile phone chargers and personal computers It can be used for gaskets such as rubber feet, air conditioners and printers, and can be used for parts such as excellent dust proofing, vibration proofing and anti-slip.

  The thermoplastic elastic composition of the present invention removes the thermoplastic elastic molded product portion comprising the thermoplastic elastic composition from the base resin molded product, particularly when recycling the product integrated with the resin molded product. Without being done, it has the advantage that it can be subjected to a melt regeneration process as it is.

  In this case, suitable resin base materials for this resin molded product include ABS resin, ASA resin, AES resin, HIPS resin, MBS resin, and other rubber-reinforced styrene resins, as well as AS resin, polystyrene resin, and polycarbonate resin. , Nylon resin, methacrylic resin, polyvinyl chloride resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyphenylene ether, and the like. Moreover, what blended these 2 or more types may be sufficient, and also what mix | blended the said resin modified | denatured with the compatibilizing agent, the functional group, etc. may be sufficient. Among them, the thermoplastic elastomer composition of the present invention is excellent in compatibility with a resin molded product based on a styrene resin, and particularly excellent in compatibility with an ABS resin, and thus is suitable for an ABS resin molded product. .

  In addition, since the thermoplastic elastomer composition of the present invention is also excellent in weldability to resin molded products, welding can be suitably used for joining to these resin molded products, but not limited to welding. Depending on the case, other joining methods such as fitting and adhesion may be employed.

  When recycling the resin molded product with an elastic body of the present invention in which the thermoplastic elastic molded product made of the thermoplastic elastic body composition of the present invention is integrated into a resin molded product, it is used as it is, that is, with an elastic body. Without requiring disassembly and separation of the resin molded product and the resin molded product, only a fragmentation process such as crushing, pulverization, and cutting can be performed as needed to be used for the melt regeneration process.

  The recycled thermoplastic resin composition thus obtained can be molded as it is to obtain a recycled thermoplastic resin molded product, but may be blended with various resins as necessary. Further, when the resin molded article with an elastic body is melted and recycled, another resin can be melted and kneaded to obtain a recycled thermoplastic resin composition.

  In this case, other resins that can be blended include those exemplified as the base resin of the resin molded product to which the thermoplastic elastomer composition of the present invention is applied, and these are recovered by virgin material or separately recycled. Any of these resins may be used, or a mixture thereof may be used. When other resins are blended in this way, the mixing ratio is not particularly limited, and can be appropriately blended so as to obtain desired characteristics.

  However, the component derived from the thermoplastic elastic body composition of the present invention in the recycled thermoplastic resin composition is preferably 10% by weight or less, particularly preferably 5% by weight or less. If this range is exceeded, the base resin characteristics of the resin molded product, particularly the hardness and rigidity, may be impaired, making it unsuitable for use in a housing or the like.

  In addition, the recycled thermoplastic resin composition of the present invention can also be blended with various other additives, and the additive is described above as an additive that can be blended with the thermoplastic elastomer composition of the present invention. Can be used.

  There are no particular restrictions on the pelletization and molding method of the recycled thermoplastic resin composition of the present invention, and the above-described methods can be applied as the pelletization and molding method of the thermoplastic elastic composition of the present invention.

  The recycled thermoplastic resin molded article of the present invention is excellent in mechanical properties and appearance of the molded article, and can be used for various applications including housings for information equipment and general office equipment.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples, comparative examples, and reference examples. However, the present invention is not limited to the following examples unless it exceeds the gist. Absent.

In the following, as the addition polymerization type thermoplastic block elastic body (A), the following were used.
(A-1): “Clayton G (1650)” (Shore A75) manufactured by Kraton Polymer Co., Ltd.
(A-2): “Clayton D (1155)” (Shore A87) manufactured by Kraton Polymer Co., Ltd.

Moreover, the following were used as a polyurethane-type elastomer (B).
(B-1): “Kuramylon U (8170)” manufactured by Kuraray Co., Ltd. (Shore A70)
(B-2): “Kuramyron U (2795)” manufactured by Kuraray Co., Ltd. (Shore A95)

  As the rubber-containing graft copolymer (C), those synthesized in Synthesis Examples 1 and 2 below were used.

  In the following, “parts” means “parts by weight”, the graft ratio of the obtained rubber-containing graft copolymer and the weight-average molecular weight (Mw) of the acetone-soluble component of the rubber-containing graft copolymer. Asked. This molecular weight was measured by a standard PS (polystyrene) conversion method using Tosoh Co., Ltd. product: GPC (gel permeation chromatography, solvent; THF).

