JP2024051849A - Nucleating agent for thermoplastic resin, resin composition, molded article, and method for promoting crystallization of thermoplastic resin - Google Patents

Abstract

[Problem] To provide a nucleating agent for thermoplastic resins, a resin composition, a molded article, and a method for promoting crystallization of thermoplastic resins, which have an excellent crystallization promoting effect on thermoplastic resins other than polyolefin-based resins. [Solution] A nucleating agent for thermoplastic resins (excluding polyolefin-based resins) containing a compound represented by the following general formula (1), TIFF2024051849000027.tif36154 (in general formula (1), M represents a monovalent to trivalent metal atom or the like having a specific gravity of 4.0 or less, a represents 1 or 2, b represents 1 or 3, x represents an integer of 1 to 3, and ax = 2b is satisfied. Z represents a specific group containing a cyclohexane ring or a benzene ring). [Selected Figure] None

Description

The present invention relates to a nucleating agent for thermoplastic resins, a resin composition, a molded article, and a method for promoting the crystallization of thermoplastic resins, and more specifically, to a nucleating agent for thermoplastic resins, a resin composition, a molded article, and a method for promoting the crystallization of thermoplastic resins, which have an excellent crystallization promoting effect on thermoplastic resins other than polyolefin-based resins.

Various studies have been conducted with the aim of improving the properties of thermoplastic resins. For example, the following Patent Document 1 proposes a nucleating agent for thermoplastic resins that contains a metal salt of polymerized rosins, and discloses that the use of this agent can improve the crystallization rate of thermoplastic resins and improve mechanical and optical performance. In addition, the following Patent Document 2 proposes a nucleating agent for polyolefin resins that contains a specific compound that contains an aspartic acid structure, and discloses that this nucleating agent for polyolefin resins exerts an excellent β-crystal formation effect on polyolefin resins.

JP 2014-227546 A International Publication No. 2020/137179

However, the nucleating agent for thermoplastic resins proposed in Patent Document 1 may not have sufficient crystallization-promoting properties, and further improvements are desired. In addition, the compound proposed in Patent Document 2 has not been considered at all as an additive for use in thermoplastic resins other than polyolefin-based resins.

The object of the present invention is to provide a nucleating agent for thermoplastic resins, a resin composition, a molded article, and a method for promoting the crystallization of thermoplastic resins, which have an excellent crystallization promoting effect on thermoplastic resins other than polyolefin-based resins.

As a result of intensive research aimed at solving the above problems, the inventors discovered that a specific compound containing an aspartic acid structure has an excellent crystallization promoting effect on thermoplastic resins other than polyolefin-based resins, and thus completed the present invention.

（一般式（１）中、Ｍは、比重が４．０以下である１～３価の金属原子またはヒドロキシ基が結合した比重が４．０以下である２～３価の金属原子を表し、ａは１または２を表し、ｂは１または３を表し、ｘは１～３の整数を表し、ａｘ＝２ｂを満たす。Ｚは下記一般式（２）または（３）で表される基を表す。

（一般式（２）および（３）中、＊は一般式（１）のカルボニル炭素と連結する位置を表し、Ｙは、直接結合、または炭素原子数１～４のアルキレン基を表し、Ｒ_１～Ｒ_１０はそれぞれ独立に、水素原子、ヒドロキシ基、ハロゲン原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のハロゲン化アルキル基、炭素原子数１～１０のアルコキシ基または炭素原子数２～１０のアルケニル基を表す。））で表される化合物を含むことを特徴とするものである。ただし、本発明の熱可塑性樹脂用核剤からは、ポリオレフィン系樹脂用核剤は除かれる。 That is, the nucleating agent for thermoplastic resin of the present invention is represented by the following general formula (1):

(In general formula (1), M represents a monovalent to trivalent metal atom having a specific gravity of 4.0 or less, or a divalent to trivalent metal atom having a hydroxyl group bonded thereto and having a specific gravity of 4.0 or less, a represents 1 or 2, b represents 1 or 3, x represents an integer of 1 to 3, and ax=2b is satisfied. Z represents a group represented by the following general formula (2) or (3):

(in general formulas (2) and (3), * represents the position at which it is linked to the carbonyl carbon in general formula (1), Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms, and R ₁ to R ₁₀ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms.) However, the nucleating agent for thermoplastic resins of the present invention excludes nucleating agents for polyolefin resins.

The nucleating agent for thermoplastic resins of the present invention is suitable as a nucleating agent for polyamide-based resins, polyester-based resins, or polylactic acid-based resins.

（一般式（１）中、Ｍは、比重が４．０以下である１～３価の金属原子またはヒドロキシ基が結合した比重が４．０以下である２～３価の金属原子を表し、ａは１または２を表し、ｂは１または３を表し、ｘは１～３の整数を表し、ａｘ＝２ｂを満たす。Ｚは下記一般式（２）または（３）で表される基を表す。

（一般式（２）および（３）中、＊は一般式（１）のカルボニル炭素と連結する位置を表し、Ｙは、直接結合、または炭素原子数１～４のアルキレン基を表し、Ｒ_１～Ｒ_１０はそれぞれ独立に、水素原子、ヒドロキシ基、ハロゲン原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のハロゲン化アルキル基、炭素原子数１～１０のアルコキシ基または炭素原子数２～１０のアルケニル基を表す。））で表される化合物と、
を含むことを特徴とするものである。 The resin composition of the present invention is a thermoplastic resin (excluding polyolefin resins) and
The following general formula (1):

(In general formula (1), M represents a monovalent to trivalent metal atom having a specific gravity of 4.0 or less, or a divalent to trivalent metal atom having a hydroxyl group bonded thereto and having a specific gravity of 4.0 or less, a represents 1 or 2, b represents 1 or 3, x represents an integer of 1 to 3, and ax=2b is satisfied. Z represents a group represented by the following general formula (2) or (3):

(in general formulas (2) and (3), * represents the position at which the group is bonded to the carbonyl carbon of general formula (1), Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms, and R ₁ to R ₁₀ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms),
The present invention is characterized in that it comprises:

In the resin composition of the present invention, it is preferable that the thermoplastic resin contains a polyamide-based resin, a polyester-based resin, or a polylactic acid-based resin.

