WO2022049809A1

WO2022049809A1 - Method for producing regenerated thermoplastic resin composition, and regenerated thermoplastic resin composition

Info

Publication number: WO2022049809A1
Application number: PCT/JP2021/009563
Authority: WO
Inventors: 大輔亀井
Original assignee: 三菱電機株式会社
Priority date: 2020-09-07
Filing date: 2021-03-10
Publication date: 2022-03-10
Also published as: JPWO2022049809A1; JP7352218B2

Abstract

A method for producing a regenerated thermoplastic resin composition according to the present disclosure comprises a mixing step for mixing, with respect to 100 parts by weight of a used thermoplastic resin composition, at least one among: 0.4-1.8 parts by weight of a silane coupling agent having an epoxy group; 0.4-1.8 parts by weight of a silane coupling agent having an amino group; 1.0-1.8 parts by weight of a silane coupling agent having an isocyanate group; and 0.2-5.0 parts by weight of an epoxy resin.

Description

Manufacturing method of regenerated thermoplastic resin composition and regenerated thermoplastic resin composition

The present disclosure relates to a method for producing a regenerated thermoplastic resin composition and a regenerated thermoplastic resin composition.

For home appliances and OA (Office Automation) equipment, thermoplastic resins such as styrene resin or olefin resin are generally used as lightweight, high-strength, mass-produceable materials for housings and parts. Has been done. When these products are disposed of after use, most of them have been disposed of by landfill or incinerator without being remanufactured, except for the parts that can be disassembled and recovered by hand. However, in recent years, from the viewpoints of enforcement of the Home Appliance Recycling Law, effective use of resources, formation of a sound material-cycle society, and reduction of carbon dioxide emissions, the thermoplastic resin of the recovered product is melt-kneaded and reused as a resin molded product. Material recycling is being carried out. The recycled thermoplastic resin is used, for example, in televisions, air conditioners, refrigerators, vacuum cleaners, and the like.

The thermoplastic resin recovered from home appliances, etc. is a mixture of two or more types of thermoplastic resin. Therefore, each resin type is separated through various sorting processes, and is reused after melt-kneading. In the sorting process, the thermoplastic resin crushed into mixed flakes is, for example, an olefin resin having a specific gravity of 1.0 or less and a specific gravity larger than 1.0 by utilizing the difference in specific gravity, 1.1. It is separated into smaller polystyrene and ABS resin (Acrylonirile Butadiene Copolymer Synthetic Resin), and a weight specific gravity resin having a specific gravity of 1.1 or more. Then, the mixed flakes of polystyrene and ABS resin are separated by an electrostatic sorting device that utilizes the charge when the mixed flakes are rubbed together.

Normally, when processing a thermoplastic resin, it is necessary to plasticize the thermoplastic resin by heating from the outside, and the heating temperature is generally as high as 200 ° C. or higher. At this time, a lubricant is added to the thermoplastic resin in order to increase the fluidity of the thermoplastic resin. There are various types of lubricants, but when the thermoplastic resin is a styrene resin or an olefin resin, for example, a fatty acid and a fatty acid metal salt are added as the lubricant. The lubricant enhances the productivity of the thermoplastic resin, but in the thermoplastic resin to which a large amount of the lubricant is added, the lubricant bleeds out, which causes the appearance of the resin molded product to be spoiled.

In addition, fatty acids used as lubricants also cause the generation of tar components as gas during resin molding. Therefore, the fatty acids contained in the used thermoplastic resin composition, which is a thermoplastic resin recovered from the product after being used for home appliances at least once and separated for each resin type, are oil-absorbent inorganic. A regenerated thermoplastic resin composition that suppresses gas generation during resin molding and suppresses the adhesion of tar to a mold by adsorbing it on a compound is disclosed (see, for example, Patent Document 1). Here, the regenerated thermoplastic resin composition refers to a thermoplastic resin composition produced from a used thermoplastic resin composition.

Japanese Unexamined Patent Publication No. 2015-160900

However, in the technique described in Patent Document 1, the fatty acid remains in the regenerated thermoplastic resin composition while being adsorbed by the oil-absorbing inorganic compound. Therefore, if the resin molded product is continuously exposed to a hot water environment containing metal ions, fatty acids may bleed out and the appearance and design may be impaired.

Further, in the new thermoplastic resin, by suppressing the content of the lubricant added in the manufacturing process of the resin molded product, it is possible to suppress the bleed-out of the fatty acid as the lubricant, but the used heat. In the thermoplastic resin composition, it was difficult to control the content of the lubricant already contained.

The present disclosure has been made to solve the above-mentioned problems, and provides a method for producing a regenerated thermoplastic resin composition and a regenerated thermoplastic resin composition capable of suppressing bleed-out of fatty acids and improving the appearance design. The purpose is.

In the method for producing a regenerated thermoplastic resin composition according to the present disclosure, 0.4 parts by weight or more and 1.8 parts by weight or less of a silane coupling agent having an epoxy group is added to 100 parts by weight of the used thermoplastic resin composition. , 0.4 parts by weight or more and 1.8 parts by weight or less of the silane coupling agent having an amino group, 1.0 part by weight or more and 1.8 parts by weight or less of the silane coupling agent having an isocyanate group, and 0 parts of the epoxy resin. It has a mixing step of mixing at least one of 2 parts by weight or more and 5.0 parts by weight or less.

The regenerated thermoplastic resin composition according to the present disclosure has the following chemical formulas 1, 2 and 3

A regenerated thermoplastic resin composition comprising at least one of the above.
(In chemical formulas 1, 2 and 3,
l = 1-13,
-R ^1- : Substituent represented by Chemical Formula 4,
-R ² :-(CH ₂ ) _n CH ₃ (any of n = 10, 12, 14, 16) or-(CH ₂ ) ₇ CH = CH (CH ₂ ) _m CH ₃ (m = 5, 7) either))

The regenerated thermoplastic resin composition according to the present disclosure has the following chemical formulas 5, 6 and 7.

A regenerated thermoplastic resin composition comprising at least one of the above.
(In chemical formulas 5, 6 and 7,
k = 1 to 13
-R ² :-(CH ₂ ) _n CH ₃ (any of n = 10, 12, 14, 16) or-(CH ₂ ) ₇ CH = CH (CH ₂ ) _m CH ₃ (m = 5, 7) either))

According to the present disclosure, it is possible to suppress the bleed-out of fatty acids and improve the appearance design.

The figure which shows the addition amount of each compound which concerns on Embodiment 1. FIG.

Embodiment 1.
The inventors have diligently studied to obtain a regenerated thermoplastic resin composition capable of improving the appearance design by reacting the used thermoplastic resin composition with a compound having an epoxy group, an amino group, or an isocyanate group. I found that I could do it. That is, the fatty acid contained in the used thermoplastic resin composition is reacted with the epoxy group, amino group, or isocyanate group contained in the added compound to make it a substance different from the fatty acid, thereby suppressing the bleed-out of the fatty acid. I found that I could do it.

Details will be described later, but for 100 parts by weight of the used thermoplastic resin composition having a fatty acid content of 0.23% by weight, a mixture of bisphenol A type epoxy resin trimer (2 to 14 weights), which is a kind of epoxy resin, is used. The fatty acid content of the resin molded product (Example 58 described later) to which 1.2 parts by weight of the resin molded product (which contains the largest amount of the trimmer) is higher than the fatty acid content of the resin molded product to which the epoxy resin is not added. It was found that the ratio can be reduced by about 80%. That is, the fatty acid content of the resin molded product (Example 58 described later) was about 0.046% by weight. Moreover, the reaction product of the epoxy resin and the fatty acid was extracted from the regenerated thermoplastic resin composition (described later), and qualitative analysis was performed by MALDI-MS. As a result, as reaction products, epoxy resin trimer + palmitic acid, epoxy resin trimer + stearic acid, epoxy resin trimer + palmitic acid + palmitic acid, epoxy resin trimer + palmitic acid + stearic acid, And it was found that an epoxy resin trimer + stearic acid + stearic acid was contained. Assuming that all the fatty acids in the used thermoplastic resin composition ideally react with the epoxy resin, the reaction product corresponding to the fatty acid content of 0.23% by weight contained in the used thermoplastic resin composition is produced. It will occur.

In the following description, the "recycled thermoplastic resin composition" refers to a thermoplastic resin composition produced from a used thermoplastic resin composition. Further, a thermoplastic resin composition that has not yet been used in home appliances and the like is referred to as an “unused thermoplastic resin composition”.

First, the mechanism by which fatty acids bleed out in a hot water environment will be explained. When the thermoplastic resin composition is exposed to a hot water environment containing metal ions, the fatty acids contained in the thermoplastic resin composition are released from the thermoplastic resin composition into hot water. Then, since the metal ions in the hot water and the released fatty acid form a fatty acid metal salt, the solubility of the fatty acid in the hot water decreases, and the fatty acid precipitates on the surface of the resin molded product. Since the fatty acid metal salt deposited on the surface of the resin molded product can be visually recognized as a white powder, the appearance design of the resin molded product is impaired.

