KR20070032384A - Thermoplastic resin composition - Google Patents

Abstract

The present invention provides a thermoplastic resin composition containing a metal soap and a thermoplastic resin. The metal soap contained in such a composition is obtained by reacting a fatty acid alkali compound salt obtained by reacting a monovalent alkali compound at a ratio of 0.90 mol to 0.99 mol with respect to 1 mol of a fatty acid having 6 to 24 carbon atoms in an aqueous solution. do. The composition contains metal soap in a ratio of 0.01 parts by weight to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Such a composition is excellent in dispersibility, such as a pigment and a filler, and also the fall of the molecular weight of resin is small.

Metal soaps, thermoplastics, alkali compounds, pigments, fillers, dispersibility,

Description

Thermoplastic resin composition

The present invention relates to a thermoplastic resin composition containing a metal soap and a thermoplastic resin.

Conventionally, additives for thermoplastic resins have been used for the purpose of improving the releasability, improving the molding of the resin such as preventing fusion of the resin to the molding machine, or improving the dispersibility of the pigment or filler to the resin, for example, Compounds, amide compounds, metal soaps, silicone compounds and the like are used for the above purposes.

Among these additives, metal soaps and silicone compounds are used for the purpose of improving the dispersibility of the pigments and fillers in the resin. For example, Japanese Laid-Open Patent Publication No. 2003-155405 discloses a method for dispersing titanium oxide using polyorganosiloxane.

However, when used together with phenolic antioxidants (e.g., 3,5-di-t-butyl-4-hydroxytoluene, etc.), which are widely used in thermoplastic resins, metal soaps may yellow the resins, If it is colored or used simultaneously with a phosphorus antioxidant (for example, triphenyl phosphate etc.), there exists a problem of loss of antioxidant capability. Moreover, when metal soap is disperse | distributed when manufacturing molded articles of polyester resins, such as polyethylene terephthalate and a polycarbonate, the molecular weight of resin falls and this becomes a factor and there exists a problem that the intensity | strength of a resin molded article falls.

Also with respect to the silicone compound, there is a problem that the free silicone compound floats on the surface of the molded article obtained.

As described above, it is difficult to disperse pigments and fillers in thermoplastic resins without causing problems of coloring of antioxidants, reduction of antioxidant effects, reduction of molecular weight of resins, and floating of additives on the surface of molded articles. It was.

Disclosure of the Invention

An object of the present invention is excellent in dispersibility of pigments, fillers and the like, and even if it contains an antioxidant, the coloration of the resin resulting from yellowing of the antioxidant and a decrease in the antioxidant effect are less likely to occur. It is providing the thermoplastic resin composition with little molecular weight fall.

The thermoplastic resin composition of the present invention contains a metal soap and a thermoplastic resin, wherein the metal soap is a fatty acid obtained by reacting a monovalent alkali compound at a ratio of 0.90 mol to 0.99 mol with respect to 1 mol of a C6-C24 fatty acid. It is obtained by reacting an alkali compound salt and a divalent metal salt in an aqueous solution, and the metal soap is contained in a proportion of 0.01 parts by weight to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin.

In a preferred embodiment, the metal constituting the metal soap is calcium or magnesium.

In a preferred embodiment, such a thermoplastic resin composition is an ester compound of pentaerythritol and a monovalent saturated fatty acid having 14 to 24 carbon atoms (hereinafter sometimes referred to as a pentaerythritol ester compound) based on 100 parts by weight of the thermoplastic resin. It is contained in a ratio of 0.001 to 5 parts by weight.

In a preferred embodiment, the acid value of the ester compound is 5.0 or less, and the hydroxyl value is 20.0 or less.

In a preferred embodiment, the thermoplastic resin is a polyester resin.

The thermoplastic resin composition of this invention containing a metal soap and a thermoplastic resin is excellent in dispersibility, such as a pigment and a filler, and also the molecular weight fall of resin hardly arises. Even in the case of containing the antioxidant in the thermoplastic resin composition of the present invention, the antioxidant effect is not suppressed, and in particular, when the phenolic antioxidant is contained, it is difficult to cause coloring in the resin as compared with the conventional thermoplastic resin composition. . In the case where the thermoplastic resin composition further contains a pentaerythritol ester compound, the lubricity is increased when heat-melting the mixture containing each component of the composition.

Best Mode for Carrying Out the Invention

The thermoplastic resin composition of this invention contains a metal soap and a thermoplastic resin, and contains pentaerythritol ester compound, an additive, etc. as needed. Hereinafter, these are demonstrated sequentially.

(1) metal soap

Metal soaps used in the present invention are prepared by a metathesis method in which a fatty acid alkali compound salt is reacted with a divalent metal salt. The metal soap is obtained by reacting a fatty acid alkali compound salt obtained by reacting a monovalent alkali compound at a ratio of 0.90 mol to 0.99 mol with respect to 1 mol of a fatty acid having 6 to 24 carbon atoms in an aqueous solution. There is this.