Furthermore, the molded article of the present invention is characterized by being obtained by molding the above-mentioned resin composition.

（一般式（１）中、Ｍは、比重が４．０以下である１～３価の金属原子またはヒドロキシ基が結合した比重が４．０以下である２～３価の金属原子を表し、ａは１または２を表し、ｂは１または３を表し、ｘは１～３の整数を表し、ａｘ＝２ｂを満たす。Ｚは下記一般式（２）または（３）で表される基を表す。

（一般式（２）および（３）中、＊は一般式（１）のカルボニル炭素と連結する位置を表し、Ｙは、直接結合、または炭素原子数１～４のアルキレン基を表し、Ｒ_１～Ｒ_１０はそれぞれ独立に、水素原子、ヒドロキシ基、ハロゲン原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のハロゲン化アルキル基、炭素原子数１～１０のアルコキシ基または炭素原子数２～１０のアルケニル基を表す。））で表される化合物を、熱可塑性樹脂用核剤として使用することを特徴とするものである。 Furthermore, the method for promoting crystallization of a thermoplastic resin of the present invention is a method for promoting crystallization of a thermoplastic resin (excluding polyolefin-based resins), comprising the steps of:
The following general formula (1):

(In general formula (1), M represents a monovalent to trivalent metal atom having a specific gravity of 4.0 or less, or a divalent to trivalent metal atom having a hydroxyl group bonded thereto and having a specific gravity of 4.0 or less, a represents 1 or 2, b represents 1 or 3, x represents an integer of 1 to 3, and ax=2b is satisfied. Z represents a group represented by the following general formula (2) or (3):

(in general formulas (2) and (3), * represents the position at which it is linked to the carbonyl carbon in general formula (1), Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms, and R ₁ to R ₁₀ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms)) as a nucleating agent for thermoplastic resins.

In the method for promoting crystallization of a thermoplastic resin of the present invention, it is preferable that the thermoplastic resin contains a polyamide-based resin, a polyester-based resin, or a polylactic acid-based resin.

The present invention provides a nucleating agent for thermoplastic resins, a resin composition, a molded article, and a method for promoting the crystallization of thermoplastic resins that have an excellent crystallization promoting effect on thermoplastic resins other than polyolefin-based resins.

The following describes in detail an embodiment of the present invention. First, we will explain the nucleating agent for thermoplastic resins.

<Nucleating agent for thermoplastic resin>
The nucleating agent for thermoplastic resins according to the present embodiment contains a compound represented by the following general formula (1): However, the nucleating agent for thermoplastic resins excludes nucleating agents for polyolefin resins.

The nucleating agent for thermoplastic resins of this embodiment has an excellent crystallization promoting effect on thermoplastic resins other than polyolefin-based resins. As a result, the nucleating agent for thermoplastic resins of this embodiment can impart properties such as heat resistance, rigidity, and transparency to molded articles made of resin compositions containing thermoplastic resins other than polyolefin-based resins.

In the general formula (1), M represents a monovalent to trivalent metal atom having a specific gravity of 4.0 or less, or a divalent to trivalent metal atom having a hydroxyl group bonded thereto and having a specific gravity of 4.0 or less, a represents 1 or 2, b represents 1 or 3, and x represents an integer of 1 to 3, such that ax=2b is satisfied. Furthermore, Z represents a group represented by the following general formula (2) or (3).

In general formulas (2) and (3), * represents the position at which the carbonyl carbon in general formula (1) is bonded, Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms, and R ₁ to R ₁₀ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms.

Examples of the alkylene group having 1 to 4 carbon atoms represented by Y in general formulas (2) and (3) include a methylene group, an ethylene group, a propylene group, a butylene group, and an isobutylene group. From the viewpoint of obtaining a nucleating agent for thermoplastic resins having an even more excellent crystallization-promoting effect, Y is preferably a direct bond or a methylene group, and more preferably a direct bond.

Examples of the halogen atom represented by R ₁ to R ₁₀ in the general formulae (2) and (3) include fluorine, chlorine, bromine and iodine. Among these, chlorine is particularly preferred.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ₁ to R ₁₀ in general formulas (2) and (3) include a linear or branched alkyl group, and a cycloalkyl group having 3 to 10 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a cyclobutyl group, an n-amyl group, a tert-amyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, a cycloheptyl group, an n-octyl group, an isooctyl group, a tert-octyl group, a 2-ethylhexyl group, an n-nonyl group, an isononyl group, and an n-decyl group.

Examples of the halogenated alkyl group having 1 to 10 carbon atoms represented by R ₁ to R ₁₀ in general formulas (2) and (3) include the above alkyl groups in which some or all of the hydrogen atoms have been substituted with halogen atoms, and examples of the halogen atoms include fluorine, chlorine, bromine and iodine.

Examples of the alkoxy group having 1 to 10 carbon atoms represented by R ₁ to R ₁₀ in general formulas (2) and (3) include a linear or branched alkoxy group, or a cycloalkoxy group having 5 to 10 carbon atoms. Specific examples include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-hexyloxy group, a 1-methylethoxy group, a 2-methylpropoxy group, a 1-methylbutoxy group, a 4-methylpentyloxy group, and a cyclohexyloxy group.