On the other hand, when pure water or ion-exchanged water containing no metal ions is used for the thermoplastic resin composition, the fatty acids dissolve in the hot water, so that the appearance design of the resin molded product is not impaired. .. Therefore, by passing tap water through a filter or the like that reduces the ion concentration to reduce the metal ions in the water, it is possible to solve the problem of impairing the appearance and design of the resin molded product. However, if the metal ion concentration in water increases due to the life of the filter or the like, the appearance design of the resin molded product is impaired, which is insufficient as a countermeasure against fatty acid bleed-out.

The inventors added stearic acid to the unused thermoplastic resin composition to change the fatty acid content in the unused thermoplastic resin composition, and when exposed to hot water containing metal ions at 75 ° C. or higher. , It was verified whether or not the fatty acid bleeds out. As a result, it was found that when the content of fatty acid contained in the unused thermoplastic resin composition was 0.2% by weight or more, white powder was deposited on the surface of the unused thermoplastic resin composition. That is, it was found that the fatty acid bleeds out when the content of the fatty acid contained in the thermoplastic resin composition is 0.2% by weight or more. The fatty acid content in the thermoplastic resin composition is the total value of the contents of palmitic acid and stearic acid, and is obtained by quantitative analysis by GC-MS after extraction from the thermoplastic resin composition. In the following Examples and Comparative Examples, the regenerated thermoplastic resin composition was exposed to hot water (tap water) at 100 ° C. for 8 hours, but instead of being exposed to hot water at 100 ° C. for 8 hours, 75 It has been confirmed that the same result can be obtained when the regenerated thermoplastic resin composition is exposed to hot water (tap water) at ° C or higher for 20 minutes or longer. It has also been confirmed that the same result can be obtained when the regenerated thermoplastic resin composition is exposed not only to the hot water in the closed container but also to the hot water in running water.

Next, the thermoplastic resin composition will be illustrated. The thermoplastic resin composition is, for example, a polyolefin-based (polypropylene, polyethylene). Examples of the polyolefin-based resin constituting the polyolefin-based resin composition include polyethylene, homopolypropylene, a propylene-ethylene block copolymer, a propylene-butene block copolymer, a propylene-α-olefin block copolymer, and a propylene-ethylene random compound. Examples thereof include a polymer, a propylene-butene random copolymer, a propylene-α-olefin random copolymer, a propylene-α-olefin graft copolymer and the like.

Further, the thermoplastic resin composition includes, for example, polystyrene-based HIPS (High Impact Polystylene) and GPPS (General Purpose Polystyrene), acrylonitrile-based ABS and AS (Acrylonitrile Style style copolymer), polycarbonate-based polycarbonate, and polycarbonate-based polycarbonate. , Or an acrylic acid-based resin composition or the like.

Next, examples of fatty acids and their derivatives will be given. The fatty acid and its derivative are fatty acids such as, for example, lauryl acid, myristic acid, palmitic acid, stearic acid, oleic acid, or palmitoleic acid. Further, the fatty acid and its derivative include higher alcohols such as cetyl alcohol, stearyl alcohol, and oleyl alcohol, fatty acid amides such as stearate amides, oleic acid amides, erucic acid amides, or hexadecane amides, squalanes, and bisphenol A. Point to. In the present disclosure, fatty acids and their derivatives in the used thermoplastic resin composition were qualitatively analyzed by pyrolysis GC-MS.

Next, the coloring pigment will be described. The coloring pigment is added to the used thermoplastic resin composition at the time of manufacturing the regenerated thermoplastic resin composition in order to improve the appearance of the resin molded product by toning. When the recycled thermoplastic resin composition is produced using the used thermoplastic resin composition, when the used thermoplastic resin composition is mixed (kneaded) with a compound having an epoxy group, an amino group, or an isocyanate group. In addition, non-melting foreign matter may cause a poor appearance of the regenerated thermoplastic resin composition. Therefore, by adding a coloring pigment to the used thermoplastic resin composition, foreign substances in the produced regenerated thermoplastic resin composition can be concealed. As the coloring pigment, for example, an inorganic pigment may be used. The inorganic pigment is, for example, titanium oxide, titanium yellow, carbon black, ultramarine, or the like.

Further, when producing a regenerated thermoplastic resin composition, a coloring pigment containing a dispersant may be used. By including the dispersant, the colored pigment can improve the dispersibility and can further bring out the performance and properties of the colored pigment. The dispersant is, for example, magnesium stearate, ethylene bisstearate amide, polyethylene wax, or the like.

Here, the inventors produce a regenerated thermoplastic resin composition using a polypropylene resin as a used thermoplastic resin composition, and an inorganic pigment containing 17% by weight of magnesium stearate as a dispersant in the inorganic pigment. Was used, and the fatty acid content of the inorganic pigment was calculated when 17% by weight of ethylene bisstearic acid amide was used as the dispersant in the inorganic pigment. As a result, when an inorganic pigment containing 17% by weight of magnesium stearate was used as a dispersant, the fatty acid content of the inorganic pigment was 8.2% by weight, whereas 17% by weight of ethylene bis was used as a dispersant. When stearic acid amide was used, the fatty acid content of the inorganic pigment was 0.53% by weight.

From the above, when polypropylene resin is used as the used thermoplastic resin composition, the fatty acid content of the inorganic pigment is lower when ethylene bisstearate amide is used as the dispersant for the coloring pigment, but magnesium stearate as the dispersant. The dispersion of the inorganic pigment and the inorganic filler in the used thermoplastic resin composition is improved by using the above method as compared with the case of using ethylene bisstearic acid amide. The fatty acid content of the produced regenerated thermoplastic resin composition is the total value of the contents of palmitic acid and stearic acid, and after extracting palmitic acid and stearic acid from the regenerated thermoplastic resin composition, GC- It was obtained by quantitative analysis by MS.

In addition, when a coloring pigment containing magnesium stearate is added as a dispersant and a poor appearance occurs in the regenerated thermoplastic resin composition, the poor appearance is not due to the bleed-out of magnesium stearate, but the used thermoplasticity. It is considered that this is because the fatty acids in the resin and the coloring pigment bleed out in a hot water environment.

Next, a compound having an epoxy group, an amino group, or an isocyanate group to be added to the used thermoplastic resin composition will be exemplified. Examples of the compound having an epoxy group, an amino group, or an isocyanate group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycyridoxypropylmethyldimethoxysilane, and 3-glyciridoxypropyltrimethoxysilane. , 3-Glycyridoxypropylmethyldiethoxysilane, 3-Glycyridoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3- Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyl A silane coupling agent such as trimethoxysilane or 3-isoxapropyltriethoxysilane is preferred. Further, it may be an epoxy resin such as a bisphenol A type epoxy resin or a novolak type epoxy resin. Further, it may be a diisocyanate such as naphthalene-1,5-diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, or 1,4-phenylenediisocyanate, or a polyamine such as spermine, spermidine, or putrescine. .. These compounds may be added alone to the used thermoplastic resin composition, or may be mixed in a plurality and added to the used thermoplastic resin composition.

Next, a method for mixing (kneading) the used thermoplastic resin composition with a compound having an epoxy group, an amino group, or an isocyanate group will be described. Examples of the mixing method include a method using a physical blend such as a melt-kneading method, a solvent cast blend, a latex blend, or a polymer complex, and a melt-kneading method is particularly preferable.

In addition, as an apparatus for mixing the used thermoplastic resin composition with a compound having an epoxy group, an amino group, or an isocyanate group, a tumbler, a henschel mixer, a rotary mixer, a super mixer, a ribbon tumbler, a V blender, or the like can be used. Can be mentioned. Using such a kneading device, each material is uniformly dispersed, melt-kneaded, and then the mixed used thermoplastic resin composition and a compound having an epoxy group, an amino group, or an isocyanate group are pelletized. Is preferable.

A single-screw, multi-screw or tandem extruder is generally used for pelletization, but in addition to these extruders, a Banbury mixer, a roller, a co-kneader, a blast mill, a lavender brout graph, etc. may be used. It can also be used. Then, the mixed used thermoplastic resin composition and the compound having an epoxy group, an amino group, or an isocyanate group may be pelletized by operating these devices in batches or continuously.

Further, as described above, each material may be mixed or, without melt-kneading, a resin pellet, a compound having an epoxy group, an amino group, or an isocyanate group, an antioxidant, a metal inactivating agent, and coloring. A so-called mold blend may be used in which the pigment and other additives are mixed, and the mixed materials are used as the molding resin and melt-kneaded in the heating cylinder of the molding machine.

The method for molding the resin molded product of the regenerated thermoplastic resin composition according to the present disclosure is not particularly limited and can be molded by a known molding method, but for example, injection molding may be used.

Hereinafter, the present disclosure will be described in more detail with reference to Examples and Comparative Examples, but the present disclosure is not limited thereto. In Examples and Comparative Examples, FT-IR evaluation and physical property evaluation (each described later) were performed in order to confirm that the obtained regenerated thermoplastic resin composition was excellent in appearance design, and comprehensively. Judgment. The fatty acid content of the used thermoplastic resin composition was 0.23% by weight. The used thermoplastic resin composition is derived from large household appliances recovered from the market, such as TVs, air conditioners, refrigerators, washing machines, etc., and the fatty acid content in the used thermoplastic resin composition is large household appliances. It may fluctuate slightly depending on the collection location, season, base material variation, etc. at the time of product collection.