Synthesis Example 1: Production of rubber-containing graft copolymer (c-1) An ABS copolymer was synthesized by the emulsion polymerization method with the following composition.
[Combination]
Styrene (ST) 21 parts Chloronitrile (AN) 9 parts Polybutadiene latex 70 parts (as solids)
Disproportionated potassium rosinate 1 part Potassium hydroxide 0.03 part Tertiary decyl mercaptan (t-DM) 0.3 part Cumene hydroperoxide 0.3 part Ferrous sulfate 0.007 part Sodium pyrophosphate 0.1 Part Crystalline glucose 0.3 part Distilled water 190 part

  Charge autoclave with distilled water, disproportionated potassium rosinate, potassium hydroxide and polybutadiene latex (gel 85%, average particle size 0.3 μm), heat to 60 ° C., ferrous sulfate, sodium pyrophosphate, crystalline glucose While maintaining at 60 ° C., ST, AN, t-DM and cumene hydroperoxide were continuously added over 2 hours, and then the temperature was raised to 70 ° C. and maintained for 1 hour to complete the reaction. An antioxidant was added to the ABS latex obtained by this reaction, then coagulated with sulfuric acid, sufficiently washed with water, and dried to obtain an ABS graft copolymer (c-1).

Synthesis Example 2: Production of rubber-containing graft copolymer (c-2) In the same manner as above except that the rubber amount was 20 parts, styrene was 56 parts, and acrylonitrile was 24 parts, an ABS graft copolymer ( c-2) was obtained.

The graft ratio of the rubber-containing graft copolymer produced in Synthesis Examples 1 and 2 and the molecular weight of the acetone-soluble component were measured. The results are as follows.
(C-1): Graft ratio 40%, molecular weight 110,000
(C-2): Graft rate 95%, molecular weight 35,0000

The following were used as oil (D).
(D): “Diana Process Oil (PW-90)” manufactured by Idemitsu Kosan Co., Ltd.

Examples 1-9, Comparative Examples 1-20 and Reference Examples 1-3
After the mixture was melt-kneaded with the formulation shown in Table 1, a primary sheet was formed on a heating roll, and a sheet having a thickness of 2 mm was formed by a heating / pressing press. In Reference Examples 1 to 3, commercially available products shown in Table 1 were used.

  Each of the obtained sheets was subjected to the following evaluation tests. In Reference Examples 1 to 3, only the weldability and recyclability were evaluated.

  The evaluation results are shown in Table 2.

[Shore hardness] JIS K7215 (A scale)
[Tear Strength] JIS K7128-3 (N / cm)
[Tensile strength] JIS K7113 (N / cm2)
[Elongation] JIS K7113 (%)
[Weldability] A 2 mm thick ABS (UMG ABS Psycolac AM; natural color) resin plate and a 2 mm thick thermoplastic elastic composition were thermally welded at 180 ° C. and 2.9 MPa, and a tensile tester. The strength peeled off and the appearance after peeling were observed. The peel strength was defined as the welding strength (unit: N / 25 mm), the material destruction was indicated by ○, and the weld interface peeling was indicated by ×.
[Weather resistance] Using a sunshine weather meter ("WEL-SUN-HC type" manufactured by Suga Test Instruments Co., Ltd.) with a 2 mm thick thermoplastic elastomer composition, discoloration after 100 hours exposure was observed, and good Was marked with ◯, markedly discolored with Δ, and further with a deteriorated surface.
[Friction Coefficient] The static friction coefficient of the 2 mm-thick thermoplastic elastomer composition with respect to the metal plate was measured by a gradient method (“Static friction coefficient measuring machine TYPE HEIDON 10” manufactured by Shinto Kagaku Co., Ltd.). The coefficient of static friction was less than 0.8, x was less than 1.2, and Δ was 1.2 or more. In addition, since it cannot measure 1.6 or more on a measurement, when it is larger than this value, it described as (double-circle).
[Recyclability] In order to facilitate the visual determination of dispersibility, a 2 mm thick sheet of thermoplastic elastomer composition colored black by adding 1 part of carbon black to the same composition as in each example was newly added. Created. ABS resin (UMG
A sheet of black thermoplastic elastomer composition was prepared by welding to 100 parts of ABS “Psycholac AM” (natural color) sheet and blended into 3 parts. The mixture was crushed and melted and mixed as it was to produce pellets. This pellet is molded into a resin plate using an injection molding machine at 240 ° C., and visually observed through the surface of the molded product and through the light. Obviously, those with poor dispersion were marked with x.

[Discussion]
As is clear from Tables 1 and 2, the thermoplastic elastomer compositions of Examples 1 to 9 are excellent in balance in hardness, tear strength, tensile strength, and elongation. Moreover, the weldability with the ABS resin is excellent, and the recyclability is also excellent.