The fatty acid as a raw material of the fatty acid alkali compound salt is not particularly limited as long as it is a fatty acid having 6 to 24 carbon atoms. That is, it may be any one of natural fatty acids and synthetic fatty acids, any one of saturated fatty acids and unsaturated fatty acids, and may be either linear or branched. In addition, a hydroxyl group, an aldehyde group, an epoxy group, and the like may be contained in the structure of the fatty acid. Preferably, they are C10-C22 straight chain fatty acid. When the carbon number is less than 6, the effect as a dispersant of the obtained metal soap is not obtained, and fatty acids having more than 24 carbon atoms are difficult to obtain industrially. These fatty acids can be used independently and can be used in combination of 2 or more type.

As fatty acids, for example, caproic acid, caprylic acid, capric acid, oleic acid, myristic acid, myristic oleic acid, palmitic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, aramic acid, bebe Henic acid, erucic acid, hydroxystearic acid, montanic acid, isostearic acid, 2-ethylhexanoic acid and epoxystearic acid.

Examples of the monovalent alkali compound as a raw material of the fatty acid alkali compound salt include hydroxides of alkali metals (sodium and potassium) and amines such as ammonia, monoethanolamine, diethanolamine, and triethanolamine. When it is a fatty acid alkali compound salt, since it has high solubility in water, Preferably it is hydroxide of alkali metals, such as sodium and potassium.

The fatty acid alkali compound salt may be obtained by reacting a fatty acid with a monovalent alkali compound at a ratio of 0.90 mol to 0.99 mol, preferably 0.95 mol to 0.98 mol, with respect to 1 mol of fatty acids. When a metal soap is prepared using a fatty acid alkali compound salt obtained by reacting a monovalent alkali compound with less than 0.90 mole or more than 0.99 mole per 1 mole of fatty acid, and the resin is molded using this metal soap. There is a fear that a desired resin molded article may not be obtained. In particular, metal soaps are prepared using fatty acid alkali compound salts obtained by reacting monohydric alkali compounds in an amount of more than 0.99 moles with respect to 1 mole of fatty acids, and these metal soaps are added to a thermoplastic resin and molded to form a resin. When the molecular weight is lowered or when the thermoplastic resin composition contains an antioxidant, the antioxidant effect is lowered or a defect occurs that the resin is colored.

The fatty acid alkali compound salt used in the present invention is a monovalent alkali compound and a fatty acid at the above-mentioned ratio, and are generally at or above the melting point of the fatty acid, and the temperature at which the fatty acid is not decomposed, preferably 100 ° C. or lower, and more preferably It is obtained by making it react at 50 degreeC-100 degreeC, More preferably, 80 degreeC-95 degreeC.

The metal soap used in the present invention is obtained by reacting a fatty acid alkali compound salt and a divalent metal salt in an aqueous solution. The divalent metal salt is specifically a salt of a divalent inorganic metal with an inorganic acid or an organic acid. Examples of the divalent inorganic metal include alkaline earth metals such as magnesium, calcium, and barium, titanium, zinc, iron, manganese, cadmium, mercury, zirconium, lead, copper, cobalt, and nickel. Among them, calcium, magnesium, barium and zinc are preferable because they are less colored and decomposed by heating and can be easily obtained industrially. Particular preference is given to calcium or magnesium in terms of pigment dispersibility.

As a divalent metal salt, calcium chloride, calcium acetate, magnesium chloride, magnesium sulfate, copper sulfate, barium chloride, zinc chloride, zinc sulfate etc. are mentioned, for example. In particular, chlorides, sulfates and nitrates such as calcium and magnesium are preferable in terms of good solubility in water and efficient reaction with carboxylates.

Specifically, the reaction is carried out by separately preparing a divalent metal salt-containing aqueous solution and a fatty acid alkali compound salt-containing aqueous solution and mixing them. For example, it is performed by dropwise addition of an aqueous fatty acid alkali compound salt-containing aqueous solution into a divalent metal salt-containing aqueous solution in which a divalent metal salt-containing aqueous solution is added dropwise into an aqueous fatty acid alkali compound salt-containing aqueous solution or simultaneously added dropwise to the reactor.

The concentration of the fatty acid alkali compound salt in the production of the metal soap is usually 1% to 20% by weight, preferably 5 in terms of productivity of the metal soap and handling properties of the aqueous solution containing the fatty acid alkali compound salt or the resulting metal soap slurry. Wt% to 15 wt%. When the fatty acid alkali compound salt concentration is less than 1% by weight, the productivity of the metal soap is low, which is not practically preferable. When it exceeds 20 weight%, since the viscosity of a fatty acid alkali compound salt containing aqueous solution or the obtained metal soap slurry rises, it will become difficult to perform a uniform reaction. Further, the concentration of the divalent metal salt in the divalent metal salt-containing liquid is usually 1% by weight to 50% by weight, in terms of productivity of the metal soap and handling properties of the aqueous solution containing a fatty acid alkali compound salt or the obtained metal soap slurry. Preferably from 10% to 40% by weight.