Examples of the alkenyl group having 2 to 10 carbon atoms represented by R ₁ to R ₁₀ in general formulas (2) and (3) include vinyl, propenyl, butenyl, hexenyl, octenyl, decenyl, etc. The position of the double bond may be the α-position, internal position, or ω-position.

In formulae (2) and (3), R ₁ to R ₁₀ are preferably a hydrogen atom or a halogen atom, and particularly preferably a hydrogen atom.

Examples of M in the general formula (1) include metal atoms such as lithium, sodium, potassium, magnesium, calcium, barium, and aluminum. The divalent to trivalent metal atom may be bonded to a hydroxy group. Examples of divalent to trivalent metal atoms bonded to a hydroxy group include hydroxyaluminum and dihydroxyaluminum. From the viewpoint of obtaining a nucleating agent for thermoplastic resins having a further excellent crystallization promoting effect, M in the general formula (1) is preferably lithium, sodium, potassium, magnesium, calcium, barium, aluminum, hydroxyaluminum, or dihydroxyaluminum, more preferably lithium, sodium, potassium, calcium, or hydroxyaluminum, and particularly preferably sodium.

In general formula (1), b is preferably 1. Also, x is preferably 1 or 2.

From the viewpoint of obtaining a nucleating agent for thermoplastic resins having an even more excellent crystallization-promoting effect, Z in general formula (1) is preferably a group represented by general formula (3).

Specific examples of compounds represented by general formula (1) include the following. However, the nucleating agent for thermoplastic resins of this embodiment is not limited to these.

The compound represented by general formula (1) can be produced, for example, by reacting a metal salt of aspartic acid with a carboxylic acid chloride such as benzoic acid chloride or cyclohexane carboxylic acid chloride in the presence of a base.

The nucleating agent for thermoplastic resin in this embodiment may be, for example, a nucleating agent for crystalline thermoplastic resin. Examples of nucleating agents for crystalline thermoplastic resin include nucleating agents for polyamide-based resins, nucleating agents for polyester-based resins, nucleating agents for polyacetal-based resins, nucleating agents for polylactic acid-based resins, and nucleating agents for polyphenylene sulfide-based resins.

Here, examples of nucleating agents for polyamide-based resins include nucleating agents for aliphatic polyamide-based resins such as polyamide 6 (PA6), polyamide 46 (PA46), polyamide 66 (PA66), polyamide 11 (PA11), and polyamide 12 (PA12), nucleating agents for polyamide 4T (PA4T), polyamide 6T (PA6T), polyamide 9T (PA9T), polyamide 10T (PA10T), polyamide 12T (PA12T), and semi-aromatic polyamide-based resins such as polyamide MXD6 (PAMXD6).

Examples of nucleating agents for polyester resins include nucleating agents for polyethylene terephthalate (PET), nucleating agents for polytrimethylene terephthalate (PTT), nucleating agents for polybutylene terephthalate (PBT), and nucleating agents for polyethylene naphthalate (PEN).

Examples of nucleating agents for polylactic acid-based resins include nucleating agents for polylactic acid (PLA).

The nucleating agent for thermoplastic resins of this embodiment is suitable as a nucleating agent for polyamide-based resins, a nucleating agent for polyester-based resins, or a nucleating agent for polylactic acid-based resins, and is more preferably a nucleating agent for polyamide-based resins or a nucleating agent for polyester-based resins.

More specifically, the thermoplastic resin nucleating agent of this embodiment is preferably a nucleating agent for polyamide 6 (PA6), a nucleating agent for polyamide 66 (PA66), a nucleating agent for polyamide 11 (PA11), a nucleating agent for polyamide 12 (PA12), a nucleating agent for polyamide 9T (PA9T), a nucleating agent for polyethylene terephthalate (PET), a nucleating agent for polytrimethylene terephthalate (PTT), a nucleating agent for polybutylene terephthalate (PBT), a nucleating agent for polyethylene naphthalate (PEN), or a nucleating agent for polylactic acid (PLA), and more specifically, a nucleating agent for polyamide 6 (PA6), a nucleating agent for polyamide 66 (PA66), a nucleating agent for polyamide 11 (PA11), a nucleating agent for polyamide 12 (PA12), a nucleating agent for polyamide 9T (PA9T), a nucleating agent for polyethylene It is more preferable that the nucleating agent is a nucleating agent for polyethylene terephthalate (PET), a nucleating agent for polytrimethylene terephthalate (PTT), a nucleating agent for polybutylene terephthalate (PBT) or a nucleating agent for polyethylene naphthalate (PEN), and it is even more preferable that the nucleating agent is a nucleating agent for polyamide 6 (PA6), a nucleating agent for polyamide 66 (PA66), a nucleating agent for polyethylene terephthalate (PET) or a nucleating agent for polybutylene terephthalate (PBT), and it is even more preferable that the nucleating agent is a nucleating agent for polyamide 6 (PA6), a nucleating agent for polyamide 66 (PA66) or a nucleating agent for polyethylene terephthalate (PET), and it is particularly preferable that the nucleating agent is a nucleating agent for polyamide 6 (PA6) or a nucleating agent for polyethylene terephthalate (PET).

<Resin Composition>
Next, the resin composition of the present embodiment will be described. The resin composition of the present embodiment contains a thermoplastic resin and a compound represented by the above general formula (1). However, the thermoplastic resin excludes polyolefin resins.

The resin composition of this embodiment promotes the crystallization of the thermoplastic resin. As a result, the resin composition of this embodiment can impart properties such as heat resistance, rigidity, and transparency to the molded product.

Thermoplastic resins contained in the resin composition of this embodiment include, for example, crystalline resins such as polyester resins, polyamide resins, polyacetal resins, polylactic acid resins, and polyphenylene sulfide, non-crystalline resins such as polycarbonate resins, styrene resins, acrylic resins, urethane resins, halogen-containing resins, petroleum resins, coumarone resins, polyvinyl alcohol, polyvinyl acetate, and polyphenylene oxide, and thermoplastic elastomers.