Here, the evaluation method adopted this time will be described. In the FT-IR evaluation, a part of the ISO dumbbell test piece (35 mm × 10 mm × thickness 4 mm) produced by an injection molding machine, that is, a resin molded product of a regenerated thermoplastic resin composition (hereinafter, simply referred to as a regenerated thermoplastic resin composition). (May be noted) was exposed for 8 hours in 50 mL of hot water (tap water) at 100 ° C. in a pressure resistant container (capacity 80 mL) coated with Teflon® and evaluated. Here, when tap water is quantitatively analyzed by an ion chromatograph, Na ⁺ is 19 mg / L, Ca ²⁺ is 11 mg / L, K ⁺ is 2.7 mg / L, and Mg ²⁺ is 2.3 mg / L as metal ions. It was.

The FT-IR / ATR method was performed on the regenerated thermoplastic resin composition exposed to hot water at 100 ° C. for 8 hours. In the spectrum obtained by the FT-IR / ATR method, among the peaks of C = O stretching vibration of the fatty acid metal salt with respect to the absorbance of 2918 cm ^-1 , which is one of the peaks of CH stretching vibration of polypropylene. When the intensity ratio of the absorbance of one peak of 1541 cm ^-1 was 0.1 or less, it was regarded as acceptable, and it was determined that the fatty acid was not bleeding out. That is, it was determined that the obtained regenerated thermoplastic resin composition had excellent appearance design. The FT-IR evaluation and the appearance evaluation (evaluation of whether or not the bleed-out was visually observed) were in good agreement. In the table below, pass is indicated by A and failure (fatty acid is bleeding out) is indicated by B.

In the physical property evaluation, in order to evaluate the physical properties of the regenerated thermoplastic resin composition, an ISO dumbbell test piece A type is produced by an injection molding machine, and the tensile elongation at break by a tensile test is measured to measure the used thermoplastic resin composition. And the tensile elongation at break with the regenerated thermoplastic resin composition not mixed with additives other than the inorganic filler.

The tensile test was performed by a method according to JIS K7161. The tensile test was carried out at a test speed of 50 mm / min using a universal testing machine, and the tensile elongation at break was determined. With respect to the obtained tensile elongation at break, the tensile elongation at break retention rate (%) with respect to the tensile elongation at break of the recycled thermoplastic resin composition not mixed with the used thermoplastic resin composition and additives other than the inorganic filler was determined. Here, as a criterion for determining the physical properties of the regenerated thermoplastic resin composition, a case where the tensile elongation at break retention rate is reduced to less than 75% is regarded as a failure (B in the table), and a case of 75% or more is passed (A in the table). And said.

Based on the results of the above FT-IR evaluation and physical property evaluation, a comprehensive judgment is made. If both pass (A), the comprehensive judgment is passed (A), and the regenerated thermoplastic resin composition having excellent appearance design is obtained. It was said that. If either the FT-IR evaluation or the physical property evaluation result was unsuccessful (B), the comprehensive judgment was unsuccessful (B). Examples 1 to 64 and Comparative Examples 1 to 44 are shown below.

<Examples 1 to 8>
In Examples 1 to 8, a silane coupling agent (3-glycyridoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), N-2-) was used with respect to the used thermoplastic resin composition. (Aminoethyl) -3-aminopropyltrimethoxysilane (KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) or 3-Ixoxide propyltriethoxysilane (KBE-9007N, manufactured by Shin-Etsu Chemical Co., Ltd.)) is added. The mixture was kneaded in a kneader at 210 ° C. while being heated and melted. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. In each example, 100 parts by weight of the used thermoplastic resin composition is composed of a polypropylene resin composition sorted and recovered from used home appliances. The silane coupling agent is usually a compound that improves physical properties by covalently binding an inorganic filler and a thermoplastic resin.

Examples 1 and 1.0 added 0.4 parts by weight of 3-glycyridoxypropyltrimethoxysilane, which is a silane coupling agent having an epoxy group, to 100 parts by weight of the used thermoplastic resin composition. Example 2 was added in parts by weight, and Example 3 was added in 1.8 parts by weight. Further, 0.4 parts by weight of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, which is a silane coupling agent having an amino group, was added to 100 parts by weight of the used thermoplastic resin composition. Examples 4 and 1.0 parts by weight were added to Example 5, and 1.8 parts by weight were added to Example 6. Further, Examples 7 and 1.8 added 1.0 part by weight of 3-isocyanatepropyltriethoxysilane, which is a silane coupling agent having an isocyanate group, to 100 parts by weight of the used thermoplastic resin composition. Example 8 was prepared by adding parts by weight.

Table 1 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Examples 1 to 8, the results of the FT-IR evaluation and the physical property evaluation of all the regenerated thermoplastic resin compositions were acceptable (A). That is, it was found that the appearance and physical properties of the regenerated thermoplastic resin compositions obtained under the conditions of Examples 1 to 8 were good.

<Examples 9 to 16>
In Examples 9 to 16, a silane coupling agent (3-glycyridoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), N-2-) was used with respect to the used thermoplastic resin composition. (Aminoethyl) -3-aminopropyltrimethoxysilane (KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) or 3-Ixoxide propyltriethoxysilane (KBE-9007N, manufactured by Shin-Etsu Chemical Co., Ltd.)) is added. The mixture was kneaded in a kneader at 210 ° C. while being heated and melted. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. In Examples 9 to 16, the difference from Examples 1 to 8 is that the used thermoplastic resin composition contains an inorganic filler. In each example, 100 parts by weight of the used thermoplastic resin composition, 80 parts by weight of the polypropylene resin composition sorted and recovered from the used home appliances, and an inorganic filler (general-purpose talc MS-K, Japan Talc Co., Ltd.) (Made) is included in 20 parts by weight.

Examples 9, 1.0, added 0.4 parts by weight of 3-glycyridoxypropyltrimethoxysilane, which is a silane coupling agent having an epoxy group, to 100 parts by weight of the used thermoplastic resin composition. The product to which a weight was added was designated as Example 10, and the product to which a weight of 1.8 parts was added was designated as Example 11. Further, 0.4 parts by weight of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, which is a silane coupling agent having an amino group, was added to 100 parts by weight of the used thermoplastic resin composition. Those added by 1.0 part by weight were designated as Example 13, and those added by 1.8 parts by weight were designated as Example 14. Further, 1.0 part by weight of 3-isocyanatepropyltriethoxysilane, which is a silane coupling agent having an isocyanate group, is added to 100 parts by weight of the used thermoplastic resin composition in Examples 15 and 1.8 by weight. The partially added product was designated as Example 16.

Table 2 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Examples 9 to 16, the results of the FT-IR evaluation and the physical property evaluation of all the regenerated thermoplastic resin compositions were acceptable (A). That is, it was found that the appearance and physical properties of the regenerated thermoplastic resin composition obtained under the conditions of Examples 9 to 16 were good.

Further, even when the used thermoplastic resin composition contains an inorganic filler, the regenerated thermoplastic resin composition obtained in Examples 9 to 16 has a good appearance and an excellent appearance design. It turned out to be a composition.

<Examples 17 to 24>
In Examples 17 to 24, an epoxy resin (bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) (1001, manufactured by Mitsubishi Chemical Corporation) or bisphenol A novolak type epoxy is used with respect to the used thermoplastic resin composition. A resin (157S70, manufactured by Mitsubishi Chemical Corporation) was added and mixed, and the mixture was kneaded in a kneader while being heated and melted at 210 ° C. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. In Examples 17 to 24, the difference from Examples 1 to 8 is that an epoxy resin is added to the used thermoplastic resin composition instead of the silane coupling agent. In each example, 100 parts by weight of the used thermoplastic resin composition is composed of a polypropylene resin composition sorted and recovered from used home appliances.

Example 17, 1.8 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) added to 100 parts by weight of the used thermoplastic resin composition was added. Examples 18 and 3.0 parts by weight were added to Example 19, and 5.0 parts by weight were added to Example 20. In addition, Example 21 was added with 0.2 parts by weight of bisphenol A novolak type epoxy resin to 100 parts by weight of the used thermoplastic resin composition, and Examples 22 and 3 were added with 1.8 parts by weight. The product to which 0.0 parts by weight was added was designated as Example 23, and the product to which 5.0 parts by weight was added was designated as Example 24.

Table 3 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Examples 17 to 24, the results of the FT-IR evaluation and the physical property evaluation of all the regenerated thermoplastic resin compositions were acceptable (A). That is, it was found that the appearance and physical properties of the regenerated thermoplastic resin composition obtained under the conditions of Examples 17 to 24 were good.

<Examples 25 to 32>
In Examples 25 to 32, an epoxy resin (bisphenol A type epoxy resin (epoxy equivalent: 875 to 975) (1004, manufactured by Mitsubishi Chemical Co., Ltd.) or bisphenol A type epoxy resin) is used with respect to the used thermoplastic resin composition. (Epoxy equivalent: 1750 to 2200) (1007, manufactured by Mitsubishi Chemical Corporation)) was added and mixed, and the mixture was kneaded in a kneader while being heated and melted at 210 ° C. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. In Examples 25 to 32, the difference from Examples 17 to 20 is the value of the epoxy equivalent of the bisphenol A type epoxy resin. In each example, 100 parts by weight of the used thermoplastic resin composition is composed of a polypropylene resin composition sorted and recovered from used home appliances.

