JP6908892B2 - Polyamide resin composition containing a metal salt of a phenylphosphonic acid compound - Google Patents

Description

The present invention relates to a polyamide resin composition, and more particularly to a polyamide resin composition containing a crystal nucleating agent composed of a metal salt of a phenylphosphonic acid compound, and a polyamide resin molded product obtained from the resin composition.

Polyamide resins are generally widely used as engineering plastics having excellent mechanical properties, chemical resistance, oil resistance, and the like. Among them, polyamide 610, which is classified as biomass plastics, has excellent properties such as chemical resistance, metal chloride resistance (for example, calcium chloride resistance), low water absorption, and dimensional stability. For example, food containers, bearings, connectors, etc. It is expected as a molding material for fuel tubes and hoses for automobiles, interior materials, housings and parts of electrical and electronic products.

However, since the polyamide resin has a slow crystallization rate, it has a drawback that it softens at a temperature equal to or higher than the glass transition point (Tg) when it is not sufficiently crystallized. In addition, the crystallinity of the polyamide resin is improved by heat treatment (annealing) at a predetermined temperature in the mold during injection molding, but the crystallization rate is slow, so the molding cycle is poor and productivity is a problem. There is.

In order to solve these problems, a method of adding a crystal nucleating agent to a polyamide resin is being studied. The crystal nucleating agent becomes the primary crystal nuclei of the crystalline polymer, promotes crystal growth, miniaturizes the spherulite size, and promotes crystallization.
So far, layered silicates (Patent Document 1), talc (Patent Document 2) and the like have been disclosed as crystal nucleating agents for polyamide resins.

Special Table 2002-527593 Japanese Unexamined Patent Publication No. 2003-89773

As described above, various crystal nucleating agents have been proposed to increase the crystallization rate of the polyamide resin, but in recent years, more effective crystal nucleating agents have been proposed in order to realize higher molding processability of the polyamide resin. It is desired.
Therefore, the present invention comprises a polyamide resin composition to which a crystal nucleating agent suitable for promoting crystallization of the polyamide resin is added, which has a faster crystallization rate than the polyamide resin and can improve molding processability. An object of the present invention is to provide a polyamide resin molded product obtained by crystallizing a polyamide resin composition.

As a result of diligent studies to achieve the above object, the present inventors promote crystallization of the polyamide resin by adding a metal salt of a specific phenylphosphonic acid compound as a crystal nucleating agent to the polyamide resin. Found that is possible.

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、又は炭素原子数２乃至１１のアルコキシカルボニル基を表す。）
第２観点として、前記フェニルホスホン酸化合物の金属塩が、リチウム塩、ナトリウム塩、カリウム塩、マグネシウム塩、カルシウム塩、バリウム塩、マンガン塩、鉄塩、コバルト塩、ニッケル塩、銅塩、亜鉛塩、銀塩、アルミニウム塩、及びスズ塩からなる群から選ばれる少なくとも一種の金属塩である、第１観点に記載のポリアミド樹脂組成物に関する。
第３観点として、前記フェニルホスホン酸化合物の金属塩が、カルシウム塩、マンガン塩、亜鉛塩及びスズ塩からなる群から選ばれる少なくとも一種の金属塩である、第２観点に記載のポリアミド樹脂組成物に関する。
第４観点として、前記フェニルホスホン酸化合物の金属塩がマンガン塩である、第３観点に記載のポリアミド樹脂組成物に関する。
第５観点として、前記結晶核剤の含有量が、前記ポリアミド樹脂１００質量部に対して０．００１〜１０質量部である、第１観点乃至第４観点のうち何れか一項に記載のポリアミド樹脂組成物に関する。
第６観点として、前記ポリアミド樹脂が、ポリアミド６、ポリアミド１１、ポリアミド１２、ポリアミド４６、ポリアミド６６、ポリアミド６１０、ポリアミド６１２、ポリアミド１０１０、ポリアミド１２１２、ポリアミド４Ｔ、ポリアミドＭ５Ｔ、ポリアミド６Ｔ、ポリアミド６I、ポリアミド９Ｔ、ポリアミド１０Ｔ、及びポリアミドＭＸＤ６からなる群から選択される少なくとも一種を含むものである、第１観点乃至第５観点のうち何れか一項に記載のポリアミド樹脂組成物に関する。
第７観点として、前記ポリアミド樹脂が、ポリアミド６１０を少なくとも含むものである、第６観点に記載のポリアミド樹脂組成物に関する。
第８観点として、第１観点乃至第７観点のうち何れか一項に記載のポリアミド樹脂組成物を結晶化してなる、ポリアミド樹脂成形体に関する。That is, the present invention relates to a polyamide resin composition containing a polyamide resin and a crystal nucleating agent composed of a metal salt of a phenylphosphonic acid compound represented by the formula [1] as a first aspect.