The reaction of the fatty acid alkali compound salt and the divalent metal salt is preferably carried out in a ratio of 0.45 mol to 0.7 mol with respect to 1 mol of the monovalent alkali compound used to obtain the fatty acid alkali compound salt. The more preferable ratio of divalent metal salt is 0.49 to 0.6 mol, and still more preferably 0.49 to 0.55 mol. When the divalent metal salt deviates from the range of 0.45 mol to 0.7 mol, when the obtained metal soap is added to the thermoplastic resin and molded, there is a fear that the molecular weight of the obtained resin may be lowered, and when the antioxidant is contained, the oxidation is prevented. There exists a possibility that the effect may fall or the defect which a resin colors may generate | occur | produce.

The reaction of the fatty acid alkali compound salt and the divalent metal salt is carried out under temperature conditions usually performed by those skilled in the art in consideration of the solubility of the fatty acid alkali compound salt. Preferably it is 50-100 degreeC, More preferably, it is 70-95 degreeC.

According to the method a metal soap slurry is obtained. The metal soap slurry is separated as it is, or the solvent is separated by a centrifugal dehydrator, a filter press, a vacuum rotary filter, or the like, and washed as necessary to remove the by-product inorganic salt, followed by a rotary drying apparatus, an airflow drying apparatus, and a ventilation type. It is dried by a drying device, a spray drying device, a fluidized bed drying device or the like. The drying method can be either continuous or batch, or under atmospheric pressure or vacuum. In the same manner, the metal soap of the present invention can be obtained.

The pH at which the metal soap thus obtained is dispersed in water at a concentration of 2% by weight is in the range of 5.0 to 7.5. The obtained metal soap can be used alone, and metal soaps containing other metals can be mixed and used.

(2) thermoplastic resin

The thermoplastic resin used in the present invention is not particularly limited, and examples thereof include the following resins: chlorine-containing resins such as polyvinyl chloride, chlorinated polyvinyl chloride, chlorinated polyethylene, and vinyl chloride / vinyl acetate copolymers; Polymer blends of the chlorine-containing resins with other resins; Polyolefin resins such as low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, polymer blends of polyolefin resins, polymer blends of polyolefin resins and other resins, and the monomers (α-olefins) constituting these resins with other monomers coalescence; Polyamide resins, polymer blends of a plurality of polyamide resins, polymer blends of polyamide resins with other resins, and copolymers of monomers constituting the polyamide resin with other monomers; Polyester resins such as polycarbonate resins and polyethylene terephthalate resins, polymer blends of plural polyester resins, polymer blends of polyester resins and other resins, and copolymers of monomers constituting polyester resins with other monomers; ABS resins, polymer blends of a plurality of ABS resins, polymer blends of ABS resins with other resins, and copolymers of monomers constituting the ABS resin with other monomers; A polyacetal resin, a polymer blend of a plurality of polyacetal resins, a polymer blend of a polyacetal resin and another resin, and a copolymer of monomers and other monomers constituting the polyacetal resin. Among these, polyester resins, polymer blends of a plurality of polyester resins, polymer blends of polyester resins and other resins, and copolymers of monomers constituting the polyester resins with other monomers are preferable, and polyester resins are more preferred. desirable.

(3) pentaerythritol ester compound

The thermoplastic resin composition of this invention contains a pentaerythritol ester compound as needed. Such pentaerythritol ester compounds are esters of pentaerythritol and monovalent saturated fatty acids having 14 to 24 carbon atoms. By containing such an ester compound, the lubricity with a processing machine or a metal mold | die improves at the time of processing. The acid value of such an ester compound becomes like this. Preferably it is 5.0 or less, More preferably, it is 3.0 or less, The hydroxyl value becomes like this. Preferably it is 20.0 or less, More preferably, it is 15.0 or less. When the acid value exceeds 5.0 or when the hydroxyl value exceeds 20.0, the obtained thermoplastic resin composition may be colored or cause a decrease in strength.

(4) additive

As an additive contained as needed in the thermoplastic resin composition of this invention, the following compound or material is mentioned, for example: fillers, such as talc, mica, calcium carbonate, potassium titanate, calcium silicate; Inorganic pigments such as titanium oxide, carbon black, iron oxide, and ultramarine; Organic pigments such as phthalocyanine compounds, quinacridone compounds, anthraquinone compounds, and pyrrole compounds; Antioxidants such as phenol compounds, phosphite compounds, hindered phenol compounds, phosphite ester compounds, phosphate ester compounds and amine compounds; Light stabilizers such as hindered amine compounds; External lubricants such as aliphatic fatty acid ester compounds other than pentaerythritol ester compounds, paraffinic compounds and organic fatty acids; Flame retardants; Mold release agents; Antistatic agent, etc.