  On the other hand, the thermoplastic elastomer compositions of Comparative Examples 1 to 20 have a balance of hardness, tear strength, tensile strength, elongation rate, weldability with ABS resin, and recyclability. Not. In particular, in Comparative Examples 1 to 3 containing only the component (A) and the component (C), the hardness tends to be high and the elongation rate tends to be low depending on the blending amount. Further, in Comparative Examples 4 to 6 using only the component (A) and the component (B), the welding peelability is interfacial peeling, and the recyclability is also poor. Comparative Examples 7 and 8 consisting of only the component (B) and the component (C) have high hardness, low elongation, and light resistance.

  In addition, the weldability and recyclability of the commercial products of Reference Examples 1 to 3 are not sufficient.

  From the thermoplastic elastomer composition of the present invention which is excellent in flexibility, anti-slip property, molding processability, durability, heat resistance, etc., and also excellent in compatibility and dispersibility in a resin base material such as ABS resin. The thermoplastic elastic molded article according to the present invention, particularly using its excellent performance of dustproof, vibration proof, anti-slip, etc., is used for parts for vehicles and general equipment, especially for electric and electronic equipment and electronic equipment parts, OA equipment such as computers, printers, copiers, etc. In addition, the lids of casings of portable information devices such as mobile computers, desktop holders, rubber feet for mobile phone chargers and personal computers, gaskets for air conditioners and printers, etc. Can be used for applications.

  In addition, the resin molded product with an elastic body of the present invention in which this thermoplastic elastic molded product is integrated with a resin molded product can be easily recycled, and the regenerated thermoplastic resin of the present invention obtained from this resin molded product with an elastic body. The resin composition is useful as a molding material for casings of electrical and electronic equipment and electronic equipment parts, particularly OA equipment and information equipment.

Claims (15)

100 parts by weight of an addition polymerization type thermoplastic block elastic body (A) comprising a polystyrene block and a hydrogenated or non-hydrogenated polyisoprene and / or polybutadiene block;
20 to 200 parts by weight of polyurethane elastomer (B),
A thermoplastic elastomer comprising 20 to 100 parts by weight of a rubber-containing graft copolymer (C) obtained by polymerizing a vinyl cyanide monomer and an aromatic vinyl monomer on a rubber polymer. Composition.   The thermoplastic elastomer composition according to claim 1, wherein the addition polymerization thermoplastic block elastomer (A) comprises two or three blocks of a polystyrene block and a hydrogenated or non-hydrogenated polyisoprene block.   The thermoplastic elastomer composition according to claim 1, wherein the addition polymerization type thermoplastic block elastic body (A) comprises a polystyrene block and a hydrogenated or non-hydrogenated polybutadiene block.   The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the addition polymerization type thermoplastic block elastic body (A) has a hardness (Shore A) of 80 or less.   The polyurethane elastomer (B) has a diisocyanate, a hard segment composed of a short-chain glycol, and a soft segment composed of a long-chain polyol, and the long-chain polyol is a polyether-based and / or polyester-based polyol. The thermoplastic elastic body composition of any one of thru | or 4.   The thermoplastic elastomer composition according to any one of claims 1 to 5, wherein the polyurethane elastomer (B) has a hardness (Shore A) of 80 or less.   The rubber component of the rubber-containing graft copolymer (C) is composed of one or more selected from the group consisting of polybutadiene rubber, acrylic rubber, olefin rubber, and silicon rubber, and the content of the rubber component The thermoplastic elastic composition according to any one of claims 1 to 6, wherein is 40 to 80% by weight.   The weight ratio of vinyl cyanide monomer and aromatic vinyl monomer polymerized to the rubber-containing graft copolymer (C) is vinyl cyanide monomer / aromatic vinyl monomer = 15 / 85-40 / The thermoplastic elastic composition according to any one of claims 1 to 7, which has a graft ratio of 60 to 60 and a graft ratio of 15 to 85%.   The thermoplastic elastic composition according to any one of claims 1 to 8, further comprising 50 parts by weight or less of oil (D).   The oil (D) is one or more selected from the group consisting of a process oil, a mineral oil rubber softener, an aromatic oil, a paraffin oil, and a naphthenic oil. Thermoplastic elastic body composition.   A thermoplastic elastic molded article obtained by molding the thermoplastic elastic composition according to any one of claims 1 to 10.   A resin molded product with an elastic body, wherein the thermoplastic elastic molded product of claim 11 is joined to a resin molded product.   A method for recycling a resin molded product with an elastic body according to claim 12, wherein the resin molded product with an elastic body is melted and recycled without removing the thermoplastic elastic molded product joined to the resin molded product.   A recycled thermoplastic resin composition obtained by melting the thermoplastic elastic molded product of the resin molded product with an elastic body according to claim 13 without removing it from the resin molded product.   A recycled thermoplastic resin molded article obtained by molding the recycled thermoplastic resin composition according to claim 14 or a thermoplastic resin composition containing the recycled thermoplastic resin composition.