JP2023026250A - Flow improver, thermoplastic resin composition, and molding - Google Patents

Abstract

To provide: a flow improver which in a small amount added can improve melt flowability of a thermoplastic resin without deteriorating impact resistance or causing bloom of an additive; a thermoplastic resin composition containing the flow improver; and a molding based on the thermoplastic resin composition.SOLUTION: A flow improver contains a dialkyl acid phosphate (B), and optionally contains a monoalkyl acid phosphate (A), where the (A) component is a compound represented by a general formula (1) in the figure, the (B) component is a compound represented by a general formula (2) in the figure, and a content ratio between the (A) and (B) components is between 0:100 and 30:70 in a mass ratio. (In the formulas, R1 to R3 are C14-C40 alkyl groups.)SELECTED DRAWING: None

Description

The present invention provides a fluidity improver for improving the melt fluidity of a thermoplastic resin, a thermoplastic resin composition containing this fluidity improver (hereinafter also simply referred to as "resin composition"), and this The present invention relates to a molded article using a thermoplastic resin composition.

Thermoplastic resins, especially engineering plastics represented by condensation polymers such as polycarbonate resins and polyester resins, are excellent in heat resistance and mechanical properties. It is widely used as a building material. However, when manufacturing parts from these engineering plastics, it is necessary to carry out molding processes at high temperatures, and the heat applied during that process causes thermo-oxidative deterioration of the plastics, resulting in a decrease in molecular weight and mechanical properties. Are known.

On the other hand, it has been proposed to add a fluidity improver to the thermoplastic resin. A fluidity improver is an additive that improves the melt fluidity of a thermoplastic resin, and is an additive that makes it possible to obtain the high fluidity originally brought about by high-temperature molding even at a relatively low temperature. As a result, molding can be performed at a lower temperature than before, which is useful for suppressing thermal oxidation deterioration and reducing energy costs.

For example, Patent Document 1 proposes blending a copolymer of styrene and phenyl methacrylate as a fluidity improver into a polycarbonate resin. Patent Document 2 proposes blending a blend of a polyester resin and a polycarbonate resin with a compound having lignin and/or a phosphonium sulfonate group as a fluidity improving additive.

Further, Patent Documents 3 and 4 disclose examples of blending a mixture of monostearyl acid phosphate and distearyl acid phosphate into a thermoplastic resin such as polycarbonate for the purpose of improving the thermal stability and chemical resistance of the resin composition. Are listed.

JP 2009-120789 A Japanese Patent Publication No. 2004-515629 JP 2020-026449 A JP 2020-172635 A

However, in the technique described in Patent Document 1, in order to obtain good fluidity, 5 parts by mass or more of the fluidity improver is blended with 100 parts by mass of the thermoplastic resin, which is disadvantageous in terms of production cost. is. In addition, the technique described in Patent Document 2 has a problem that the lignin is discolored by the influence of light and oxygen, and a problem that the strong acidity of the sulfonate makes the ester bond and carbonate bond of the resin susceptible to hydrolysis.

On the other hand, Patent Documents 3 and 4 do not describe the melt fluidity of the resin, and do not describe or suggest the effect of the content ratio of monostearyl acid phosphate and distearyl acid phosphate on the melt fluidity of the resin.

In addition, it is generally known that when additives are added to resins to improve fluidity, problems such as deterioration of mechanical properties such as impact resistance and blooming of additives in molded products occur. There has been a desire for a flow improver that does not cause the problem of

Therefore, the object of the present invention is to provide a fluidity improver capable of improving the melt fluidity of a thermoplastic resin in a low addition amount without causing a decrease in impact resistance or blooming of the additive. An object of the present invention is to provide a thermoplastic resin composition containing an agent and a molded article using this thermoplastic resin composition.

As a result of intensive studies, the present inventors have found that by blending a fluidity improver containing a specific alkyl acid phosphate into a thermoplastic resin, it is possible to reduce the impact resistance and prevent additive bloom. The inventors have found that the melt fluidity of thermoplastic resins can be improved by increasing the amount thereof, and have completed the present invention.

According to the present invention, the fluidity improver contains a dialkyl acid phosphate (B) and may contain a monoalkyl acid phosphate (A), wherein the component (A) is represented by the following general formula (1). wherein the (B) component is a compound represented by the following general formula (2), and the content ratio of the (A) component and the (B) component is 0 in mass ratio :100 to 30:70 flow improver is provided.

一般式（１）中、Ｒ^１は、炭素原子数１４～４０のアルキル基を表す。

In general formula (1), R ¹ represents an alkyl group having 14 to 40 carbon atoms.

一般式（２）中、Ｒ^２およびＲ^３は、それぞれ独立に炭素原子数１４～４０のアルキル基を表す。

In general formula (2), R ² and R ³ each independently represent an alkyl group having 14 to 40 carbon atoms.