Example 25, 1.8 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 875 to 975) added to 100 parts by weight of the used thermoplastic resin composition was added. Examples 26 and 3.0 parts by weight were added to Example 27, and 5.0 parts by weight were added to Example 28. Further, 1.6 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 1750 to 2200) was added to 100 parts by weight of the used thermoplastic resin composition, and 1.8 parts by weight of Example 29 was added. Examples 30 and 3.0 parts by weight were added to Example 31, and 5.0 parts by weight were added to Example 32.

Table 4 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Examples 25 to 32, the results of the FT-IR evaluation and the physical property evaluation of all the regenerated thermoplastic resin compositions were acceptable (A). That is, it was found that the appearance and physical properties of the regenerated thermoplastic resin compositions obtained under the conditions of Examples 25 to 32 were good.

Here, the epoxy equivalents of the epoxy resins used in Examples 17 to 20 are 450 to 500, the molecular weight is 900, and the softening point is 64 ° C. Since the temperature at the time of kneading is 210 ° C., when the epoxy resin used in Examples 17 to 20 is used, the epoxy resin may be softened and increased in viscosity at the charging port, which may clog the charging port. On the other hand, the epoxy equivalents of the epoxy resins used in Examples 25 to 28 are 875 to 975, the molecular weight is 1650, and the softening point is 97 ° C. The epoxy equivalents of the epoxy resins used in Examples 29 to 32 are 1750 to 2200, the molecular weight is 2900, and the softening point is 128 ° C. Therefore, if the epoxy resin used in Examples 25 to 32 is used in the production of the regenerated thermoplastic resin composition, the epoxy resin is softened at the inlet as compared with the epoxy resin used in Examples 17 to 20. It is possible to suppress the increase in viscosity.

In the bisphenol A type epoxy resin, which is the epoxy resin used in Examples 17 to 20 and 25 to 32, the softening point increases as the molecular weight increases, but the epoxy equivalent increases. The bisphenol A type epoxy resin has only the end of the epoxy group to react, and the larger the epoxy equivalent, the smaller the ratio of the reacting epoxy group. Therefore, the bisphenol A type epoxy resin having a high molecular weight requires a necessary addition rate. Will be higher.

<Examples 33 to 35>
In Examples 33 to 35, the used thermoplastic resin composition is subjected to an epoxy resin (bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) (1001, manufactured by Mitsubishi Chemical Co., Ltd.)) and stearer as a dispersant. 5 parts by weight of an inorganic pigment containing magnesium acid was added and mixed, and the mixture was kneaded in a kneader while being heated and melted at 210 ° C. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. In Examples 33 to 35, the difference from Examples 17 to 20 is that an inorganic pigment is added. In each example, the used thermoplastic resin composition contains 100 parts by weight of the polypropylene resin composition sorted and recovered from the used home electric appliances.

Example 33, 3.0 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) added to 100 parts by weight of the used thermoplastic resin composition was added. Example 34, 5.0 parts by weight was added as Example 35.

Table 5 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Examples 33 to 35, the results of the FT-IR evaluation and the physical property evaluation of all the regenerated thermoplastic resin compositions were acceptable (A). That is, it was found that the appearance and physical properties of the regenerated thermoplastic resin compositions obtained under the conditions of Examples 33 to 35 were good.

When 17% by weight magnesium stearate is used as a dispersant for the inorganic pigment which is a coloring pigment, the fatty acid content of the inorganic pigment is 8.2% by weight. When 5 parts by weight of the inorganic pigment is added to the used thermoplastic resin composition, the fatty acid content with respect to 100 parts by weight of the used thermoplastic resin composition is 0.41% by weight. The fatty acid content in 100 parts by weight of the used thermoplastic resin composition is 0.23% by weight. Therefore, when the fatty acid contained in 5 parts by weight of the inorganic pigment and the fatty acid contained in 100 parts by weight of the used thermoplastic resin composition are combined, the fatty acid content of the regenerated thermoplastic resin composition is 0.64% by weight. Become. Therefore, when an inorganic pigment is used, in order to improve the appearance of the resin molded product of the regenerated thermoplastic resin composition, the fatty acid content is increased by the amount of the added inorganic pigment, so that more epoxy resin is added. It is necessary to do.

<Examples 36 to 43>
In Examples 36 to 43, an epoxy resin (bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) (1001, manufactured by Mitsubishi Chemical Corporation) or bisphenol A novolak type epoxy is used with respect to the used thermoplastic resin composition. A resin (157S70, manufactured by Mitsubishi Chemical Corporation) was added and mixed, and the mixture was kneaded in a kneader while being heated and melted at 210 ° C. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. In Examples 36 to 43, the difference from Examples 17 to 24 is that the used thermoplastic resin composition contains an inorganic filler. In each example, 100 parts by weight of the used thermoplastic resin composition, 80 parts by weight of the polypropylene resin composition sorted and recovered from the used home appliances, and an inorganic filler (general-purpose talc MS-K, Japan Talc Co., Ltd.) (Made) is included in 20 parts by weight.

Example 36, 1.8 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) added to 100 parts by weight of the used thermoplastic resin composition was added. Examples 37 and 3.0 parts by weight were added to Example 38, and 5.0 parts by weight were added to Example 39. In addition, 0.2 parts by weight of bisphenol A novolak type epoxy resin was added to 100 parts by weight of the used thermoplastic resin composition in Examples 40, and 1.8 parts by weight was added in Examples 41 and 3. The product to which 0.0 parts by weight was added was designated as Example 42, and the product to which 5.0 parts by weight was added was designated as Example 43.

Table 6 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Examples 36 to 43, the results of the FT-IR evaluation and the physical property evaluation of all the regenerated thermoplastic resin compositions were acceptable (A). That is, it was found that the appearance and physical properties of the regenerated thermoplastic resin compositions obtained under the conditions of Examples 36 to 43 were good.

Further, even when the used thermoplastic resin composition contains an inorganic filler, the regenerated thermoplastic resin compositions obtained in Examples 36 to 43 have a good appearance and excellent appearance design. It turned out to be a resin composition.

The epoxy equivalent of the bisphenol A novolak type epoxy resin 157S70 is 200 to 220, which is about half of the epoxy equivalent of the bisphenol A type epoxy resin 1001 of 450 to 500. That is, when compared by the weight of the resin containing 1 g equivalent of the epoxy group, the bisphenol A novolak type epoxy resin 157S70 is about half that of the bisphenol A type epoxy resin 1001, so that the effective minimum addition rate is as shown in Table 6. The amount of bisphenol A novolak type epoxy resin 157S70 was 0.2 parts by weight, which was half of 0.4 parts by weight of bisphenol A type epoxy resin 1001.

Here, an example of the regenerated thermoplastic resin composition obtained when the bisphenol A type epoxy resin is added to the used thermoplastic resin composition containing the polypropylene resin composition is shown below (chemical formula). In 1, 2 and 3,
l = 1-13,
-R ^1- : Substituent represented by Chemical Formula 4-R ² :-(CH ₂ ) _n CH ₃ (any of n = 10, 12, 14, 16) or-(CH ₂ ) ₇ CH = CH ( CH ₂ ) _m CH ₃ (m = 5, 7)). As the regenerated thermoplastic resin composition, one type of regenerated thermoplastic resin composition may be obtained from the following chemical formulas 1, 2 and 3, or a plurality of types of regenerated thermoplastic resin compositions may be obtained. In some cases.

Further, an example of the regenerated thermoplastic resin composition obtained when the bisphenol A novolak type epoxy resin is added to the used thermoplastic resin composition containing the polypropylene resin composition is shown below (chemical formula). In 5, 6 and 7,
k = 1 to 13
-R ² :-(CH ₂ ) _n CH ₃ (any of n = 10, 12, 14, 16) or-(CH ₂ ) ₇ CH = CH (CH ₂ ) _m CH ₃ (m = 5, 7) either)). As the regenerated thermoplastic resin composition, one type of regenerated thermoplastic resin composition may be obtained from the following chemical formulas 5, 6 and 7, or a plurality of types of regenerated thermoplastic resin compositions may be obtained. In some cases.

<Examples 44 to 51>
In Examples 44 to 51, an epoxy resin (bisphenol A type epoxy resin (epoxy equivalent: 875 to 975) (1004, manufactured by Mitsubishi Chemical Co., Ltd.) or bisphenol A type epoxy resin) is used with respect to the used thermoplastic resin composition. (Epoxy equivalent: 1750 to 2200) (1007, manufactured by Mitsubishi Chemical Corporation)) was added and mixed, and the mixture was kneaded in a kneader while being heated and melted at 210 ° C. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. In Examples 44 to 51, the difference from Examples 25 to 32 is that the used thermoplastic resin composition contains an inorganic filler. In each example, 100 parts by weight of the used thermoplastic resin composition, 80 parts by weight of the polypropylene resin composition sorted and recovered from the used home appliances, and an inorganic filler (general-purpose talc MS-K, Japan Talc Co., Ltd.) (Made) is included in 20 parts by weight.