Here, examples of polyamide-based resins include aliphatic polyamide-based resins such as polyamide 6 (PA6), polyamide 46 (PA46), polyamide 66 (PA66), polyamide 11 (PA11), and polyamide 12 (PA12), and semi-aromatic polyamide-based resins such as polyamide 4T (PA4T), polyamide 6T (PA6T), polyamide 9T (PA9T), polyamide 10T (PA10T), polyamide 12T (PA12T), and polyamide MXD6 (PAMXD6).

Examples of polyester resins include polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN).

Furthermore, examples of polylactic acid-based resins include polylactic acid (PLA).

The thermoplastic resin may be one type alone or two or more types in combination. The thermoplastic resin may be a copolymer or a polymer alloy. The molecular weight, degree of polymerization, density, softening point, proportion of insoluble matter in a solvent, degree of stereoregularity, presence or absence of catalyst residue, types and blending ratios of monomers as raw materials, and types of catalysts used in polymerization of the thermoplastic resin are not particularly limited and may be selected as appropriate.

The thermoplastic resin of this embodiment preferably contains a polyamide-based resin, a polyester-based resin, or a polylactic acid-based resin, and more preferably contains a polyamide-based resin or a polyester-based resin.

More specifically, the thermoplastic resin of this embodiment preferably contains polyamide 6 (PA6), polyamide 66 (PA66), polyamide 11 (PA11), polyamide 12 (PA12), polyamide 9T (PA9T), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) or polylactic acid (PLA), and more preferably contains polyamide 6 (PA6), polyamide 66 (PA66), polyamide 11 (PA11), polyamide 12 (PA12), polyamide 9T (PA9T), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) or polylactic acid (PLA). More preferably, it contains polyamide 6 (PA6), polyamide 66 (PA66), polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), more preferably, it contains polyamide 6 (PA6), polyamide 66 (PA66) or polyethylene terephthalate (PET), and even more preferably, it contains polyamide 6 (PA6), polyamide 66 (PA66) or polyethylene terephthalate (PET), and particularly preferably, it contains polyamide 6 (PA6) or polyethylene terephthalate (PET).

The compound represented by general formula (1) contained in the resin composition of this embodiment may be the same as the compounds exemplified as those contained in the nucleating agent for thermoplastic resins described above.

In the resin composition of this embodiment, the content of the compound represented by general formula (1) may be, for example, 0.001 to 10 parts by mass per 100 parts by mass of the thermoplastic resin. From the viewpoint of further promoting the crystallization of the thermoplastic resin and suppressing the occurrence of bloom and the extractability of the compound, the content of the compound represented by the general formula (1) is preferably 0.005 to 1 part by mass, more preferably 0.02 to 0.5 parts by mass, and even more preferably 0.05 to 0.3 parts by mass per 100 parts by mass of the thermoplastic resin.

The resin composition of this embodiment may further contain at least one of additives such as phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, other antioxidants, hindered amine compounds, UV absorbers, fatty acid metal salts, flame retardants, flame retardant assistants, lubricants, fillers, hydrotalcites, antistatic agents, fluorescent brighteners, pigments, and dyes (hereinafter referred to as "other additives"). The content of the other additives is not particularly limited, and it is sufficient that each additive is contained in an appropriate concentration in the resin composition.

Examples of phenol-based antioxidants include 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-thiobis-(6-tert-butyl-4-methylphenol), 2,2'-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2-methyl-4,6-bis(octylsulfanylmethyl)phenol, 2,2'-isobutylidenebis(4,6-dimethylphenol), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,2'-oxamide-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2-ethylhexyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 2,2'-ethylenebis(4,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxybenzenepropanoic acid and C13-15 alkyl ester, 2,5-di-tert-amylhydroquinone, hindered phenol polymer (manufactured by ADEKA POLYMER ADDITIVES EUROPE SAS) Product name "AO.OH.98"), 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol], 2-tert-butyl-6-(3-tert-butyl-2-hydroxy5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 6-[3-(3-tert-butyl-4-hydroxy-5-methyl)propoxy]-2,4,8,10-tetra-tert-butyl Chilbenz[d,f][1,3,2]-dioxaphosphobin, hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate]calcium salt, reaction product of 5,7-bis(1,1-dimethylethyl)-3-hydroxy-2(3H)-benzofuranone with o-xylene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-yl azothiocarbamate, phenol, DL-a-tocopherol (vitamin E), 2,6-bis(α-methylbenzyl)-4-methylphenol, bis[3,3-bis-(4'-hydroxy-3'-tert-butyl-phenyl)butanoic acid] glycol ester, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) Phosphonate, tridecyl-3,5-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(6-tert-butyl-m-cresol), 2-octylthio-4,6-di(3,5-di-tert-butyl-4-hydroxyphenoxy)-s-triazine, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-tert- butylphenyl)butyric acid] glycol ester, 4,4'-butylidenebis(2,6-di-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]tere Phthalate, 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, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3', 5'-tert-butyl-4'-hydroxyphenyl)propionate]methane, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, 3,9-bis[2-(3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane pionate], stearyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide, palmityl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide, myristyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide, lauryl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide, and other 3-(3,5-dialkyl-4-hydroxyphenyl)propionic acid derivatives.