(5) thermoplastic resin composition

The thermoplastic resin composition of the present invention contains a metal soap and a thermoplastic resin as described above, and may contain a pentaerythritol ester compound and other additives as necessary.

Metal soap is contained in the ratio of 0.01-10 weight part, Preferably it is 0.1-5 weight part with respect to 100 weight part of thermoplastic resins. When the content ratio of the metal soap is less than 0.01 part by weight, sufficient pigment dispersion cannot be exhibited. When it exceeds 10 parts by weight, the metal soap floats on the resin surface, causing a decrease in appearance. The content of the pentaerythritol ester compound is not particularly limited. Preferably, the pentaerythritol ester compound is contained in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin. When content of an ester compound is less than 0.001 weight part, the lubricity of the obtained thermoplastic resin composition is inadequate, and the adhesion to a processing machine and the external appearance of a molded article may arise. When it exceeds 5 parts by weight, the ester compound may float on the surface of the resin, resulting in poor appearance and a decrease in strength. In addition, the metal soap used in the present invention hardly colors the ester compound.

Each component of the thermoplastic resin composition, i.e. the thermoplastic resin, the metal soap and the additives contained as necessary, are kneading methods commonly used by those skilled in the art such as ribbon blenders, Henschel mixers, Banbury mixers, drum tumblers, single screw extruders, It is kneaded by a twin screw extruder, a kneader, a multi screw extruder, or the like. Subsequently, it may be molded by a molding method commonly used by those skilled in the art, for example, injection molding, compression molding, calender molding, rotational molding, and the like, and may be used in various molded articles, for example, in the automobile field and OA parts field. It is used for manufacture.

An Example is given to the following and this invention is demonstrated in detail.

(Manufacture example 1: manufacture of metal soap)

250 g of mixed fatty acid (2.5% by weight of myritic acid, 30.0% by weight of palmitic acid, 66.4% by weight of stearic acid, 0.8% by weight of arachnic acid and 0.3% by weight of behenic acid) in a 3L glass separate flask 0.90 mol) and 2500 g of water are added, and it heats up to 90 degreeC. Subsequently, 72.5 g (0.87 mol) of 48% aqueous sodium hydroxide solution was added, and the mixture was stirred at the same temperature (90 ° C) for 1 hour. Subsequently, while maintaining at 90 degreeC, 221g (0.46 mol) of 25% magnesium sulfate aqueous solution is added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 90 ° C for 1 hour. 1500 g of water is added to the obtained mixed fatty acid magnesium slurry, and it cools to 65 degrees C or less. It is then filtered through a suction filter, washed twice with 1000 g of water, and dried at 65 ° C. for 48 hours using a blow dryer to obtain a metal soap.

The free fatty acid content, metal content, melting point, moisture, and pH of the obtained metal soap are analyzed by the following method. The results are shown in Table 1.

(1) free fatty acids

5 g of metal soap is precisely taken into a beaker, 50 ml of diethyl ether / ethanol mixed solvent is added, and left to stir for 30 minutes after stirring. Subsequently, the mixture is filtered using 5B filter paper, the filtrate is titrated with 1 / 10N potassium hydroxide ethanol solution, and the amount of free fatty acid is calculated according to the following general formula. In the following general formula, MW is the molecular weight of a fatty acid, A is the addition amount of potassium hydroxide titrant, and f shows the factor of potassium hydroxide titrant.

Free fatty acid (%) = MW x A (ml) x f / 100

(2) metal content

0.1 g of metal soap is precisely weighed and heated in pottery crucible at 650 ° C. for 4 hours to remove organics. 1 ml of hydrochloric acid is added to the residue to dissolve, and water is added to make 100 ml. Using this solution as a sample, the metal content is measured by atomic absorption photometry.

(3) melting point

It measures by the method of JIS-K0064.

(4) moisture

It measures by the method of JIS-K0067. Drying is performed at 105 ° C using 2 g of metal soap as a sample.

(5) pH

An aqueous dispersion containing 2% by weight of metal soap was prepared using an aqueous solution containing 0.2% by weight of nonionic surfactant (Nonion NS-210, manufactured by Nippon Oil Chemical Co., Ltd.), and the pH was measured at 25 ° C. do.

Preparation Example 2: Preparation of Metal Soap

250 g (0.90 mol) of mixed fatty acids and 2500 g of water of the manufacture example 1 were thrown into a 3 L glass separation flask, and it heated up to 90 degreeC. Next, 73 g (0.87 mol) of 48% aqueous sodium hydroxide solution was added, and the mixture was stirred at the same temperature (90 ° C.) for 1 hour. Subsequently, 291 g (0.45 mol) of 25% zinc sulfate aqueous solution was added dropwise over 1 hour while maintaining at 90 ° C. The obtained mixed fatty acid zinc slurry was filtered with a suction filter, washed three times with 1000 g of water, and dried at 80 ° C. for 30 hours using a blow dryer to obtain a metal soap. The free fatty acid content, the metal content, the melting point, the moisture, and the pH of the obtained metal soap were analyzed in the same manner as in Production Example 1. The results are shown in Table 1.