Example 44, 1.8 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 875 to 975) added to 100 parts by weight of the used thermoplastic resin composition was added. Examples 45 and 3.0 parts by weight were added to Example 46, and 5.0 parts by weight were added to Example 47. Further, 1.6 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 1750 to 2200) was added to 100 parts by weight of the used thermoplastic resin composition, and 1.8 parts by weight of Example 48 was added. Examples 49 and 3.0 parts by weight were added to Example 50, and 5.0 parts by weight were added to Example 51.

Table 7 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Examples 44 to 51, the results of the FT-IR evaluation and the physical property evaluation of all the regenerated thermoplastic resin compositions were acceptable (A). That is, it was found that the appearance and physical properties of the regenerated thermoplastic resin compositions obtained under the conditions of Examples 44 to 51 were good.

Further, even when the used thermoplastic resin composition contains an inorganic filler, the regenerated thermoplastic resin compositions obtained in Examples 44 to 51 have a good appearance and excellent appearance design. It turned out to be a resin composition.

<Examples 52 to 54>
In Examples 52 to 54, the used thermoplastic resin composition is subjected to an epoxy resin (bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) (1001, manufactured by Mitsubishi Chemical Corporation)) and stearer as a dispersant. 5 parts by weight of an inorganic pigment containing magnesium acid was added and mixed, and the mixture was kneaded in a kneader while being heated and melted at 210 ° C. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. In Examples 52 to 54, the difference from Examples 33 to 35 is that the used thermoplastic resin composition contains an inorganic filler. In each example, 100 parts by weight of the used thermoplastic resin composition, 80 parts by weight of the polypropylene resin composition sorted and recovered from the used home appliances, and an inorganic filler (general-purpose talc MS-K, Japan Talc Co., Ltd.) (Made) is included in 20 parts by weight.

Example 52, 3.0 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) added to 100 parts by weight of the used thermoplastic resin composition was added. Examples 53 and 5.0 parts by weight were added as Example 54.

Table 8 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Examples 52 to 54, the results of the FT-IR evaluation and the physical property evaluation of all the regenerated thermoplastic resin compositions were acceptable (A). That is, it was found that the appearance and physical properties of the regenerated thermoplastic resin compositions obtained under the conditions of Examples 52 to 54 were good.

Further, even when the used thermoplastic resin composition contains an inorganic filler, the regenerated thermoplastic resin compositions obtained in Examples 52 to 54 have a good appearance and excellent appearance design. It turned out to be a resin composition.

<Examples 55 to 57>
In Examples 55 to 57, the used thermoplastic resin composition is subjected to an epoxy resin (bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) (1001, manufactured by Mitsubishi Chemical Corporation)) and stearer as a dispersant. Two parts by weight of an inorganic pigment containing magnesium acid was added and mixed, and the mixture was kneaded in a kneader while being heated and melted at 210 ° C. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. In Examples 55 to 57, the difference from Examples 52 to 54 is the addition rate of the inorganic pigment. In each example, 100 parts by weight of the used thermoplastic resin composition, 80 parts by weight of the polypropylene resin composition sorted and recovered from the used home appliances, and an inorganic filler (general-purpose talc MS-K, Japan Talc Co., Ltd.) (Made) is included in 20 parts by weight.

Examples 55 and 3.0 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) added to 100 parts by weight of the used thermoplastic resin composition were added. Examples 56 and 5.0 parts by weight were added as Example 57.

Table 9 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Examples 55 to 57, the results of the FT-IR evaluation and the physical property evaluation of all the regenerated thermoplastic resin compositions were acceptable (A). That is, it was found that the appearance and physical properties of the regenerated thermoplastic resin compositions obtained under the conditions of Examples 55 to 57 were good.

In Example 55 containing 2 parts by weight of the inorganic pigment, the amount of bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) to be added could be reduced by 0.4 parts by weight as compared with Example 52 containing 5 parts by weight of the inorganic pigment. As a result, by reducing the addition rate of the inorganic pigment to the used thermoplastic resin composition, the fatty acid contained is also reduced, and by adding a smaller amount of epoxy resin, the appearance and physical properties of the regenerated thermoplastic resin composition can be improved. I understood.

Normally, if the addition rate of the inorganic pigment is reduced, it may not be possible to adjust the color to the desired color tone. However, for example, when recovering the used thermoplastic resin composition, only dark-colored flakes are removed in advance. If this is done, the addition rate of the inorganic pigment when toning the light-colored regenerated thermoplastic resin composition can be reduced. Further, for example, if the foreign matter that causes the appearance deterioration is removed in advance, the amount of the inorganic pigment for concealing the foreign matter can be reduced.

<Example 58>
In Example 58, 1.2 parts by weight of an epoxy resin (bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) (1001, manufactured by Mitsubishi Chemical Corporation)) was oxidized with respect to the used thermoplastic resin composition. 0.5 part by weight of an inhibitor (A-611, ADEKA Corporation) and 0.1 part by weight of a metal inactivating agent (CDA-6, ADEKA Corporation) were added and mixed, and the mixture was mixed at 240 ° C. , Kneaded in a kneader while heating and melting. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 30 ° C. In Example 58, 100 parts by weight of the used thermoplastic resin composition, 80 parts by weight of the polypropylene resin composition sorted and recovered from the used home appliances, and an inorganic filler (general-purpose talc MS-K, Japan Talc Co., Ltd.) (Made) is included in 20 parts by weight.

Table 10 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Example 58, the results of the FT-IR evaluation and the physical property evaluation of the regenerated thermoplastic resin composition were acceptable (A). That is, it was found that the appearance and physical properties of the regenerated thermoplastic resin composition obtained under the conditions of Example 58 were good.

Furthermore, it was found that the appearance and physical properties of the obtained regenerated thermoplastic resin composition were good even when an antioxidant and a metal inactivating agent were added to the used thermoplastic resin composition.

<Examples 59 to 61>
In Examples 59 to 61, an epoxy resin (bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) (1001, manufactured by Mitsubishi Chemical Corporation)) was used as a dispersant for the used thermoplastic resin composition. 5 parts by weight of an inorganic pigment containing magnesium acid, 0.5 part by weight of an antioxidant (A-611, ADEKA Corporation) and 0.1 part by weight of a metal inactivating agent (CDA-6, ADEKA Corporation). The added and mixed product was kneaded in a kneader while being heated and melted at 220 ° C. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 30 ° C. Examples 59 to 61 differ from Examples 52 to 54 in that they contain 0.5 parts by weight of the antioxidant and 0.1 parts by weight of the metal inactivating agent. In each example, 100 parts by weight of the used thermoplastic resin composition, 80 parts by weight of the polypropylene resin composition sorted and recovered from the used home appliances, and an inorganic filler (general-purpose talc MS-K, Japan Talc Co., Ltd.) (Made) is included in 20 parts by weight.

Example 59, 3.0 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) added to 100 parts by weight of the used thermoplastic resin composition was added. Examples 60 and 5.0 parts by weight were added as Example 61.

Table 11 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Examples 59 to 61, the results of the FT-IR evaluation and the physical property evaluation of all the regenerated thermoplastic resin compositions were acceptable (A). That is, it was found that the appearance and physical properties of the regenerated thermoplastic resin compositions obtained under the conditions of Examples 59 to 61 were good.

Further, even when the used thermoplastic resin composition contains an antioxidant and a metal inactivating agent, the regenerated thermoplastic resin compositions obtained in Examples 59 to 61 have a good appearance and an appearance design. It was found to be a regenerated thermoplastic resin composition having excellent properties.

<Examples 62 to 64>
In Examples 62 to 64, an epoxy resin (bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) (1001, manufactured by Mitsubishi Chemical Corporation)) was used as a dispersant for the used thermoplastic resin composition. 2 parts by weight of an inorganic pigment containing magnesium acid, 0.5 part by weight of an antioxidant (A-611, ADEKA Corporation) and 0.1 part by weight of a metal inactivating agent (CDA-6, ADEKA Corporation). The added and mixed product was kneaded in a kneader while being heated and melted at 220 ° C. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 30 ° C. Examples 62 to 64 differ from Examples 55 to 57 in that they contain 0.5 parts by weight of the antioxidant and 0.1 parts by weight of the metal inactivating agent. In each example, 100 parts by weight of the used thermoplastic resin composition, 80 parts by weight of the polypropylene resin composition sorted and recovered from the used home appliances, and an inorganic filler (general-purpose talc MS-K, Japan Talc Co., Ltd.) (Made) is included in 20 parts by weight.

Example 62, 3.0 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) added to 100 parts by weight of the used thermoplastic resin composition was added. Examples 63 and 5.0 parts by weight were added as Example 64.

Table 12 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Examples 62 to 64, the results of the FT-IR evaluation and the physical property evaluation of all the regenerated thermoplastic resin compositions were acceptable (A). That is, it was found that the appearance and physical properties of the regenerated thermoplastic resin composition obtained under the conditions of Examples 62 to 64 were good.

Further, even when the used thermoplastic resin composition contains an antioxidant and a metal inactivating agent, the regenerated thermoplastic resin compositions obtained in Examples 62 to 64 have a good appearance and an appearance design. It was found to be a regenerated thermoplastic resin composition having excellent properties.