In the fluidity improver of the present invention, R ¹ in general formula (1) is an alkyl group having 16 to 36 carbon atoms, and R ² and R ³ in general formula (2) are , are preferably alkyl groups each independently having 16 to 36 carbon atoms.

In the fluidity improver of the present invention, R ¹ in the general formula (1) is an octadecyl group, docosyl group or 2-tetradecyl-1-octadecyl group, and R It is preferred that ² and R ³ are each independently octadecyl, docosyl or 2-tetradecyl-1-octadecyl groups.

In the fluidity improver of the present invention, the content ratio of the component (A) and the component (B) is preferably 0:100 to 25:75 by mass.

Further, according to the present invention, there is provided a thermoplastic resin composition containing 100 parts by mass of a thermoplastic resin and 0.02 to 5 parts by mass of the fluidity improver.

In the thermoplastic resin composition of the present invention, the thermoplastic resin is preferably one or more selected from the group consisting of polycarbonate resins, polyester resins and polyamide resins.

Furthermore, according to the present invention, there is provided a molded article obtained by molding the thermoplastic resin composition.

According to the present invention, a fluidity improver capable of improving the melt fluidity of a thermoplastic resin at a low addition amount without causing a decrease in impact resistance or blooming of the additive, and this fluidity improver are provided. It was possible to provide the containing thermoplastic resin composition and a molded article using this thermoplastic resin composition.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.

<Fluidity improver>
The fluidity improver of the present invention contains a dialkyl acid phosphate (B) and may contain a monoalkyl acid phosphate (A).

一般式（１）中、Ｒ^１は、炭素原子数１４～４０のアルキル基を表す。 The (A) component according to the present invention is a compound represented by the following general formula (1).

In general formula (1), R ¹ represents an alkyl group having 14 to 40 carbon atoms.

Examples of alkyl groups having 14 to 40 carbon atoms that can be taken by R ¹ in the general formula (1) include linear, branched and cyclic alkyl groups.

Examples of straight-chain alkyl groups having 14 to 40 carbon atoms that can be represented by R ¹ in general formula (1) include tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups. , henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, hentriacontyl group, dotriacontyl group, tritriacontyl group, tetratriacontyl group, Examples include a pentatriacontyl group and a hexatriacontyl group.

As the branched alkyl group having 14 to 40 carbon atoms that can be taken by R ¹ in the general formula (1), one or more of the hydrogen atoms of the linear alkyl group is A group substituted with an alkyl group can be mentioned.

Examples of the cyclic alkyl group having 14 to 40 carbon atoms that R ¹ in the general formula (1) can take include cyclic alkyl groups corresponding to the linear alkyl groups described above.

In the compound represented by the general formula (1), when the number of carbon atoms in R ¹ is 14 or more, the thermal stability of the alkyl acid phosphate is increased, causing decomposition and volatilization during molding and causing smoke emission. It becomes difficult to cause problems such as occurring. Also, the alkyl acid phosphate is less likely to bloom from the thermoplastic resin. On the other hand, when the number of carbon atoms in R ¹ is 40 or less, the ratio of phosphate groups in the structure increases, and the fluidity improving effect of the thermoplastic resin increases.

As the compound represented by the general formula (1), from the viewpoint of thermal stability and availability of raw materials, it is preferable that R ¹ is an alkyl group having 16 to 36 carbon atoms, such as 16 to 16 carbon atoms. A linear or branched alkyl group of 36 is more preferable, and a linear or branched alkyl group of 18 to 32 carbon atoms is more preferable. From the viewpoint of compatibility with thermoplastic resins and bloom resistance, Octadecyl group, docosyl group or 2-tetradecyl-1-octadecyl group is even more preferred, and octadecyl group is particularly preferred.

一般式（２）中、Ｒ^２およびＲ^３は、それぞれ独立に、炭素原子数１４～４０のアルキル基を表す。 The (B) component according to the present invention is a compound represented by the following general formula (2).

In general formula (2), R ² and R ³ each independently represent an alkyl group having 14 to 40 carbon atoms.

The alkyl group having 14 to 40 carbon atoms that can be taken by R ² and R ³ in the general formula (2) includes linear, branched or cyclic alkyl groups.

The linear, branched or cyclic alkyl group having 14 to 40 carbon atoms that R ² and R ³ in the above general formula (2) can take is a straight alkyl group that R ¹ in the above general formula (1) can take. The same can be mentioned as chain, branched or cyclic alkyl groups.

In the compound represented by the general formula (2), when the number of carbon atoms in R ² or R ³ is 14 or more, the thermal stability of the alkyl acid phosphate increases, causing decomposition or volatilization during molding. It is less likely to cause problems such as smoke generation. Also, the alkyl acid phosphate is less likely to bloom from the thermoplastic resin. On the other hand, when the number of carbon atoms in R ² or R ³ is 40 or less, the proportion of phosphoric acid groups in the structure increases, and the effect of improving the fluidity of the thermoplastic resin increases.