(Manufacture example 3: manufacture of metal soap)

250 g (1.25 mol) of lauric acid and 2500 g of water are thrown into a 5 L glass separation flask, and it heats up to 90 degreeC. Subsequently, 99 g (1.19 mol) of 48% aqueous sodium hydroxide solution was added, and the mixture was stirred at the same temperature (90 ° C.) for 1 hour. Next, it heats up to 95 degreeC. While maintaining at 95 ° C., 200 g (0.63 mol) of 35% calcium chloride aqueous solution was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 95 ° C for 1 hour. The obtained calcium laurate slurry is cooled to 60 ° C. or lower while stirring. Subsequently, the filter was filtered using a table-type filter press having a volume of 75 cm ³ , washed three times with 100 g of water, and dried at 70 ° C. for 48 hours using a blow dryer to obtain a metal soap. The free fatty acid content, the metal content, the melting point, the moisture, and the pH of the obtained metal soap were analyzed in the same manner as in Production Example 1. The results are shown in Table 1.

(Manufacture example 4: manufacture of metal soap)

250 g (0.90 mol) of mixed fatty acids and 2500 g of water of the manufacture example 1 were thrown into a 5 L glass separation flask, and it heated up to 90 degreeC. Subsequently, 71.7 g (0.86 mol) of 48% aqueous sodium hydroxide solution is added, and the mixture is stirred at the same temperature (90 ° C) for 1 hour. Subsequently, 917 g (0.44 mol) of 10% aqueous barium chloride solution is added dropwise over 1 hour while maintaining at 90 ° C. After completion of the dropwise addition, the mixture was stirred at 90 ° C for 1 hour. The obtained mixed fatty acid barium slurry was filtered with a suction filter, washed three times with 1000 g of water, and dried at 80 ° C. for 30 hours using a blow dryer to obtain a metal soap. The free fatty acid content, the metal content, the melting point, the moisture, and the pH of the obtained metal soap were analyzed in the same manner as in Production Example 1. The results are shown in Table 1.

(Manufacture example 5: manufacture of metal soap)

250 g (0.90 mol) of mixed fatty acids and 2500 g of water of the manufacture example 1 were thrown into a 5 L glass separation flask, and it heated up to 90 degreeC. Next, 73 g (0.87 mol) of 48% aqueous sodium hydroxide solution was added, and the mixture was stirred at the same temperature (90 ° C.) for 1 hour. Subsequently, while maintaining at 90 degreeC, 146g (0.46 mol) of 35% calcium chloride aqueous solution is added dropwise over 1 hour. After completion of the dropwise addition, the mixture is further stirred at 90 ° C. for 1 hour. 1500 g of water is added to the obtained slurry, and it cools to 65 degrees C or less. It is then filtered through a suction filter, washed twice with 1000 g of water, and dried at 65 ° C. for 48 hours using a blow dryer to obtain a metal soap. The free fatty acid content, the metal content, the melting point, the moisture, and the pH of the obtained metal soap were analyzed in the same manner as in Production Example 1. The results are shown in Table 1.

Comparative Example 1

250 g (0.90 mol) of mixed fatty acids and 2500 g of water of the manufacture example 1 were thrown into a 5 L glass separation flask, and it heated up to 90 degreeC. Next, 77 g (0.92 mol) of 48% aqueous sodium hydroxide solution is added, and the mixture is stirred at the same temperature (90 ° C) for 1 hour. Subsequently, 355 g (0.55 mol) of 25% zinc sulfate aqueous solution was added dropwise over 1 hour while maintaining at 90 ° C. After completion of the dropwise addition, the mixture is further stirred at 90 ° C. for 1 hour. The obtained mixed fatty acid zinc slurry is filtered with a suction filter, washed three times with 1000 g of water, and dried at 80 ° C. for 30 hours using a blow dryer to obtain a metal soap. The free fatty acid content, the metal content, the melting point, the moisture, and the pH of the obtained metal soap were analyzed in the same manner as in Production Example 1. The results are shown in Table 1.

(Comparative Production Example 2)

250 g (0.90 mol) of mixed fatty acids and 2500 g of water of the manufacture example 1 were thrown into a 5 L glass separation flask, and it heated up to 90 degreeC. Next, 77 g (0.92 mol) of 48% aqueous sodium hydroxide solution is added, and the mixture is stirred at the same temperature (90 ° C) for 1 hour. Subsequently, while maintaining at 90 degreeC, 221g (0.46 mol) of 25% magnesium sulfate aqueous solution is added dropwise over 1 hour. After completion of the dropwise addition, the mixture is further stirred at 90 ° C. for 1 hour. 1500 g of water is added to the obtained slurry, and it cools to 65 degrees C or less. It is then filtered through a suction filter, washed twice with 1000 g of water, and dried at 65 ° C. for 48 hours using a blow dryer to obtain a metal soap. The free fatty acid content, the metal content, the melting point, the moisture, and the pH of the obtained metal soap were analyzed in the same manner as in Production Example 1. The results are shown in Table 1.