Examples of phosphorus-based antioxidants include triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenyl isooctyl phosphite, diisooctyl phenyl phosphite, diphenyl tridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, dioleyl hydrogen phosphite, trilauryl trithio phosphite, bis (tridecyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, diphenyl decyl phosphite, dinonyl phenyl bis (nonyl phenyl) phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyl dipropylene glycol diphosphite, tris nonyl phenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, Tris(2,4-di-tert-butyl-5-methylphenyl)phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tri(decyl)phosphite, octyldiphenylphosphite, di(decyl)monophenylphosphite, mixture of distearyl pentaerythritol and calcium stearate, alkyl(C10)bisphenol A phosphite, tetra Phenyl-tetra(tridecyl)pentaerythritol tetraphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, tetra(tridecyl)isopropylidenediphenol diphosphite, tetra(tridecyl)-4,4'-n-butylidenebis(2-tert-butyl-5-methylphenol)diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butadiene triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (1-methyl-1-propenyl-3-ylidene)tris(1,1-dimethylethyl)-5-methyl-4,1-phenylene)hexatridecylphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexylphosphite, 2,2'- methylenebis(4,6-di-tert-butylphenyl)-octadecyl phosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, 4,4'-butylidenebis(3-methyl-6-tert-butylphenylditridecyl)phosphite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, 3,9-bis(4 -nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphespiro[5,5]undecane, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly 4,4'-isopropylidenediphenol C12-15 alcohol phosphite, bis(diisodecyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, bis(octadecyl)pentaerythritol diphosphite, Examples of such diphosphite include thritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

Examples of sulfur-based antioxidants include tetrakis[methylene-3-(laurylthio)propionate]methane, bis(methyl-4-[3-n-alkyl(C12/C14)thiopropionyloxy]5-tert-butylphenyl)sulfide, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, lauryl/stearyl thiodipropionate, 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-thiobis(6-tert-butyl-p-cresol), and distearyl disulfide.

Other antioxidants include nitrone compounds such as N-benzyl-α-phenyl nitrone, N-ethyl-α-methyl nitrone, N-octyl-α-heptyl nitrone, N-lauryl-α-undecyl nitrone, N-tetradecyl-α-tridecyl nitrone, N-hexadecyl-α-pentadecyl nitrone, N-octyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α-heptadecyl nitrone, and N-octadecyl-α-heptadecyl nitrone; 3-arylbenzofuran-2(3H)-one, 3-(alkoxyphenyl)benzofuran-2-one, 3-(acyloxyphenyl)benzofuran-2(3H)-one, and 5,7-di-tert Benzofuran compounds such as 5-butyl-3-(3,4-dimethylphenyl)-benzofuran-2(3H)-one, 5,7-di-tert-butyl-3-(4-hydroxyphenyl)-benzofuran-2(3H)-one, 5,7-di-tert-butyl-3-{4-(2-hydroxyethoxy)phenyl}-benzofuran-2(3H)-one, 6-(2-(4-(5,7-di-tert-2-oxo-2,3-dihydrobenzofuran-3-yl)phenoxy)ethoxy)-6-oxohexyl-6-((6-hydroxyhexanoyl)oxy)hexanoate, and 5-di-tert-butyl-3-(4-((15-hydroxy-3,6,9,13-tetraoxapentadecyl)oxy)phenyl)benzofuran-2(3H)one are included.

Examples of hindered amine compounds 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, 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)-di(tridecyl)-1,2,3,4-butane tetracarboxylate, and bis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate. Methyl-4-piperidyl)-di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-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-ylamino]undecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-ylamino]undecane Decane, 3,9-bis[1,1-dimethyl-2-{tris(2,2,6,6-tetramethyl-4-piperidyloxycarbonyl)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-bis[1,1-dimethyl-2-{tris(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, bis(1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 2,2,6,6-tetramethyl-4-piperidylhexadecanoate, 2,2,6,6-tetramethyl-4-piperidyloctadecanoate, etc.

Examples of ultraviolet absorbers include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)benzotriazole, )-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolylphenol), polyethylene glycol ester of 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole, 2-[2-hydroxy-3-(2-acryloyloxyethyl)-5-methylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)- 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-octylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole 2-[2-hydroxy-3-tert-amyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(3-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-4-(2-methacryloyloxymethyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropyl)phenyl]benzotriazole azoles, 2-(2-hydroxyphenyl)benzotriazoles such as 2-[2-hydroxy-4-(3-methacryloyloxypropyl)phenyl]benzotriazole; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy)benzoate, dodecyl (3,5-di-tert-butyl-4-hydroxy)benzoate, tetradecyl ( Benzoates such as 3,5-di-tert-butyl-4-hydroxy)benzoate, hexadecyl (3,5-di-tert-butyl-4-hydroxy)benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy)benzoate, and behenyl (3,5-di-tert-butyl-4-hydroxy)benzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β,β-diphenylacrylate, methyl-2 -cyano-3-methyl-3-(p-methoxyphenyl)acrylate and other cyanoacrylates; 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, trioctyl-2,2',2"-((1,3,5-triazine-2,4,6-triyl)tris(3-hydroxybenzene-4-,1-diyl)tripropionate), 2-(4,6- Examples of triazines include diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, and 1,12-bis[2-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)-3-hydroxyphenoxy]ethyl]dodecanedioate; various metal salts or metal chelates, particularly nickel and chromium salts or chelates.

Examples of fatty acid metal salts include metal salts of fatty acids having 12 to 30 carbon atoms and containing linear or branched fatty acid residues. Examples of metal ions constituting fatty acid metal salts include sodium ions, potassium ions, lithium ions, dihydroxyaluminum ions, calcium ions, zinc ions, barium ions, magnesium ions, and hydroxyaluminum ions, among which sodium ions, potassium ions, lithium ions, and calcium ions are preferred. Examples of fatty acids constituting fatty acid metal salts include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, arachidonic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, and melissic acid, among which myristic acid and stearic acid are preferred. The fatty acid constituting fatty acid metal salts may be one in which one or more of the hydrogen atoms of the fatty acid residue are substituted with a hydroxyl group. Examples of such fatty acids include 12-hydroxystearic acid and 12-hydroxyoleic acid.