From the viewpoint of thermal stability and availability of raw materials, the compounds represented by the general formula (2) are those in which R ² and R ³ are each independently an alkyl group having 16 to 36 carbon atoms. A linear or branched alkyl group having 16 to 36 carbon atoms is preferable, and a linear or branched alkyl group having 18 to 32 carbon atoms is more preferable, and compatibility with thermoplastic resins and From the viewpoint of bloom resistance, octadecyl group, docosyl group or 2-tetradecyl-1-octadecyl group is more preferred, and octadecyl group is particularly preferred.

The fluidity improver of the present invention can exhibit the effect of improving the melt fluidity of the thermoplastic resin by containing the component (B), but may contain the component (A).

The lower limit of the content of component (A) with respect to 100 parts by mass of the total content of components (A) and (B) in the fluidity improver of the present invention is 0 parts by mass or more, but 0.1 parts by mass. or more, or 0.5 parts by mass or more.

The upper limit of the content of component (A) per 100 parts by mass of the total content of components (A) and (B) in the fluidity improver of the present invention is 30 parts by mass or less, preferably 25 parts by mass or less. , 20 parts by mass or less is more preferable. Assuming that the total content of components (A) and (B) in the fluidity improver of the present invention is 100 parts by mass, component (A) is blended at a content ratio of 30 parts by mass or less. Mechanical properties such as impact resistance of the plastic resin are sufficiently maintained.

The content ratio of component (A) and component (B) in the fluidity improver of the present invention is 0:100 to 30:70, preferably 0:100 to 25:75, in mass ratio. 0.1:99.9 to 25:75 is more preferred, and 0.5:99.5 to 20:80 is even more preferred.

Monoalkyl acid phosphate (A) and dialkyl acid phosphate (B) can be obtained by known synthetic methods. These can be obtained, for example, by reacting a phosphorus oxyhalide and an alcohol in an arbitrary ratio and removing the hydrogen halide produced as a by-product. At this time, a catalyst may be used. The fluidity improver of the present invention can be obtained by mixing the components (A) and (B) thus obtained in the above ratio.

Further, for example, by reacting diphosphorus pentoxide or phosphoric acid with an alcohol, the fluidity improver of the present invention can be obtained directly as a mixture of components (A) and (B). In this case, the composition ratio may be adjusted to the above composition ratio by adjusting the charging amount of the raw materials, or the composition ratio may be adjusted to the above composition ratio by recrystallizing the composition obtained by the synthesis. Recrystallization may be performed multiple times. As a recrystallization method, a known method can be used. For example, recrystallization may be performed by heating and cooling in a solvent. Also, a highly pure dialkyl acid phosphate (B) may be used as a seed crystal during recrystallization.

When the fluidity improver of the present invention is obtained by mixing the components (A) and (B), as a method of mixing, generally used known methods can be applied as they are. For example, the components (A) and (B) may be dry-blended or melt-blended. In the case of melt blending, for example, the fluidity improver of the present invention can be obtained by adding an arbitrary amount of component (B) to a reaction tank after synthesizing component (A), stirring, and then cooling and solidifying. can. In the case of dry blending, for example, a method of mixing using a mixer such as a tumbler mixer, a Henschel mixer, a ribbon blender, a V-type mixer, a W-type mixer, a super mixer, and a Nauta mixer can be used.

The mass ratio of the (A) component and the (B) component in the fluidity improver can be determined by high performance liquid chromatography (hereinafter also referred to as "HPLC") or gel permeation chromatography (hereinafter also referred to as "GPC"). ), analysis using a nuclear magnetic resonance apparatus (hereinafter also referred to as “NMR”), or the like.

<Thermoplastic resin composition>
The thermoplastic resin composition of the present invention contains the above fluidity improver and thermoplastic resin.

The lower limit of the content of the fluidity improver is usually 0.02 parts by mass or more, preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass, relative to 100 parts by mass of the thermoplastic resin. It is at least 0.1 part by mass, and more preferably at least 0.1 part by mass. When the lower limit of the content is 0.02 parts by mass or more, the effect of improving the fluidity of the thermoplastic resin can be sufficiently obtained.

The upper limit of the content of the fluidity improver is usually 5 parts by mass or less, preferably 3 parts by mass or less, and more preferably 1 part by mass or less with respect to 100 parts by mass of the thermoplastic resin. When the upper limit of the content is 5 parts by mass or less, it becomes difficult for the blended fluidity improver to bloom from the resin.

Examples of thermoplastic resins include synthetic resins such as polyolefin resins, styrene resins, polyester resins, polyether resins, polycarbonate (PC) resins, polyamide resins, and halogen-containing resins. These may be used alone or in combination of two or more.

Still other examples of the above thermoplastic resins include petroleum resins, coumarone resins, polyvinyl acetate, acrylic resins, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyphenylene sulfide, polyurethane, cellulose resins, Thermoplastic resins such as polyimide resins, polysulfones, liquid crystal polymers, and blends thereof can be mentioned.