<Comparative Examples 1 to 12>
In Comparative Examples 1 to 12, a silane coupling agent (3-glycyridoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), N-2-) was used with respect to the used thermoplastic resin composition. (Aminoethyl) -3-aminopropyltrimethoxysilane (KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-Ixocyanatepropyltriethoxysilane (KBE-9007N, manufactured by Shin-Etsu Chemical Co., Ltd.), vinyl triethoxy Silane (KBE-1003, manufactured by Shin-Etsu Chemical Co., Ltd.) or 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed, and the mixture was added and mixed at 210 ° C. It was kneaded in a kneader while being heated and melted. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. The ISO dumbbell test piece was molded under the same conditions as above even when nothing was added to the polypropylene resin composition sorted and recovered from used home appliances. In each comparative example, 100 parts by weight of the used thermoplastic resin composition is composed of a polypropylene resin composition sorted and recovered from used home appliances.

Comparative Example 1 in which nothing was added to 100 parts by weight of the used thermoplastic resin composition, 0.2 weight of 3-glycyridoxypropyltrimethoxysilane, which is a silane coupling agent having an epoxy group. Comparative Example 2 was added in parts, Comparative Example 3 was added in an amount of 3.0 parts by weight, and Comparative Example 4 was added in an amount of 5.0 parts by weight. Further, 0.2 part by weight of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, which is a silane coupling agent having an amino group, was added to 100 parts by weight of the used thermoplastic resin composition. Comparative Example 5, the one to which 3.0 parts by weight was added was designated as Comparative Example 6, and the one to which 5.0 parts by weight was added was designated as Comparative Example 7. Further, Comparative Examples 8 and 3.0 were prepared by adding 0.8 parts by weight of 3-isocyanatepropyltriethoxysilane, which is a silane coupling agent having an isocyanate group, to 100 parts by weight of the used thermoplastic resin composition. The one to which a part by weight was added was designated as Comparative Example 9, and the one to which 5.0 parts by weight was added was designated as Comparative Example 10. Further, 1.0 part by weight of vinyltriethoxysilane, which is a silane coupling agent having a functional group (vinyl group) that does not react with the carboxyl group in the fatty acid, was added to 100 parts by weight of the used thermoplastic resin composition. Comparative Example 11 was prepared by adding 1.0 part by weight of 3-methacryloxypropyltrimethoxysilane, which is a silane coupling agent having a functional group (methacryl group) that does not react with the carboxyl group in the fatty acid, as Comparative Example 12. And said.

Table 13 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Comparative Examples 1, 2, 5, 8, 11 and 12, the tensile elongation at break retention rate was 75% or more, and the physical property determination was acceptable (A), but the FT-IR evaluation was unacceptable (B). Because of this, the overall judgment was rejected (B). In Comparative Examples 3, 4, 6, 7, 9 and 10, the FT-IR evaluation was acceptable (A), but the tensile elongation at break retention rate was less than 75% and failed (B). The judgment was rejected (B).

From the results of Comparative Example 1, it was found that when the silane coupling agent was not added, fatty acid bleed-out occurred, so that the appearance of the regenerated thermoplastic resin composition could not be improved. Further, from the results of Comparative Examples 2, 5 and 8, the silane coupling agent having an epoxy group or an amino group has more than 0.2 parts by weight with respect to the used thermoplastic resin composition, and the silane cup having an isocyanate group. It was found that the appearance of the regenerated thermoplastic resin composition could not be improved unless the ring agent was added in an amount of more than 0.8 parts by weight. Further, from the results of Comparative Examples 3, 4, 6, 7, 9 and 10, 3.0 parts by weight of a silane coupling agent having an epoxy group, an amino group and an isocyanate group was added to the used thermoplastic resin composition. It was found that the above addition deteriorated the physical characteristics of the obtained regenerated thermoplastic resin composition. Further, from the results of Comparative Examples 11 and 12, the silane coupling agent having a vinyl group and a methacrylic group, which are functional groups that do not react with the carboxyl group in the fatty acid, is 1.0 with respect to the used thermoplastic resin composition. It was found that the appearance of the obtained regenerated thermoplastic resin composition could not be improved even if it was added by weight.

<Comparative Examples 13 to 22>
In Comparative Examples 13 to 22, a silane coupling agent (3-glycyridoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), N-2-) was used with respect to the used thermoplastic resin composition. (Aminoethyl) -3-aminopropyltrimethoxysilane (KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) or 3-Ixoxide propyltriethoxysilane (KBE-9007N, manufactured by Shin-Etsu Chemical Co., Ltd.)) is added. The mixture was kneaded in a kneader at 210 ° C. while being heated and melted. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. The ISO dumbbell test piece was molded under the same conditions as above even when nothing other than 20 parts by weight of the inorganic filler was added to the polypropylene resin composition sorted and recovered from the used home appliances. In Comparative Examples 13 to 22, the difference from Comparative Examples 1 to 10 is that the used thermoplastic resin composition contains an inorganic filler. In each comparative example, 100 parts by weight of the used thermoplastic resin composition, 80 parts by weight of the polypropylene resin composition sorted and recovered from the used home appliances, and an inorganic filler (general-purpose talc MS-K, Nippon Talc Co., Ltd.) (Made) is included in 20 parts by weight.

Comparative Example 13 was obtained by adding nothing to 100 parts by weight of the used thermoplastic resin composition, and 0.2 weight of 3-glycyridoxypropyltrimethoxysilane, which is a silane coupling agent having an epoxy group. Comparative Example 14 was added in parts, Comparative Example 15 was added in an amount of 3.0 parts by weight, and Comparative Example 16 was added in an amount of 5.0 parts by weight. Further, 0.2 part by weight of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, which is a silane coupling agent having an amino group, was added to 100 parts by weight of the used thermoplastic resin composition. Those added in Comparative Example 17 and 3.0 parts by weight were designated as Comparative Example 18, and those to which 5.0 parts by weight were added were designated as Comparative Example 19. Further, Comparative Examples 20 and 3.0 were prepared by adding 0.8 parts by weight of 3-isocyanatepropyltriethoxysilane, which is a silane coupling agent having an isocyanate group, to 100 parts by weight of the used thermoplastic resin composition. The one added by weight was designated as Comparative Example 21, and the one added by 5.0 parts by weight was designated as Comparative Example 22.

Table 14 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Comparative Examples 13, 14, 17 and 20, the tensile elongation at break retention rate was 75% or more, and the physical property determination was acceptable (A), but the FT-IR evaluation was unacceptable (B). The judgment was rejected (B). In Comparative Examples 15, 16, 18, 19, 21 and 22, the FT-IR evaluation was acceptable (A), but the tensile elongation at break retention rate was less than 75% and failed (B). The judgment was rejected (B).

From the results of Comparative Example 13, it was found that when the silane coupling agent was not added to the used thermoplastic resin composition, fatty acid bleed-out occurred and the appearance could not be improved. Further, from the results of Comparative Examples 14, 17 and 20, the silane coupling agent having an epoxy group or an amino group had more than 0.2 parts by weight, and the silane coupling agent having an isocyanate group had more than 0.8 parts by weight. It was found that the appearance of the regenerated thermoplastic resin composition could not be improved without the addition. Further, from the results of Comparative Examples 15, 16, 18, 19, 21 and 22, when 3.0 parts by weight or more of a silane coupling agent having an epoxy group, an amino group and an isocyanate group was added, the obtained thermoplastic resin composition was added. It was found that the physical properties of the object deteriorated.

Further, from the results of Comparative Examples 1 to 10 and the results of Comparative Examples 13 to 22, the inorganic filler contained in the used thermoplastic resin composition affects the results of the FT-IR evaluation and the physical property evaluation. It turned out not.

<Comparative Examples 23 to 26>
In Comparative Examples 23 to 26, the epoxy resin (bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) (1001, manufactured by Mitsubishi Chemical Co., Ltd.) and bisphenol A novolak type epoxy) were used with respect to the used thermoplastic resin composition. A resin (157S70, manufactured by Mitsubishi Chemical Corporation) was added and mixed, and the mixture was kneaded in a kneader while being heated and melted at 210 ° C. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. In Comparative Examples 23 to 26, the difference from Comparative Examples 1 to 12 is that an epoxy resin is added to the used thermoplastic resin composition instead of the silane coupling agent. In each comparative example, 100 parts by weight of the used thermoplastic resin composition is composed of a polypropylene resin composition sorted and recovered from used home appliances.

Comparative Example 23, 10 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) added to 100 parts by weight of the used thermoplastic resin composition, Comparative Example. It was set to 24. Further, Comparative Example 25 was prepared by adding 0.1 part by weight of bisphenol A novolak type epoxy resin to 100 parts by weight of the used thermoplastic resin composition, and Comparative Example 26 was added by 10 parts by weight.

Table 15 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Comparative Examples 23 and 25, the tensile elongation at break retention rate was 75% or more, and the physical property judgment was passed (A), but the FT-IR evaluation was failed (B), so the comprehensive judgment was rejected. It was designated as (B). In Comparative Examples 24 and 26, the FT-IR evaluation was passed (A), but the tensile elongation at break retention rate was less than 75% and failed (B), so the comprehensive judgment was rejected (B). did.