(Comparative Production Example 3)

250 g (0.90 mol) of mixed fatty acids and 2500 g of water of the manufacture example 1 were thrown into a 5 L glass separation flask, and it heated up to 90 degreeC. Next, 77 g (0.92 mol) of 48% aqueous sodium hydroxide solution is added, and the mixture is stirred at the same temperature (90 ° C) for 1 hour. Subsequently, 152 g (0.46 mol) of 35% calcium chloride aqueous solution was added dropwise over 1 hour while maintaining at 90 ° C. After completion of the dropwise addition, the mixture is further stirred at 90 ° C. for 1 hour. 1500 g of water is added to the obtained slurry, and it cools to 65 degrees C or less. It is then filtered through a suction filter, washed twice with 1000 g of water, and dried at 65 ° C. for 48 hours using a blow dryer to obtain a metal soap. The free fatty acid content, the metal content, the melting point, the moisture, and the pH of the obtained metal soap were analyzed in the same manner as in Production Example 1. The results are shown in Table 1.

Raw Fatty Acid Alkali Compound Salts Metal soap Measurement result Carbon number of fatty acids Alkali / Sulfonic Acid ^{* 1} (molar ratio) Free fatty acid content (%) Metal content (%) Melting point (℃) moisture (%) pH Production Example One 18 0.97 Mixed Fatty Acid Magnesium 1.2 4.1 122 5.7 6.7 2 18 0.98 Mixed fatty acid zinc 0.2 10.3 122 0.1 7.2 3 12 0.95 Calcium laurate 3.5 8.6 155 3.9 6.6 4 18 0.96 Mixed fatty acid barium 2.5 20.3 ≥200 0.2 6.8 5 18 0.97 Mixed fatty acid calcium 0.8 6.6 153 2.7 6.9 Comparative Production Example One 18 1.02 Mixed fatty acid zinc 0.2 10.4 122 0.1 7.7 2 18 1.02 Mixed Fatty Acid Magnesium 0.3 4.2 122 5.7 9.6 3 18 1.02 Mixed fatty acid calcium 0.1 6.8 155 2.7 9.8

 * 1 ‥‥ 1 molar ratio of the alkali compound and fatty acid

(Examples 1 to 5 and Comparative Examples 1 to 4: Preparation and Evaluation of Thermoplastic Resin Composition)

1 part by weight of each metal soap obtained in Production Examples 1 to 5 and Comparative Production Examples 1 to 3, 100 parts by weight of polycarbonate resin pellets (Yupiron manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and titanium oxide (Taipek, Ishihara Sangyo Co., Ltd.) 10 parts by weight and 1 part by weight of carbon black (Toka Carbon, manufactured by Tokai Carbon Co., Ltd.) are mixed with a drum tumbler. Subsequently, using a twin-screw extruder having an internal diameter of 20 mm, the melt kneading is extruded at 280 ° C. and pelletized by a pelletizer. After the obtained pellets were sufficiently dried, injection molding was carried out using a vertical injection molding machine at a molding temperature of 280 ° C. and a mold temperature of 9 ° C., and a polycarbonate piece of 70 mm × 70 mm × 2 mm was prepared (these are manufactured examples 1 to 5 and In the order of Comparative Production Examples 1 to 3, test specimens 1 to 8 are used respectively). In addition, except that it does not contain a metal soap, it pelletizes similarly to the above, and prepares a polycarbonate piece (test piece 9). The number average molecular weights of the obtained test specimens 1 to 9 were measured using gel permeation chromatography (GPC, manufactured by Tosoh Corp.), and the appearance and impact strength were evaluated as follows. The results are shown in Table 2.

(1) Appearance (with or without color nonuniformity)

Visually check the specimen for the occurrence of color non-uniformity. The thing which color nonuniformity is not seen at all and the thing which color nonuniformity is seen in the vicinity of an ejection opening are (triangle | delta) and the thing which color nonuniformity is seen as a whole is made into x.

(2) impact strength

The test piece obtained by injection molding is cut | disconnected, the test piece for the notched Izod test is produced, and the impact strength is measured.