The above thermoplastic resins include isoprene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, olefin elastomer, styrene elastomer, and polyester elastomer. , nitrile-based elastomer, nylon-based elastomer, vinyl chloride-based elastomer, polyamide-based elastomer, polyurethane-based elastomer, and the like, and these may be used in combination.

Specific examples of the thermoplastic resin are not particularly limited, but include polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene, ethylene. / Polyolefin resins such as α-olefin polymers such as propylene block or random copolymers; Polyester resins such as polyethylene terephthalate, polybutylene terephthalate (PBT), polyhexamethylene terephthalate; Polysulfide resins such as polyphenylene sulfide; Polyhexamethylene polyamide resins such as adipamide; styrene resins such as syndiotactic polystyrene and acrylonitrile-butadiene-styrene terpolymer (ABS resin);

Among these thermoplastic resins, one or more selected from the group consisting of polyester resins, polyamide resins and polycarbonate resins is preferable from the viewpoint of obtaining an excellent fluidity improving effect, and these are used in combination with thermoplastic elastomers. is also preferred.

Examples of the polyester resin include polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, and polycyclohexanedimethylene terephthalate; polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate; and polyhydroxybutyrate. , polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, poly(2-oxetanone) and other degradable aliphatic polyesters.

Examples of the polyamide resin include aliphatic polyamides such as polyamide 410, polyamide 6, polyamide 66, polyamide 666, polyamide 610, polyamide 612, polyamide 11 and polyamide 12; polyamide 4T, polyamide 6T, polyamide 9T and polyamide 10T. Mention may be made of semi-aromatic polyamides.

The polycarbonate resin is a resin having a carbonate bond, and is obtained, for example, by a polymerization reaction between a divalent hydroxy aromatic compound and a carbonate precursor.

Examples of the divalent hydroxyaromatic compounds include dihydroxybenzenes such as resorcinol and hydroquinone; bishydroxyaryls such as 4,4'-dihydroxydiphenyl; bis(4-hydroxyphenyl)methane, 1,1-bis(4- bis(hydroxyphenyl)alkanes such as hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenoxy)ethane, 2,2-bis(4-hydroxyphenyl)propane; bis(4-hydroxyphenyl)ketone, bis Dihydroxyaryl ketones such as (4-hydroxy-3-methylphenyl) ketone; 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxy-2 ,5-dihydroxydiphenyl ether and other dihydroxyaryl ethers; 4,4'-thiodiphenol, bis(4-hydroxyphenyl) sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4' -dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 2,2-bis(4-hydroxyphenyl) sulfone, 4,4'-dihydroxydiphenyl sulfone, Examples include dihydroxyaryl sulfur compounds such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone and phenolphthalein. These may be used singly or in combination of two or more, and may also be used in combination with a polyhydric hydroxy aromatic compound having three or more hydroxy groups.

Preferred specific examples of the carbonate precursor include phosgene, diester carbonate, diphenyl carbonate, dihaloformate of dihydric phenol and mixtures thereof.

These thermoplastic resins have molecular weight, degree of polymerization, polymerization method, density, softening point, ratio of insoluble matter in solvent, degree of stereoregularity, presence or absence of catalyst residue, type and blending ratio of raw material monomers, polymerization Any type of catalyst can be used.

These thermoplastic resins may be used alone or in combination of two or more. Also, the thermoplastic resin may be alloyed.

The thermoplastic resin composition of the present invention may contain other optional components together with the fluidity improver. The timing of adding the fluidity improver and other optional components to the thermoplastic resin composition of the present invention is not particularly limited. For example, two or more selected from the blending components other than the thermoplastic resin may be packed into one pack and then blended with the thermoplastic resin, or each component other than the thermoplastic resin may be added to the thermoplastic resin. You may mix|blend one by one. When packing a plurality of components into one pack, each component may be pulverized and then mixed, or mixed and then pulverized. When the thermoplastic resin is an alloy, each component other than the thermoplastic resin may be added to the compound that is alloyed in advance, or may be added during the alloying process.

Other optional components that can be blended in the thermoplastic resin composition of the present invention are described below.

To the thermoplastic resin composition of the present invention, if necessary, a phenolic antioxidant, a phosphorus antioxidant, a thioether antioxidant, an ultraviolet absorber, a hindered amine light stabilizer, etc. are added to obtain a resin. It is preferred to stabilize the composition.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl- 4-hydroxybenzyl)phosphonate, 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 4,4′-thiobis(6-tert-butyl-m -cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis(6-tert-butylphenol) tributyl-m-cresol), 2,2′-ethylidenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1, 1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate , 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, stearyl (3,5-di- tributyl-4-hydroxyphenyl)propionate, tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate]methane, thiodiethylene glycol bis[(3,5-di-tert-butyl -4-hydroxyphenyl)propionate], 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[3,3-bis(4-hydroxy-3- tert-butylphenyl)butyric acid]glycol ester, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3, 5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4 -hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxy Suspiro[5,5]undecane, triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] and the like. The amount of these phenolic antioxidants used is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the thermoplastic resin.