From the results of Comparative Examples 23 and 25, the bisphenol A type epoxy resin was more than 0.2 parts by weight and the bisphenol A novolak type epoxy resin was more than 0.1 parts by weight with respect to 100 parts by weight of the used thermoplastic resin composition. It was found that the regenerated thermoplastic resin composition could not have a good appearance unless it was added in a large amount. Further, from the results of Comparative Examples 24 and 26, when 10 parts by weight of the bisphenol A type epoxy resin and the bisphenol A novolak type epoxy resin were added to 100 parts by weight of the used thermoplastic resin composition, the regenerated thermoplastic resin composition was obtained. It was found that the physical properties of

<Comparative Examples 27 to 30>
In Comparative Examples 27 to 30, an epoxy resin (bisphenol A type epoxy resin (epoxy equivalent: 875 to 975) (1004, manufactured by Mitsubishi Chemical Corporation) or bisphenol A type epoxy resin) was used with respect to the used thermoplastic resin composition. (Epoxy equivalent: 1750 to 2200) (1007, manufactured by Mitsubishi Chemical Corporation)) was added and mixed, and the mixture was kneaded in a kneader while being heated and melted at 210 ° C. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. In Comparative Examples 27 to 30, the difference from Comparative Examples 23 and 24 is the value of the epoxy equivalent of the epoxy resin. In each comparative example, 100 parts by weight of the used thermoplastic resin composition is composed of a polypropylene resin composition sorted and recovered from used home appliances.

Comparative Example 27, 10 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 875 to 975) added to 100 parts by weight of the used thermoplastic resin composition, Comparative Example. It was set to 28. Further, in Comparative Example 29, 10 parts by weight of a bisphenol A type epoxy resin (epoxy equivalent: 1750 to 2200) added to 100 parts by weight of the used thermoplastic resin composition was added. It was designated as Comparative Example 30.

Table 16 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Comparative Examples 27 and 29, the tensile elongation at break retention rate was 75% or more, and the physical property judgment was passed (A), but the FT-IR evaluation was failed (B), so the comprehensive judgment was rejected. It was designated as (B). In Comparative Examples 28 and 30, the FT-IR evaluation was passed (A), but the tensile elongation at break retention rate was less than 75% and failed (B), so the comprehensive judgment was rejected (B). did.

From the results of Comparative Examples 27 and 29, the bisphenol A type epoxy resin (epoxy equivalent: 875 to 975) was more than 0.6 parts by weight with respect to 100 parts by weight of the used thermoplastic resin composition, and the bisphenol A type epoxy resin. It was found that the regenerated thermoplastic resin composition could not have a good appearance unless (epoxy equivalent: 1750 to 2200) was added in an amount of more than 1.4 parts by weight. Further, from the results of Comparative Examples 28 and 30, when 10 parts by weight of a bisphenol A type epoxy resin (epoxy equivalent: 875 to 975 or 1750 to 2200) was added to 100 parts by weight of the used thermoplastic resin composition, it was regenerated. It was found that the physical properties of the thermoplastic resin composition deteriorated.

<Comparative Examples 31 and 32>
In Comparative Examples 31 and 32, the used thermoplastic resin composition was used as an epoxy resin (bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) (1001, manufactured by Mitsubishi Chemical Co., Ltd.)) and as a dispersant. 5 parts by weight of an inorganic pigment containing magnesium stearate was added and mixed, and the mixture was kneaded in a kneader while being heated and melted at 210 ° C. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. In Comparative Examples 31 and 32, the difference from Comparative Examples 23 and 24 is that an inorganic pigment is added. In each comparative example, the used thermoplastic resin composition contains 100 parts by weight of the polypropylene resin composition sorted and recovered from the used home electric appliances.

Comparative Example 31 and 10 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) added to 100 parts by weight of the used thermoplastic resin composition. It was set to 32.

Table 17 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Comparative Example 31, the tensile elongation at break retention rate was 75% or more, and the physical property judgment was passed (A), but the FT-IR evaluation was failed (B), so the comprehensive judgment was rejected (B). ). In Comparative Example 32, the FT-IR evaluation was passed (A), but the tensile elongation at break retention rate was less than 75% and failed (B), so the comprehensive judgment was rejected (B).

From the results of Comparative Example 31, the regenerated thermoplastic resin composition must be added in an amount of more than 2.0 parts by weight of the bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) with respect to 100 parts by weight of the used thermoplastic resin composition. It turned out that things couldn't look good. Further, from the results of Comparative Example 32, when 10 parts by weight of a bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) was added to 100 parts by weight of the used thermoplastic resin composition, the regenerated thermoplastic resin composition was prepared. It was found that the physical properties deteriorated.

<Comparative Examples 33 to 36>
In Comparative Examples 33 to 36, the epoxy resin (bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) (1001, manufactured by Mitsubishi Chemical Corporation) and bisphenol A novolak type epoxy were used with respect to the used thermoplastic resin composition. A resin (157S70, manufactured by Mitsubishi Chemical Corporation) was added and mixed, and the mixture was kneaded in a kneader while being heated and melted at 210 ° C. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. Comparative Examples 33 to 36 differ from Comparative Examples 23 to 26 in that the used thermoplastic resin composition contains an inorganic filler. In each comparative example, 100 parts by weight of the used thermoplastic resin composition, 80 parts by weight of the polypropylene resin composition sorted and recovered from the used home appliances, and an inorganic filler (general-purpose talc MS-K, Nippon Talc Co., Ltd.) (Made) is included in 20 parts by weight.

Comparative Example 33, 10 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) added to 100 parts by weight of the used thermoplastic resin composition, Comparative Example. It was set to 34. Further, Comparative Example 35 was added with 0.1 part by weight of bisphenol A novolak type epoxy resin to 100 parts by weight of the used thermoplastic resin composition, and Comparative Example 36 was added with 10 parts by weight.

Table 18 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Comparative Examples 33 and 35, the tensile elongation at break retention rate was 75% or more, and the physical property judgment was passed (A), but the FT-IR evaluation was failed (B), so the comprehensive judgment was rejected. It was designated as (B). In Comparative Examples 34 and 36, the FT-IR evaluation was passed (A), but the tensile elongation at break retention rate was less than 75% and failed (B), so the comprehensive judgment was rejected (B). did.

From the results of Comparative Examples 33 and 35, the bisphenol A type epoxy resin is not added more than 0.2 parts by weight and the bisphenol A novolak type epoxy resin is not added more than 0.1 parts by weight with respect to the used thermoplastic resin composition. It was found that the regenerated thermoplastic resin composition could not have a good appearance. Further, from the results of Comparative Examples 34 and 36, when 10 parts by weight of the bisphenol A type epoxy resin and the bisphenol A novolak type epoxy resin were added to the used thermoplastic resin composition, the physical properties of the regenerated thermoplastic resin composition were improved. It turned out to decrease.

Further, from the results of Comparative Examples 23 to 26 and the results of Comparative Examples 33 to 36, the inorganic filler contained in the used thermoplastic resin composition affects the results of the FT-IR evaluation and the physical property evaluation. It turned out not.

<Comparative Examples 37-40>
In Comparative Examples 37 to 40, an epoxy resin (bisphenol A type epoxy resin (epoxy equivalent: 875 to 975) (1004, manufactured by Mitsubishi Chemical Co., Ltd.) or bisphenol A type epoxy resin) was used with respect to the used thermoplastic resin composition. (Epoxy equivalent: 1750 to 2200) (1007, manufactured by Mitsubishi Chemical Corporation)) was added and mixed, and the mixture was kneaded in a kneader while being heated and melted at 210 ° C. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. In Comparative Examples 37 to 40, the difference from Comparative Examples 27 to 30 is that the used thermoplastic resin composition contains an inorganic filler. In each comparative example, 100 parts by weight of the used thermoplastic resin composition, 80 parts by weight of the polypropylene resin composition sorted and recovered from the used home appliances, and an inorganic filler (general-purpose talc MS-K, Nippon Talc Co., Ltd.) (Made) is included in 20 parts by weight.

Comparative Example 37, 10 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 875 to 975) added to 100 parts by weight of the used thermoplastic resin composition, Comparative Example. It was set to 38. Further, in Comparative Example 39, 10 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 1750 to 2200) was added to 100 parts by weight of the used thermoplastic resin composition. It was designated as Comparative Example 40.

Table 19 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Comparative Examples 37 and 39, the tensile elongation at break retention rate was 75% or more, and the physical property judgment was passed (A), but the FT-IR evaluation was failed (B), so the comprehensive judgment was rejected. It was designated as (B). In Comparative Examples 38 and 40, the FT-IR evaluation was passed (A), but the tensile elongation at break retention rate was less than 75% and failed (B), so the comprehensive judgment was rejected (B). did.