(In the formula, R ¹ and R ² independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxycarbonyl group having 2 to 11 carbon atoms.)
As a second aspect, the metal salt of the phenylphosphonic acid compound is a lithium salt, a sodium salt, a potassium salt, a magnesium salt, a calcium salt, a barium salt, a manganese salt, an iron salt, a cobalt salt, a nickel salt, a copper salt, or a zinc salt. The polyamide resin composition according to the first aspect, which is at least one metal salt selected from the group consisting of silver salt, aluminum salt, and tin salt.
As a third aspect, the polyamide resin composition according to the second aspect, wherein the metal salt of the phenylphosphonic acid compound is at least one metal salt selected from the group consisting of calcium salt, manganese salt, zinc salt and tin salt. Regarding.
The fourth aspect relates to the polyamide resin composition according to the third aspect, wherein the metal salt of the phenylphosphonic acid compound is a manganese salt.
As a fifth aspect, the polyamide according to any one of the first to fourth aspects, wherein the content of the crystal nucleating agent is 0.001 to 10 parts by mass with respect to 100 parts by mass of the polyamide resin. Regarding the resin composition.
As a sixth aspect, the polyamide resin is polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 1212, polyamide 4T, polyamide M5T, polyamide 6T, polyamide 6I, polyamide. The polyamide resin composition according to any one of the first to fifth aspects, which comprises at least one selected from the group consisting of 9T, polyamide 10T, and polyamide MXD6.
As a seventh aspect, the polyamide resin composition according to the sixth aspect, wherein the polyamide resin contains at least polyamide 610.
As an eighth aspect, the present invention relates to a polyamide resin molded product obtained by crystallizing the polyamide resin composition according to any one of the first to seventh aspects.

In the polyamide resin composition of the present invention, by using a metal salt of a specific phenylphosphonic acid compound as a crystal nucleating agent, the effect of promoting crystallization of the polyamide resin is improved, and by extension, the polyamide having excellent molding processability. It is possible to provide a resin composition and a polyamide resin molded product obtained by crystallizing the polyamide resin composition.

Hereinafter, the present invention will be described in more detail.

<Polyamide resin composition>
The polyamide (hereinafter, also referred to as PA) resin composition of the present invention is composed of a PA resin and a crystal nucleating agent composed of a metal salt of a phenylphosphonic acid compound.

[PA resin]
Examples of the PA resin used in the present invention include those made of a polymer of a diamine and a dibasic acid, a polymer of a lactam or an aminocarboxylic acid, or a copolymer of two or more of these. Be done.

The diamine has, for example, an aliphatic diamine such as tetramethylenediamine, hexamethylenediamine, octamethylenediamine, nonametyrediamine, undecamethylenediamine, dodecamethylenediamine; and an aromatic / cyclic structure such as methylylenediamine. Examples include diamine.
Examples of the dicarboxylic acid include aliphatic dicarboxylic acids such as adipic acid, heptanedicarboxylic acid, octanedicarboxylic acid, nonandicarboxylic acid, undecanedicarboxylic acid and dodecanedicarboxylic acid; and aromatic / cyclic structures such as terephthalic acid and isophthalic acid. Examples thereof include dicarboxylic acids having.

Examples of the lactam include lactams having 6 to 12 carbon atoms such as γ-butyrolactam, ε-caprolactam, ω-heptalactam, and ω-laurolactam.
Examples of the aminocarboxylic acid include aminocarboxylic acids having 6 to 12 carbon atoms such as ε-aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

Specific examples of such PA resins include polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 1212, polyamide 4T, polyamide M5T, polyamide 6T, and polyamide 6I. Homopolymers such as Polyamide 9T, Polyamide 10T and Polyamide MXD6; Copolymers such as Polyamide 6/66, Polyamide 6/12 and Polyamide 11/12 can be mentioned. Of these, polyamide 610 is preferable.
These PA resins may be used alone or in combination of two or more.