Examples of the phosphorus antioxidant include trisnonylphenyl phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] Phosphite, tridecylphosphite, octyldiphenylphosphite, didecylmonophenylphosphite, bis(tridecyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di- 3-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol Diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tetrakis(tridecyl)isopropylidene diphenol diphosphite, tetrakis(tridecyl)-4,4'-n-butylidenebis(2-tertiary butyl-5-methylphenol) diphosphite, hexakis(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di- tributylphenyl)biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis(4,6-tert-butylphenyl)-2- Ethylhexylphosphite, 2,2'-methylenebis(4,6-tert-butylphenyl)-octadecylphosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, tris( 2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, 2-ethyl- Phosphites of 2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol are included. The amount of these phosphorus-based antioxidants used is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the thermoplastic resin.

Examples of the thioether antioxidant include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetrakis (β-alkylmercaptopropionate). The amount of these thioether-based antioxidants used is preferably 0.001 to 10 parts by mass, preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the thermoplastic resin. is more preferred.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis(2-hydroxy-4-methoxybenzophenone ) and other 2-hydroxybenzophenones; 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)-5- Chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert- trioctylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazolyl) ) phenol), 2-(2′-hydroxyphenyl)benzotriazoles such as 2-(2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl)benzotriazole; phenyl salicylate, resorcinol monobenzoate, 2 ,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate , hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate and the like; 2-ethyl-2'-ethoxyoxaanilide, 2-ethoxy-4'-dodecyloxaxilide and the like cyanoacrylates such as ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; 2-(2-hydroxy-4-octoxy phenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, 2- triaryltriazines such as (2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine; The amount of these ultraviolet absorbers used is preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass, per 100 parts by mass of the thermoplastic resin.

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate , tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl) bis(tridecyl)-1,2,3,4-butane tetracarboxylate, Bis(1,2,2,6,6-pentamethyl-4-piperidyl) bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl) -4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl- 4-piperidinol/diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1, 5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]-1, 5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino )-s-triazin-6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6, 6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2, 6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl ] aminoundecane, bis(2,2,6,6-tetramethyl-1-octyloxy-4-piperidyl)decanedioate, bis(2,2,6,6-tetramethyl-1-undecyloxypiperidine- 4-yl) carbonate, TINUVIN NOR 371 manufactured by BASF, and the like. The amount of these hindered amine light stabilizers used is preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass, based on 100 parts by mass of the thermoplastic resin.

If necessary, the resin composition of the present invention may further contain additives commonly used in synthetic resins, such as cross-linking agents, antistatic agents, antifog agents, plate-out inhibitors, surface treatment agents, plasticizers, Lubricants, reinforcing materials, flame retardants, fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, mold release agents, pigments, silicone oils, silane coupling agents, etc., are added to the extent that the effects of the present invention are not impaired. and can be mixed.

Although the form of the resin composition of the present invention is not particularly limited, it is preferably in the form of pellets, powder, granules or flakes, more preferably in the form of pellets, from the viewpoint of handling properties of the resin composition.

The resin composition of the present invention can be used for molding alone or in combination with resin compositions other than the present invention, additive components, or mixtures thereof. Moreover, the resin composition of the present invention can be used as a masterbatch.

<Molded product>
The molded article of the present invention can be obtained by molding the thermoplastic resin composition of the present invention by a known method. The molding method is not particularly limited, and examples thereof include molding methods such as extrusion molding, calendering molding, injection molding, roll molding, compression molding, and blow molding. By these molding methods, moldings of various shapes such as resin plates, sheets, films, pellets, odd-shaped products, etc. can be produced.

In addition, the resin composition of the present invention and its molded article are used in electrical/electronic/communication, agriculture, forestry and fisheries, mining, construction, food, textile, clothing, medical, coal, petroleum, rubber, leather, automobile, precision equipment, wood, It can be used in a wide range of industrial fields such as building materials, civil engineering, furniture, printing, and musical instruments. More specifically, printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, copiers, facsimiles, ECRs (electronic cash registers), calculators, electronic notebooks, cards, holders, stationery, etc. Office OA equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, home appliances such as kotatsu, TVs, VTRs, video cameras, radio cassette players, tape recorders, mini discs, CD players, speakers, AV equipment such as liquid crystal displays, connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulation materials, LED encapsulation materials, electric wires, cables, transformers, deflection yokes, distribution boards, electrical and electronic parts such as clocks and for applications such as communication equipment.

The resin composition of the present invention and its molded article can also be used for optical materials such as optical discs, CD discs, DVD discs, lenses, etc., and glass substitutes.