From the results of Comparative Examples 37 and 39, the bisphenol A type epoxy resin (epoxy equivalent: 875 to 975) was more than 0.6 parts by weight with respect to 100 parts by weight of the used thermoplastic resin composition, and the bisphenol A type epoxy resin. It was found that the regenerated thermoplastic resin composition could not have a good appearance unless (epoxy equivalent: 1750 to 2200) was added in an amount of more than 1.4 parts by weight. Further, from the results of Comparative Examples 38 and 40, when 10 parts by weight of a bisphenol A type epoxy resin (epoxy equivalent: 875 to 975 or 1750 to 2200) was added to 100 parts by weight of the used thermoplastic resin composition, it was regenerated. It was found that the physical properties of the thermoplastic resin composition deteriorated.

<Comparative Examples 41 and 42>
In Comparative Examples 41 and 42, an epoxy resin (bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) (1001, manufactured by Mitsubishi Chemical Co., Ltd.)) was used as a dispersant for the used thermoplastic resin composition. 5 parts by weight of an inorganic pigment containing magnesium acid was added and mixed, and the mixture was kneaded in a kneader while being heated and melted at 210 ° C. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. The difference between Comparative Examples 41 and 42 and Comparative Examples 31 and 32 is that the used thermoplastic resin composition contains an inorganic filler. In each comparative example, the used thermoplastic resin composition is 80 parts by weight of the polypropylene resin composition sorted and recovered from the used home appliances, and 20 parts by weight of the inorganic filler (general-purpose talc MS-K, manufactured by Nippon Talc Co., Ltd.). Part is included.

Comparative Example 41, 10 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) added to 100 parts by weight of the used thermoplastic resin composition, Comparative Example. It was set to 42.

Table 20 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Comparative Example 41, the tensile elongation at break retention rate was 75% or more, and the physical property judgment was passed (A), but the FT-IR evaluation was failed (B), so the comprehensive judgment was rejected (B). ). In Comparative Example 42, the FT-IR evaluation was passed (A), but the tensile elongation at break retention rate was less than 75% and failed (B), so the comprehensive judgment was rejected (B).

From the results of Comparative Example 41, the regenerated thermoplastic resin composition must be added in an amount of more than 1.6 parts by weight of the bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) with respect to 100 parts by weight of the used thermoplastic resin composition. It turned out that things couldn't look good. Further, from the results of Comparative Example 42, when 10 parts by weight of a bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) was added to 100 parts by weight of the used thermoplastic resin composition, the regenerated thermoplastic resin composition was prepared. It was found that the physical properties deteriorated.

<Comparative Examples 43 and 44>
In Comparative Examples 43 and 44, an epoxy resin (bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) (1001, manufactured by Mitsubishi Chemical Corporation)) was used as a dispersant for the used thermoplastic resin composition. Two parts by weight of an inorganic pigment containing magnesium acid was added and mixed, and the mixture was kneaded in a kneader while being heated and melted at 210 ° C. Then, an ISO dumbbell test piece, that is, a regenerated thermoplastic resin composition was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 210 ° C. and a mold temperature of 50 ° C. In Comparative Examples 43 and 44, the difference from Comparative Examples 41 and 42 is the addition rate of the inorganic pigment. In each comparative example, the used thermoplastic resin composition is 80 parts by weight of the polypropylene resin composition sorted and recovered from the used home appliances, and 20 parts by weight of the inorganic filler (general-purpose talc MS-K, manufactured by Nippon Talc Co., Ltd.). Part is included.

Comparative Example 43, 10 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) added to 100 parts by weight of the used thermoplastic resin composition, Comparative Example. It was set to 44.

Table 21 shows the results of FT-IR evaluation and physical property evaluation after exposure to hot water using the obtained test pieces. In Comparative Example 43, the tensile elongation at break retention rate was 75% or more, and the physical property determination was acceptable (A), but the FT-IR evaluation was unacceptable (B), so the comprehensive determination was unacceptable (B). ). In Comparative Example 44, the FT-IR evaluation was passed (A), but the tensile elongation at break retention rate was less than 75% and failed (B), so the comprehensive judgment was rejected (B).

From the results of Comparative Example 43, the regenerated thermoplastic resin composition must be added in an amount of more than 1.2 parts by weight of the bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) with respect to 100 parts by weight of the used thermoplastic resin composition. It turned out that things couldn't look good. Further, from the results of Comparative Example 44, when 10 parts by weight of a bisphenol A type epoxy resin (epoxy equivalent: 450 to 500) was added to 100 parts by weight of the used thermoplastic resin composition, the regenerated thermoplastic resin composition was prepared. It was found that the physical properties deteriorated.

Here, FIG. 1 is a diagram showing the addition amount of each compound according to the first embodiment. The horizontal axis of FIG. 1 is the amount of each compound added to 100 parts by weight of the used thermoplastic resin composition. In FIG. 1, a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having an isocyanate group, and an epoxy resin were mixed with 100 parts by weight of each used thermoplastic resin composition. In this case, the relationship between the amount of each compound added and the effective range and the ineffective range is shown. Here, "effective" refers to the case of A in the above-mentioned comprehensive judgment.

In FIG. 1, the range shown in white is the effective range in each compound, and the range shown in black is the ineffective range in each compound. As shown in FIG. 1, the silane coupling agent having an epoxy group is 0.4 parts by weight or more and 1.8 parts by weight or less, and the silane cup having an amino group with respect to 100 parts by weight of the used thermoplastic resin composition. The ring agent is 0.4 parts by weight or more and 1.8 parts by weight or less, the silane coupling agent having an isocyanate group is 1.0 part by weight or more and 1.8 parts by weight or less, and the epoxy resin is 0.2 parts by weight or more. 5.0 parts by weight or less is an effective range, that is, a range that is A in the comprehensive judgment.

As described above, with respect to 100 parts by weight of the used thermoplastic resin composition, 0.4 parts by weight or more and 1.8 parts by weight or less of the silane coupling agent having an epoxy group and the silane coupling agent having an amino group are used. 0.4 parts by weight or more and 1.8 parts by weight or less, 1.0 part by weight or more and 1.8 parts by weight or less of the silane coupling agent having an isocyanate group, or 0.2 parts by weight or more and 5.0 parts by weight of the epoxy resin. By mixing the following, a regenerated epoxy resin composition is obtained. In the method for producing a regenerated thermoplastic resin composition, a used thermoplastic resin composition and a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having an isocyanate group, or an epoxy resin are used. The process of mixing the epoxides is called a mixing process.

By the above-mentioned production method, a regenerated thermoplastic resin composition capable of suppressing the bleed-out of fatty acids and improving the appearance design can be obtained.

In the present disclosure, the inorganic filler, the antioxidant, the metal deactivating agent and the coloring pigment are added to the used thermoplastic resin composition in the mixing step. By adding the inorganic filler, the heat resistance of the regenerated thermoplastic resin composition can be improved.

Further, in the present disclosure, an example in which a polypropylene resin composition is used as the thermoplastic resin composition is shown, but a polyethylene resin composition, a polystyrene resin composition, an ABS resin composition or a polycarbonate resin composition may be used.

Further, in the present disclosure, a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having an isocyanate group, or an epoxy resin is used for a used thermoplastic resin composition. An example of mixing each of them alone is shown, but at least one of a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having an isocyanate group, and an epoxy resin is used thermoplasticity. It may be mixed with the resin composition.

Further, in the present disclosure, within the scope of the invention, the first embodiment can be appropriately modified and omitted.

Claims

For 100 parts by weight of the used thermoplastic resin composition, 0.4 parts by weight or more and 1.8 parts by weight or less of the silane coupling agent having an epoxy group, and 0.4 parts by weight of the silane coupling agent having an amino group. At least one of 1.8 parts by weight or less, 1.0 part by weight or more and 1.8 parts by weight or less of the silane coupling agent having an isocyanate group, and 0.2 parts by weight or more and 5.0 parts by weight or less of the epoxy resin. Has a mixing step of mixing,
A method for producing a regenerated thermoplastic resin composition.
The used thermoplastic resin composition is a polypropylene resin composition, a polyethylene resin composition, a polystyrene resin composition, an ABS resin composition or a polycarbonate resin composition in an amount of 80 parts by weight or more out of 100 parts by weight.
The method for producing a regenerated thermoplastic resin composition according to claim 1.
The used thermoplastic resin composition contains 20 parts by weight or less of an inorganic filler out of 100 parts by weight.
The method for producing a regenerated thermoplastic resin composition according to claim 1 or 2.
In the mixing step, more than 0 parts by weight and 5.0 parts by weight or less of the coloring pigment are further added.
The method for producing a regenerated thermoplastic resin composition according to any one of claims 1 to 3.
The following chemical formulas 1, 2 and 3

A regenerated thermoplastic resin composition comprising at least one of the above.
(In chemical formulas 1, 2 and 3,
l = 1-13,
-R 1- : Substituent represented by Chemical Formula 4,
-R 2 :-(CH 2 ) n CH 3 (any of n = 10, 12, 14, 16) or-(CH 2 ) 7 CH = CH (CH 2 ) m CH 3 (m = 5, 7) either))
The following chemical formulas 5, 6 and 7

A regenerated thermoplastic resin composition comprising at least one of the above.
(In chemical formulas 5, 6 and 7,
k = 1 to 13
-R 2 :-(CH 2 ) n CH 3 (any of n = 10, 12, 14, 16) or-(CH 2 ) 7 CH = CH (CH 2 ) m CH 3 (m = 5, 7) either))