Examples of flame retardants include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinol bis(diphenyl phosphate), (1-methylethylidene)-4,1-phenylenetetraphenyl diphosphate, 1,3-phenylenetetrakis(2,6-dimethylphenyl)phosphate, and ADEKA Corporation's products under the trade names "ADEKA STAB FP-500", "ADEKA STAB FP-600", and "ADEKA STAB FP-700". Aromatic phosphate esters of "Stab FP-800", phosphonate esters such as divinyl phenylphosphonate, diallyl phenylphosphonate, and 1-butenyl phenylphosphonate, phosphinate esters such as phenyl diphenylphosphinate, methyl diphenylphosphinate, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, phosphazene compounds such as bis(2-allylphenoxy)phosphazene and dicresylphosphazene, melamine phosphate, melamine pyrophosphate, and melamine polyphosphate. amine, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compounds, red phosphorus and other phosphorus-based flame retardants, magnesium hydroxide, aluminum hydroxide and other metal hydroxides, brominated bisphenol A type epoxy resins, brominated phenol novolac type epoxy resins, hexabromobenzene, pentabromotoluene, ethylene bis(pentabromophenyl), ethylene bistetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethylene) brominated flame retardants such as 2,4,6-tris(tribromophenoxy)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene, and 2,4,6-tris(tribromophenoxy)-1,3,5-triazine, tribromophenylmaleimide, tribromophenylacrylate, tribromophenylmethacrylate, tetrabromobisphenol A dimethacrylate, pentabromobenzylacrylate, and brominated styrene. These flame retardants are preferably used in combination with anti-drip agents such as fluororesins, and flame retardant assistants such as polyhydric alcohols and hydrotalcite.

Examples of lubricants include saturated fatty acid amides such as stearic acid amide and behenic acid amide, unsaturated fatty acid amides such as oleic acid amide and erucic acid amide, ethylene bisstearic acid amide, butyl stearate, glycerol monostearate, sorbitan monopalmitate, sorbitan monostearate, stearic acid, stearyl alcohol, mannitol, and hydrogenated castor oil.

Examples of fillers include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, dolomite, silica, alumina, potassium titanate whiskers, wollastonite, fibrous magnesium oxysulfate, etc., and the particle size (fiber diameter, fiber length, and aspect ratio in the case of fibers) can be appropriately selected for use. Among these fillers, talc is particularly preferred because it has an excellent effect of imparting rigidity and is easily available. Furthermore, the fillers can be surface-treated as necessary.

Hydrotalcites may be complex salt compounds containing magnesium, aluminum, hydroxyl groups, carbonate groups, and any water of crystallization, and may be natural or synthetic. The crystal structure, particle shape, and particle size of hydrotalcites are not particularly limited. Furthermore, hydrotalcites may be those in which at least a portion of the magnesium or aluminum has been replaced with other metals such as alkali metals or zinc, or at least a portion of the hydroxyl groups or carbonate groups has been replaced with other anion groups. Furthermore, hydrotalcites may be those in which the water of crystallization has been dehydrated, and the surface may be coated with a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal salt of oleic acid, an organic sulfonic acid metal salt such as an alkali metal salt of dodecylbenzenesulfonic acid, a higher fatty acid amide, a higher fatty acid ester, or a wax.

Examples of antistatic agents include low molecular weight antistatic agents based on nonionic, anionic, cationic or amphoteric surfactants, and polymeric antistatic agents based on polymeric compounds. Examples of nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polyolefin glycol ethylene oxide adducts; polyhydric alcohol type nonionic surfactants such as polyethylene oxide, fatty acid esters of glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol or sorbitan, alkyl ethers of polyhydric alcohols, and fatty amides of alkanolamines. Examples of anionic surfactants include carboxylates such as alkali metal salts of higher fatty acids; sulfate ester salts such as higher alcohol sulfate ester salts, higher alkyl ether sulfate ester salts, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates; and phosphate ester salts such as higher alcohol phosphate ester salts. Examples of cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionate salts, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine. Among these, anionic surfactants are preferred, and sulfonates such as alkylbenzenesulfonates, alkylsulfonates, and paraffin sulfonates are particularly preferred.

Examples of polymer-type antistatic agents include ionomers and block polymers having polyethylene glycol as the hydrophilic part. Examples of ionomers include the ionomers described in JP 2010-132927 A. Examples of polymers having polyethylene glycol as the hydrophilic part include the polyether ester amides described in JP 7-10989 A, the polymers of polyolefin and polyethylene glycol described in U.S. Pat. No. 6,552,131 A, and the polymers of polyester and polyethylene glycol described in JP 2016-023254 A.

Fluorescent whitening agents are compounds that absorb ultraviolet rays from sunlight or artificial light, convert them into violet to blue visible light, and radiate them to enhance the whiteness and blueness of molded products through their fluorescent action. Examples of fluorescent whitening agents include the benzoxazole compound C.I. Fluorescent Brightener 184; the coumarin compound C.I. Fluorescent Brightener 52; and the diaminostilbene disulfonic acid compounds C.I. Fluorescent Brightener 24, 85, and 71.

The pigment is not particularly limited, and commercially available pigments can be used. Specific examples of pigments include Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 1 80, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 29, 56, 60, 61, 62, 64; Pigment Violet 1, 15, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

Dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, etc.