Furthermore, the resin composition of the present invention and molded articles thereof can be used for seats (filling, outer material, etc.), belts, ceiling coverings, compatible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, foil covers, mattress covers. , airbags, insulating materials, straps, straps, wire covering materials, electrical insulating materials, paints, coating materials, covering materials, floor materials, partition walls, carpets, wallpaper, wall covering materials, exterior materials, interior materials, Roofing materials, deck materials, wall materials, pillar materials, decking boards, fence materials, frames and moldings, window and door profiles, shingles, siding, terraces, balconies, soundproof boards, heat insulating boards, window materials, etc. Automobiles, vehicles, ships, aircraft, buildings, housing and construction materials, civil engineering materials, clothing, curtains, sheets, plywood, synthetic fiber boards, carpets, entrance mats, sheets, buckets, hoses, containers, glasses, bags, cases, It is used for various purposes such as goggles, skis, rackets, tents, musical instruments and other daily necessities, and sporting goods.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these.

<Production of fluidity improver>
Flow improvers E1-E7 and comparative flow improvers CE1-CE4 listed in Table 1 were obtained according to Preparation Examples 1-11 below. The numerical values of the compositions shown in Table 1 represent mass ratios.

In Production Examples 1 to 11 below, the mass ratio of monoalkyl acid phosphate (A) and dialkyl acid phosphate (B) was measured using ³¹ P-NMR. Measurement conditions are shown below. Among the obtained ³¹ P-NMR spectra, peaks derived from monoalkyl acid phosphate (A) (1.7 ppm to 2.5 ppm) and peaks derived from dialkyl acid phosphate (B) (0.4 ppm to 1.2 ppm ) and the amount of substance of each phosphate, the mass ratio was calculated.

[ ³¹ P-NMR measurement conditions]
Apparatus: Ascend 400 (manufactured by Bruker Corporation)
Solvent: Heavy chloroform Accumulation times: 256 times

<Production Example 1: Comparative fluidity improver CE1>
428 g of 1-octadecyl alcohol and 440 g of ortho-xylene were added to a flask equipped with a stirrer and a condenser, and after nitrogen substitution under reduced pressure, the temperature was raised to 90° C. in an oil bath while stirring. Then, 73 g of diphosphorus pentoxide was added, the temperature was raised to 110° C., and the reaction was allowed to proceed for 4 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and cooled to room temperature, so that the mass ratio of (A)-1: mono(1-octadecyl) acid phosphate and (B)-1: bis(1-octadecyl) acid phosphate was to give a comparative flow improver CE1 of 37:63.

<Production Example 2: Fluidity improver E3>
100 g of comparative fluidity improver CE1 obtained in Production Example 1 and 300 g of 2-propanol were placed in a flask and heated to 80° C. in an oil bath while stirring. After the solution became homogeneous, the heating was stopped and recrystallization was carried out at 40°C. The precipitate was filtered through a Buchner funnel, and (A)-1: mono(1-octadecyl) acid phosphate and (B)-1: bis(1-octadecyl) acid phosphate at a mass ratio of 25:75 were obtained. Flow improver E3 was obtained.

<Production Example 3: Fluidity improver E2>
By repeating the same recrystallization operation as in Production Example 2 for the fluidity improver E3 obtained in Production Example 2, (A)-1: mono(1-octadecyl) acid phosphate and (B)-1 : bis(1-octadecyl) acid phosphate in a mass ratio of 12:88 to obtain fluidity improver E2.

<Production Example 4: Fluidity improver E1>
By repeating the same recrystallization operation as in Production Example 2 on the fluidity improver E2 obtained in Production Example 3, (A)-1: mono(1-octadecyl) acid phosphate and (B)-1 : bis(1-octadecyl) acid phosphate in a mass ratio of 0:100 to obtain fluidity improver E1.

<Production Example 5: Comparative fluidity improver CE2>
(A)-2: mono(1-docosyl) acid phosphate and (B)-2: bis(1 - docosyl) acid phosphate to give a comparative fluidity improver CE2 in a weight ratio of 36:64.

<Production Example 6: Fluidity improver E5>
By performing the same recrystallization operation as in Production Example 2 on the comparative fluidity improver CE2 obtained in Production Example 5, (A)-2: mono (1-docosyl) acid phosphate and (B)- 2: bis(1-docosyl)acid phosphate in a mass ratio of 10:90 to obtain fluidity improver E5.

<Production Example 7: Fluidity improver E4>
By repeating the same recrystallization operation as in Production Example 2 on the fluidity improver E5 obtained in Production Example 6, (A)-2: mono (1-docosyl) acid phosphate and (B)-2 : bis(1-docosyl)acid phosphate in a mass ratio of 0:100 to obtain fluidity improver E4.

<Production Example 8: Comparative fluidity improver CE3>
(A)-3: mono(2-tetradecyl-1-octadecyl) acid phosphate and (B )-3: bis(2-tetradecyl-1-octadecyl) acid phosphate to obtain a comparative fluidity improver CE3 with a weight ratio of 35:65.