Raw material Thermoplastic resin composition Test result Metal soap (A) (name) Thermoplastic resin (B) ^{* 1} A / B ^{* 2} (weight ratio) Average molecular weight (Mn) of PC ^{* 1} Exterior Impact strength Example One Preparation Example 1 (Mixed Fatty Acid Magnesium) PC 1/100 Test piece 1 32600 O 48 2 Preparation Example 2 (Mixed Fatty Acid Zinc) PC 1/100 Test piece 2 31500 △ 50 3 Preparation Example 3 (Calcium Laurate) PC 1/100 Test piece 3 32400 O 45 4 Preparation Example 4 (mixed fatty acid barium) PC 1/100 Test piece 4 33100 △ 51 5 Preparation Example 5 (mixed fatty acid calcium) PC 1/100 Test piece 5 31800 O 46 Comparative example One Comparative Production Example 1 (mixed fatty acid zinc) PC 1/100 Test piece 6 25100 △ 25 2 Comparative Production Example 2 (mixed fatty acid magnesium) PC 1/100 Test piece 7 22300 O 12 3 Comparative Production Example 3 (mixed fatty acid calcium) PC 1/100 Test piece 8 19500 O 8 4 unused PC 1/100 Test piece 9 34000 × 52

* 1: PC: polycarbonate

* 2 ... metal soap / thermoplastic (weight ratio)

From the result of Table 2, the test piece containing the metal soap of a manufacture example (test pieces 1-5) is compared with the test piece containing the metal soap of comparative manufacture examples 1-3 (test pieces 6-8), and the average molecular weight of polycarbonate There is little fall of and there is little fall of impact strength. In addition, Test Piece 9 (Comparative Example 4) containing no metal soap showed a color unevenness as a whole, and was very inferior in appearance.

(Examples 6-10 and Comparative Examples 5-7: Deterioration prevention effect by combined use with a phenolic antioxidant)

1 part by weight of each metal soap obtained in Production Examples 1 to 5 and Comparative Production Examples 1 to 3, 100 parts by weight of polypropylene pellet (Mitsui Polypro, manufactured by Mitsui Chemical Co., Ltd.), and butyl hydroxytoluene (BK) 0.1 parts by weight of Yoshinox, manufactured by Apica Corporation, is stirred at 180 ° C. for 5 minutes using a Labo Plasto mill (manufactured by Toyo Seiki Seisakusho). Subsequently, it press-forms and prepares the polypropylene test piece of width 200mm, length 200mm, and thickness 2mm (these are set to test pieces 10-17, respectively, in order of manufacture example 1-5 and comparative manufacture examples 1-3). Subsequently, these test pieces are put into a blow dryer, they are stored at 60 degreeC for 10 days, and the coloring (yellowing of resin) after storage is evaluated. Evaluation is made with the naked eye and the thing which coloration is not seen at all and the thing which coloration is confirmed are x. The results are shown in Table 3.

Raw material Thermoplastic resin composition Test result Metal soap (A) (name) Thermoplastic resin (B) ^{* 1} A / B ^{* 2} (weight ratio) Yellowing of the resin Example 6 Preparation Example 1 (Mixed Fatty Acid Magnesium) PP 1/100 Test piece 10 O 7 Preparation Example 2 (Mixed Fatty Acid Zinc) PP 1/100 Test piece 11 O 8 Preparation Example 3 (Calcium Laurate) PP 1/100 Test piece 12 O 9 Preparation Example 4 (mixed fatty acid barium) PP 1/100 Test piece 13 O 10 Preparation Example 5 (mixed fatty acid calcium) PP 1/100 Test piece 14 O Comparative example 5 Comparative Production Example 1 (mixed fatty acid zinc) PP 1/100 Test piece 15 × 6 Comparative Production Example 2 (mixed fatty acid magnesium) PP 1/100 Test piece 16 × 7 Comparative Production Example 3 (mixed fatty acid calcium) PP 1/100 Test piece 17 ×

PP: Polypropylene (Pellets)

* 2 ... metal soap / thermoplastic (weight ratio)

From the result of Table 3, yellowing is not seen at all in the test piece (test pieces 10-14) using the metal soap of a manufacture example. In contrast, all of the test pieces (test pieces 15 to 17) using the metal soaps of Comparative Production Examples 1 to 3 are colored yellow.

(Reference Example: Coloration of Pentaerythritol Ester Compound with Metal Soap)

5 g of a metal soap (mixed fatty acid magnesium) obtained in Production Example 1, and 5 g of pentaerythritol stearic acid ester (manufactured by Nippon Oil Chemical Co., Ltd., Unistar H-476, acid value 2.5, hydroxyl value 14.0) in a plastic bag Shake in and mix. This mixture is transferred to an aluminum cup of 6 cm diameter and heated in a blow dryer at 200 ° C. for 60 minutes. After cooling, the surface color of the mixture was determined by using a colorimetric colorimeter ZE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS Z-8722 to determine the values of X, Y and Z. Find the yellowness (YI) by the general formula:

Yellowness (YI) = 100 (1.28X-1.06Z) / Y

The results are shown in Table 4.

The yellowness was determined in the same manner as above except that the metal soap (mixed fatty acid magnesium) obtained in Comparative Preparation Example 2 was used instead of the metal soap obtained in Preparation Example 1. The result is combined with Table 4 and described.