The resin composition of the present embodiment may further contain a compound other than the compound represented by the above general formula (1) that has an excellent crystallization promoting effect on the thermoplastic resin (hereinafter referred to as "other nucleating agent"). Examples of the other nucleating agent include sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, lithium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, dihydroxyaluminum 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, and hydroxyaluminum. Metal salts of aromatic phosphates such as bis[2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate], metal salts of carboxylates such as sodium benzoate, aluminum 4-tert-butylbenzoate, sodium adipate, disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate, and calcium cyclohexane-1,2-dicarboxylate, dibenzylidene sorbitol, bis(methylbenzylidene)sorbitol, bis(3,4-dimethylbenzylidene)sorbitol, and bis(p-ethylbenzyl)sorbitol. Examples of suitable nucleating agents include polyol derivatives such as 1,2,3-trideoxy-4,6:5,7-o-bis(4-propylbenzylidene)nonitol, bis(dimethylbenzylidene)sorbitol, and 1,2,3-trideoxy-4,6:5,7-o-bis(4-propylbenzylidene)nonitol, and amide compounds such as N,N',N"-tris[2-methylcyclohexyl]-1,2,3-propanetricarboxamide, N,N',N"-tricyclohexyl-1,3,5-benzenetricarboxamide, N,N'-dicyclohexylnaphthalenedicarboxamide, and 1,3,5-tri(dimethylisopropoylamino)benzene. The resin composition of this embodiment may not contain the above-mentioned other nucleating agents.

The method for producing the resin composition of this embodiment is not particularly limited, and examples thereof include a method of blending a thermoplastic resin powder or pellets, the compound represented by the general formula (1) above, and other additives as necessary, and dry blending the mixture using a mixing device such as an FM mixer, a mill roll, a Banbury mixer, or a super mixer, and a method of blending a thermoplastic resin powder or pellets, the compound represented by the general formula (1), and other additives as necessary, and dry blending the mixture obtained, using a melt kneading device such as a single screw extruder or a twin screw extruder, for example, at 120 to 350°C. Here, the kneaded product obtained by melt kneading may be granulated into a shape such as pellets using a granulating device such as a pelletizer.

The compound represented by the above general formula (1) may be blended as an additive composition containing the compound and one or more of the other additives described above, or may be blended as an additive master batch containing a thermoplastic resin, the compound represented by the general formula (1), and, as necessary, one or more of the other additives. Here, the additive composition may be a one-pack additive composition that is further blended with a granulation aid such as a binder, wax, a solvent, or silica and granulated.

In addition, at least one of the compounds represented by the general formula (1) and the other additives described above may be added before or during the polymerization of the thermoplastic resin monomer or oligomer, and the remaining components may be added to the resulting polymer.

<Molded products>
Next, the molded article will be described. The molded article of the present embodiment is obtained by molding the above-mentioned resin composition.

The molded product of this embodiment has excellent properties such as heat resistance, rigidity, and transparency.

Examples of molded articles of this embodiment include injection molded articles, fibers, flat yarns, biaxially oriented films, uniaxially oriented films, unoriented films, sheets, thermoforming molded articles, extrusion blow molded articles, injection blow molded articles, injection stretch blow molded articles, profile extrusion molded articles, rotational molded articles, etc. More specific examples of molded articles of this embodiment include automobile exterior parts, automobile interior parts, housings, containers, piping, etc.

The method for molding the molded product of this embodiment is not particularly limited, and examples include injection molding, extrusion molding, blow molding, rotational molding, vacuum molding, inflation molding, calendar molding, slush molding, dip molding, and thermoforming.

<Method for promoting crystallization of thermoplastic resin>
Next, a method for promoting the crystallization of a thermoplastic resin will be described. The method for promoting the crystallization of a thermoplastic resin of this embodiment is a method for promoting the crystallization of a thermoplastic resin, and is a method in which a compound represented by the above general formula (1) is used as a nucleating agent for a thermoplastic resin. However, polyolefin resins are excluded from the thermoplastic resin.

According to the method for promoting crystallization of a thermoplastic resin of this embodiment, it is possible to promote the crystallization of a thermoplastic resin other than a polyolefin-based resin. As a result, according to the method for promoting crystallization of a thermoplastic resin, it is possible to impart properties such as heat resistance, rigidity, and transparency to a molded article made of a resin composition containing a thermoplastic resin other than a polyolefin-based resin.

In the method for promoting crystallization of a thermoplastic resin according to the present embodiment, the thermoplastic resin preferably contains a polyamide-based resin, a polyester-based resin, or a polylactic acid-based resin, and more preferably contains a polyamide-based resin or a polyester-based resin.

In the method for promoting crystallization of a thermoplastic resin of this embodiment, the thermoplastic resin preferably contains, more specifically, polyamide 6 (PA6), polyamide 66 (PA66), polyamide 11 (PA11), polyamide 12 (PA12), polyamide 9T (PA9T), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) or polylactic acid (PLA), and more specifically, polyamide 6 (PA6), polyamide 66 (PA66), polyamide 11 (PA11), polyamide 12 (PA12), polyamide 9T (PA9T) , polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT) or polyethylene naphthalate (PEN), more preferably polyamide 6 (PA6), polyamide 66 (PA66), polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), even more preferably polyamide 6 (PA6), polyamide 66 (PA66) or polyethylene terephthalate (PET), and particularly preferably polyamide 6 (PA6) or polyethylene terephthalate (PET).

The present invention will be explained in more detail below with reference to examples, but the present invention is not limited in any way by the following examples.

<Production of Resin Composition>
(Examples 1 to 70 and Comparative Examples 1 to 10)
The thermoplastic resins and compounds represented by general formula (1) shown in Tables 1 to 10 were mixed in the amounts shown in Tables 1 to 10 and mixed for 1 minute at 1000 rpm using an FM mixer (FM200, manufactured by Mitsui Mining Co., Ltd.). The resulting mixture was put into a single-screw extruder (Labo Plastomill Micro, manufactured by Toyo Seiki Seisakusho Co., Ltd.), melt-kneaded under the conditions of the melting temperature and screw speed of 200 rpm shown in Tables 1 to 10, and then granulated to obtain resin pellets. The obtained resin pellets were dried at 60°C for 8 hours to obtain the resin compositions of Examples 1 to 70 and Comparative Examples 1 to 10. In Tables 1 to 10, the unit of the amount of the thermoplastic resin and the compound represented by general formula (1) is parts by mass.