<Production Example 9: Fluidity improver E7>
(A)-3: Mono(2 -tetradecyl-1-octadecyl) acid phosphate and (B)-3: bis(2-tetradecyl-1-octadecyl) acid phosphate at a weight ratio of 18:82 to obtain fluidity improver E7.

<Production Example 10: Fluidity improver E6>
(A)-3: mono(2-tetradecyl-1-octadecyl) acid phosphate and ( B)-3: Fluidity improver E6 with a mass ratio of 0:100 to bis(2-tetradecyl-1-octadecyl)acid phosphate was obtained.

<Production Example 11: Comparative fluidity improver CE4>
(A)-4: mono(1-dodecyl) acid phosphate and (B)-4: bis(1- 365 g of a composition having a mass ratio of 38:62 with dodecyl)acid phosphate was obtained. By repeating the same recrystallization operation as in Production Example 2 three times with respect to 100 g of this composition, (A)-4: mono(1-dodecyl) acid phosphate and (B)-4: bis(1-dodecyl ) to acid phosphate in a weight ratio of 1:99 to give a comparative fluidity improver CE4.

（Ａ）－２：モノ（１－ドコシル）アシッドホスフェート

（Ａ）－３：モノ（２－テトラデシル－１－オクタデシル）アシッドホスフェート

（Ａ）－４：モノ（１－ドデシル）アシッドホスフェート

（Ｂ）－１：ビス（１－オクタデシル）アシッドホスフェート

（Ｂ）－２：ビス（１－ドコシル）アシッドホスフェート

（Ｂ）－３：ビス（２－テトラデシル－１－オクタデシル）アシッドホスフェート

（Ｂ）－４：ビス（１－ドデシル）アシッドホスフェート

Details of the components in Table 1 are given below.
(A)-1: Mono (1-octadecyl) acid phosphate

(A)-2: mono (1-docosyl) acid phosphate

(A)-3: Mono (2-tetradecyl-1-octadecyl) acid phosphate

(A)-4: Mono (1-dodecyl) acid phosphate

(B)-1: bis (1-octadecyl) acid phosphate

(B)-2: bis (1-docosyl) acid phosphate

(B)-3: bis (2-tetradecyl-1-octadecyl) acid phosphate

(B)-4: bis (1-dodecyl) acid phosphate

<Method for preparing thermoplastic resin composition>
After dry blending each component described in Tables 2 to 8, heat melt kneading using a twin screw extruder (device name: 2D15W, manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a pellet-like thermoplastic resin composition. rice field. The numerical values of the compositions shown in Tables 2 to 8 represent mass ratios. Heating and melting conditions for each resin are shown below.
PC resin: 280°C
Alloy of PC resin and ABS resin: 250°C
PBT resin: 250°C

Details of the components in Tables 2-8 are provided below.
PC resin: Polycarbonate resin (Mitsubishi Engineering-Plastics Co., Ltd. Iupilon S-3000F)
ABS resin: acrylonitrile-butadiene-styrene copolymer (AT-05 manufactured by Nippon A&L Co., Ltd.)
PBT resin: Polybutylene terephthalate resin (DURANEX 2002 manufactured by Polyplastics Co., Ltd.)
Comparative fluidity improver CE5: styrene-phenyl methacrylate copolymer (mass average molecular weight (Mw) = 46,000, styrene/phenyl methacrylate = 88/12 (mass ratio))

<Method for preparing thermoplastic resin test piece>
The thermoplastic resin composition prepared above is molded using an injection molding machine (device name: NEX80, manufactured by Nissei Plastic Industry Co., Ltd.) to obtain a test piece (80 mm × 10 mm × 4 mm) for evaluating Charpy impact strength. rice field. The injection molding conditions for each resin are as shown below.
PC resin: Cylinder temperature 280°C, mold temperature 80°C
Alloy of PC resin and ABS resin: cylinder temperature 250°C, mold temperature 60°C
PBT resin: cylinder temperature 250°C, mold temperature 60°C

<Method for evaluating melt fluidity of thermoplastic resin>
The melt mass flow rate (hereinafter also referred to as "MFR") of the compound of the thermoplastic resin composition prepared above was measured using a melt indexer (device name: L-227-41, manufactured by Tateyama Science High Technologies Co., Ltd.). It was measured. The measurement results are shown in Tables 2-8. In addition, the measurement conditions for each resin are as shown below.
PC resin: cylinder temperature 300°C, load 12N
Alloy of PC resin and ABS resin: cylinder temperature 250°C, load 21.6N
PBT resin: cylinder temperature 250°C, load 21.6N