Yellowness (YI) when alone Yellowness (YI) after ester mixing Metal soap of Preparation Example 1 (mixed fatty acid magnesium) 17.1 5.9 Metal soap of Comparative Production Example 2 (mixed fatty acid magnesium) 18.2 35.5 Pentaerythritol stearic acid ester -4.9 ---

As apparent from Table 4, when the metal soap of Preparation Example 1 and the pentaerythritol stearic acid ester were mixed and heated, the yellowness was compared with the case where the metal soap and the ester of Comparative Preparation Example 2 were mixed and heated. YI) is low. Since the yellowness of the metal soap of the manufacture example 1 and the metal soap of the comparative example 2 does not have a big difference before mixing, the metal soap used for this invention colors a pentaerythritol ester compound compared with another metal soap. I found it difficult to let.

(Examples 11 to 12 and Comparative Example 8: Coloring prevention effect and surface gloss effect)

Metal soaps, titanium oxide (Ishihara Sangyo, Taipek), polycarbonate resin pellets (manufactured by Mitsubishi Engineering Plastics Co., Ltd., Eupyron) obtained in Production Example 1 and Comparative Production Example 2, and pentaerythrates used in Reference Examples. Lithol stearic acid ester is mixed using the drum tumbler in the ratio of Table 5. Next, melt-kneading extrusion is performed at 280 degreeC using the twin screw extruder of internal diameter 20mm, and it pelletizes with a pelletizer. After the obtained pellets were sufficiently dried, injection molding was carried out at a molding temperature of 280 ° C and a mold temperature of 90 ° C using a vertical injection molding machine, and a polycarbonate test piece of 70 mm x 70 mm x 2 mm was prepared (these were each test piece 18 to 18). 20). About these test pieces 18-20, the coloring and surface gloss of resin are evaluated as follows. The results are shown in Table 5.

(1) coloring of resin

Measure the yellowness (YI) using a color computer for the specimen. If the value of YI is 10.0 or less, there is no substantial coloring, and when it exceeds 10.0, it is judged that there is significant coloring.

(2) surface gloss

The surface of the test piece is visually observed, 0 when the surface is uniformly glossy, Δ when a part of the surface is lost, and x when no surface is visible at all.

Raw material Thermoplastic resin composition Test result Metal soap Polycarbonate Resin Pellets (parts by weight) Titanium oxide (parts by weight) Ester ^{* 1} (part by weight) Metal soap (name) Parts by weight Yellow Degree (YI) Surface polished Example 11 Preparation Example 1 (Mixed Fatty Acid Magnesium) 0.1 100 1.0 0.1 Test piece 18 8.9 O 12 Preparation Example 1 (Mixed Fatty Acid Magnesium) 0.1 100 1.0 - Test piece 19 8.4 △ Comparative example 8 Comparative Production Example 2 (mixed fatty acid magnesium) 0.1 100 1.0 0.1 Test piece 20 16.4 O

Pentaerythritol stearic acid ester

From the results in Table 5, it was found that Test Piece 18 containing the metal soap and Pentaerythritol ester compound of Preparation Example 1 and Test Piece 19 containing only the metal soap of Preparation Example 1 had almost no coloring. Moreover, since the test piece 18 contains the ester compound, it is also excellent in the surface glossiness. On the other hand, it turned out that the test piece 20 containing the metal soap and pentaerythritol ester compound of the comparative manufacture example 2 turned yellow.

The thermoplastic resin composition of this invention is excellent in the dispersibility of a pigment, a filler, etc., and it is hard to produce the fall of the molecular weight of resin. Moreover, also when antioxidant is contained in the thermoplastic resin composition of this invention, an antioxidant effect is not suppressed. In particular, when it contains a phenolic antioxidant, compared with the thermoplastic resin composition containing the conventional metal soap, since a phenolic antioxidant is hard to decompose, coloring is hard to occur in resin. Therefore, a phenolic antioxidant can be contained stably in a resin composition. Moreover, when it contains a pentaerythritol ester compound, lubricity improves at the time of processing. Moreover, even when a pentaerythritol ester compound is contained, coloring of resin by coloring of the said ester compound hardly arises. The thermoplastic resin composition of the present invention is used, for example, in the automobile field, the OA parts field, or the like.

Claims (5)

A thermoplastic resin composition containing a metal soap and a thermoplastic resin, The metal soap is obtained by reacting a fatty acid alkali compound salt and a divalent metal salt obtained by reacting a monovalent alkali compound at a ratio of 0.90 mol to 0.99 mol with respect to 1 mol of fatty acids having 6 to 24 carbon atoms in an aqueous solution, A thermoplastic resin composition, wherein the metal soap is contained in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin. The thermoplastic resin composition according to claim 1, wherein the metal constituting the metal soap is calcium or magnesium. The thermoplastic resin composition according to claim 1 or 2, further comprising an ester compound of pentaerythritol and a monovalent saturated fatty acid having 14 to 24 carbon atoms in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin. The thermoplastic resin composition of Claim 3 whose acid value of an ester compound is 5.0 or less and hydroxyl value is 20.0 or less. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the thermoplastic resin is a polyester resin.