The thermoplastic resins used in this example are as follows:
PA6: Polyamide 6 (manufactured by Toray Industries, product name "Amilan CM1017")
PA66: Polyamide 66 (manufactured by Toray Industries, trade name "Amilan CM3001-N")
PA11: Polyamide 11 (manufactured by Arkema, product name "Rilsan BESN P20 TL")
PA12: Polyamide 12 (manufactured by UBE, product name "UBESTA3024U")
PA9T: Polyamide 9T (manufactured by Kuraray Co., Ltd., product name "Genesta N1000A")
PET: Polyethylene terephthalate (manufactured by Teijin Limited, product name "TRN-8550FF")
PTT: Polytrimethylene terephthalate (manufactured by DuPont, product name "Sorona EP3301 NC010")
PBT: Polybutylene terephthalate (manufactured by Polyplastics Co., Ltd., product name "DURANEX 2002")
PEN: Polyethylene naphthalate (manufactured by Teijin Limited, product name "Teonex TN8050SC")
PLA: Polylactic acid (NatureWorks, product name "Ingeo Biopolymer 2003D")

In addition, in Tables 1 to 10, the "steric structure" of the compound represented by general formula (1) represents the steric structure of the aspartic acid residue, and Z represents the following group.

<Characteristics evaluation>
The crystallization temperatures of the resin compositions of Examples 1 to 70 and Comparative Examples 1 to 10 were measured using a differential scanning calorimeter (PerkinElmer, device name "Diamond"). Here, the crystallization temperature was determined as the temperature (°C) of the exothermic peak observed during the cooling process when the temperature was raised from room temperature to 300°C at a rate of 50°C/min under a nitrogen atmosphere, held for 5 minutes, and then cooled to 50°C at a rate of 10°C/min. The case where the crystallization temperature was higher than that of the polymer to which the compound represented by the general formula (1) was not added was marked as ○. The results are also shown in the column of crystallization promotion effect in Tables 1 to 10.

※１：一般式(1)で表される化合物の配合量
※２：製造時の溶融温度

*1: Amount of compound represented by general formula (1) *2: Melting temperature during production

As a result of the above measurements, it was found that the resin compositions of Examples 1 to 7, 8 to 14, 15 to 21, 22 to 28, 29 to 35, 36 to 42, 43 to 49, 50 to 56, 57 to 63, and 64 to 70 have higher crystallization temperatures than the resin compositions of Comparative Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10, respectively. Therefore, it was found that in the resin compositions of Examples 1 to 70, the compound represented by general formula (1) acts as a nucleating agent for thermoplastic resins, promoting the crystallization of the thermoplastic resin.

From the above, it was confirmed that the nucleating agent for thermoplastic resins of the present invention has an excellent crystallization promoting effect on thermoplastic resins other than polyolefin-based resins.

Claims (7)

The following general formula (1):

(In general formula (1), M represents a monovalent to trivalent metal atom having a specific gravity of 4.0 or less, or a divalent to trivalent metal atom having a hydroxyl group bonded thereto and having a specific gravity of 4.0 or less, a represents 1 or 2, b represents 1 or 3, x represents an integer of 1 to 3, and ax=2b is satisfied. Z represents a group represented by the following general formula (2) or (3):

(in general formulas (2) and (3), * represents the position at which it is linked to the carbonyl carbon in general formula (1), Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms, and R ₁ to R ₁₀ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms)) The nucleating agent for thermoplastic resins according to claim 1, which is a nucleating agent for polyamide-based resins, a nucleating agent for polyester-based resins, or a nucleating agent for polylactic acid-based resins. Thermoplastic resins (excluding polyolefin resins) and
The following general formula (1):

(In general formula (1), M represents a monovalent to trivalent metal atom having a specific gravity of 4.0 or less, or a divalent to trivalent metal atom having a hydroxyl group bonded thereto and having a specific gravity of 4.0 or less, a represents 1 or 2, b represents 1 or 3, x represents an integer of 1 to 3, and ax=2b is satisfied. Z represents a group represented by the following general formula (2) or (3):

(in general formulas (2) and (3), * represents the position at which the group is bonded to the carbonyl carbon of general formula (1), Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms, and R ₁ to R ₁₀ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms),
A resin composition comprising: The resin composition according to claim 3, wherein the thermoplastic resin comprises a polyamide resin, a polyester resin, or a polylactic acid resin. A molded article obtained by molding the resin composition according to claim 3 or 4. A method for promoting crystallization of a thermoplastic resin (excluding polyolefin-based resins), comprising the steps of:
The following general formula (1):

(In general formula (1), M represents a monovalent to trivalent metal atom having a specific gravity of 4.0 or less, or a divalent to trivalent metal atom having a hydroxyl group bonded thereto and having a specific gravity of 4.0 or less, a represents 1 or 2, b represents 1 or 3, x represents an integer of 1 to 3, and ax=2b is satisfied. Z represents a group represented by the following general formula (2) or (3):

(in general formulas (2) and (3), * represents the position at which the compound is linked to the carbonyl carbon in general formula (1), Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms, and R ₁ to R ₁₀ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms)) as a nucleating agent for thermoplastic resins. The method for promoting crystallization of a thermoplastic resin according to claim 6, wherein the thermoplastic resin includes a polyamide resin, a polyester resin, or a polylactic acid resin.