<Evaluation method for Charpy impact strength and bloom resistance>
After notching a test piece for Charpy impact strength evaluation, it was annealed for a certain period of time in a heated air blowing oven. After that, the test piece was allowed to stand in an environment of 23° C. for 48 hours, and the Charpy impact strength was measured in an environment of 23° C. according to ISO-179. Moreover, the surface of the test piece after the annealing treatment was observed with an optical microscope to confirm the presence or absence of bloom. The respective evaluation results are shown in Tables 2-8. The annealing conditions for each resin test piece are as follows.
PC resin test piece: 120°C for 1 hour Alloy test piece of PC resin and ABS resin: 120°C for 1 hour PBT resin test piece: 190°C for 1 hour

Tables 2 to 4 show the evaluation results when the fluidity improver of the present invention was blended with polycarbonate resin. From a comparison between Examples 1 to 13 and Comparative Example 1, it was confirmed that the fluidity improver of the present invention greatly improves the melt fluidity of the resin and does not cause a significant decrease in impact strength. When the amount added was less than the range of the present invention, the MFR was not improved (Comparative Examples 2 and 3). When the added amount was larger than the range of the present invention, the impact strength was remarkably lowered, and bloom was also confirmed (Comparative Example 4), although the MFR was improved. When a fluidity improver having a composition different from that of the fluidity improver of the present invention was blended, the MFR was improved, but the impact strength was remarkably lowered (Comparative Examples 5 to 8). In Comparative Example 8, blooming of the test piece and smoke emission during extrusion processing were confirmed, and it was found that the fluidity improver CE4 was inferior in compatibility with the resin and thermal stability. In the composition using the styrene-phenyl acrylate copolymer as the fluidity improver, even when the amount was as high as 5 parts by mass, the MFR was equal to or lower than that of the fluidity improver of the present invention, and the impact strength was significantly reduced. (Comparative Examples 9-10).

Tables 5 and 6 show the evaluation results when the fluidity improver of the present invention was blended into an alloy of polycarbonate resin and ABS resin. From a comparison between Examples 14 to 24 and Comparative Example 11, it was confirmed that the fluidity improver of the present invention greatly improves the melt fluidity of the resin and does not cause a significant decrease in impact strength. When a fluidity improver having a composition different from that of the fluidity improver of the present invention was blended, the MFR was improved, but the impact strength was remarkably lowered (Comparative Examples 12 to 15). In Comparative Examples 14 and 15, blooming of the test pieces and smoke emission during extrusion processing were confirmed, and it was found that the fluidity improver CE4 was inferior in compatibility with resins and thermal stability. In the composition using the styrene-phenyl acrylate copolymer as the fluidity improver, even when the amount was as high as 5 parts by mass, the MFR was equal to or lower than that of the fluidity improver of the present invention, and the impact strength was significantly reduced. (Comparative Example 15).

Tables 7 and 8 show the evaluation results when the fluidity improver of the present invention was mixed with polybutylene terephthalate resin. From a comparison between Examples 25 to 34 and Comparative Example 17, it was confirmed that the fluidity improver of the present invention greatly improved the melt fluidity of the resin and did not cause a significant decrease in impact strength. When a fluidity improver having a composition different from that of the fluidity improver of the present invention was blended, the MFR was improved, but the impact strength was remarkably lowered (Comparative Examples 18 to 21). In Comparative Examples 20 and 21, blooming of the test pieces and smoke emission during extrusion processing were confirmed, and it was found that the fluidity improver CE4 was inferior in compatibility with resins and thermal stability.

Claims (7)

A fluidity improver comprising a dialkyl acid phosphate (B),
may contain a monoalkyl acid phosphate (A),
The component (A) is a compound represented by the following general formula (1),
The component (B) is a compound represented by the following general formula (2), and
A fluidity improver characterized in that the content ratio of the component (A) and the component (B) is 0:100 to 30:70 in mass ratio.

In general formula (1), R ¹ represents an alkyl group having 14 to 40 carbon atoms.

In general formula (2), R ² and R ³ each independently represent an alkyl group having 14 to 40 carbon atoms. R ¹ in the general formula (1) is an alkyl group having 16 to 36 carbon atoms, and
2. The fluidity improver according to claim 1, wherein R ² and R ³ in the general formula (2) are each independently an alkyl group having 16 to 36 carbon atoms. R ¹ in the general formula (1) is an octadecyl group, a docosyl group or a 2-tetradecyl-1-octadecyl group, and
2. The fluidity improver according to claim 1, wherein R ² and R ³ in said general formula (2) are each independently octadecyl group, docosyl group or 2-tetradecyl-1-octadecyl group. The fluidity improver according to any one of claims 1 to 3, wherein the content ratio of the component (A) and the component (B) is 0:100 to 25:75 by mass. 100 parts by mass of a thermoplastic resin;
0.02 to 5 parts by mass of the fluidity improver according to any one of claims 1 to 4;
A thermoplastic resin composition comprising: 6. The thermoplastic resin composition according to claim 5, wherein said thermoplastic resin is one or more selected from the group consisting of polycarbonate resin, polyester resin and polyamide resin. A molded product obtained by molding the thermoplastic resin composition according to claim 5 or 6.