As these PA resins, commercially available ones can be preferably used. For example, Lilsan (registered trademark) series, Pevacs (registered trademark) series, Hipprolon series, Daicel Ebonic (registered trademark) manufactured by Alchema Co., Ltd. Daiamide series manufactured by Daiamide Co., Ltd., Vestamid (registered trademark) series, Amiran series manufactured by Toray Industries, Inc., UBE nylon series manufactured by Ube Industries, Ltd., Uvesta series, Gramide (registered trademark) series manufactured by Toyo Spinning Co., Ltd. , Genesta series manufactured by Kuraray Industries, Inc., Ultramid (registered trademark) series manufactured by BASF, Aalen series manufactured by Mitsui Chemicals, Inc., and the like.

Further, the PA resin used in the present invention may be a PA homopolymer or a PA copolymer as a main component and a blend polymer with another resin. Examples of other resins include general-purpose thermoplastic resins / thermoplastic engineering plastics and biodegradable resins, which will be described later. The content of the other resin in the blend polymer with the other resin is preferably 50% by mass or less.

Examples of the general-purpose thermoplastic resin / thermoplastic engineering plastic include polyethylene (PE), polyethylene copolymer, polypropylene (PP), polypropylene copolymer, ethylene-propylene copolymer, polybutylene (PB), and ethylene-vinyl alcohol co-weight. Polyolefin resins such as coalescing (EVOH), ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), poly (4-methyl-1-pentene); polystyrene (PS), high impact Polystyrene resins such as sex polystyrene (HIPS), acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), methyl methacrylate-styrene copolymer (MS); polymethyl methacrylate (polymethyl methacrylate (MS)) (Meta) acrylic resin such as PMMA); Polyvinyl chloride resin; Polyvinylidene chloride resin; Polyurethane resin; Polyethylene terephthalate (PET), Polybutylene terephthalate (PBT), Polyethylene naphthalate (PEN), Polybutylene naphthalate (PBN) Such as polyester resin; polyimide resin; polycarbonate resin; polyphenylene ether resin; modified polyphenylene ether resin; polyacetal resin; polysulfone resin; polyphenylene sulfide resin and the like.

Examples of the above-mentioned biodegradable resin include polyglycolic acid (PGA), polylactic acid (PLA), poly (3-hydroxybutyric acid) (PHB), and a copolymer of 3-hydroxybutyrate and 3-hydroxyhexanoic acid (P). Polyhydroxyalkanoic acid such as PHBH); polyester resin such as polycaprolactone, polybutylene succinate, polybutylene succinate / adipate, polybutylene succinate / carbonate, polyethylene succinate, polyethylene succinate / adipate; Examples thereof include polyvinyl alcohol; modified starch; cellulose acetate; chitin; chitosan; lignin and the like.

[Metal salt of phenylphosphonic acid compound]
The crystal nucleating agent used in the present invention comprises a metal salt of a phenylphosphonic acid compound represented by the formula [1].

In the phenylphosphonic acid compound represented by the above formula [1], R ¹ and R ² in the formula are independently hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, or 2 to 11 carbon atoms. Represents the alkoxycarbonyl group of. Here, the alkoxycarbonyl group having 2 to 11 carbon atoms refers to an alkoxycarbonyl group having 1 to 10 carbon atoms in the alkoxy group.

Examples of the alkyl group having 1 to 10 carbon atoms in R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group and the like. ..
Examples of the alkoxycarbonyl group having 2 to 11 carbon atoms include a methoxycarbonyl group and an ethoxycarbonyl group.

Specific examples of the phenylphosphonic acid compound represented by the above formula [1] include phenylphosphonic acid, 4-methylphenylphosphonic acid, 4-ethylphenylphosphonic acid, 4-n-propylphenylphosphonic acid, and 4-isopropylphenyl. Phosphonate, 4-n-butylphenylphosphonic acid, 4-isobutylphenylphosphonic acid, 4-tert-butylphenylphosphonic acid, 3,5-dimethoxycarbonylphenylphosphonic acid, 3,5-diethoxycarbonylphenylphosphonic acid, 2 , 5-Dimethoxycarbonylphenylphosphonic acid, 2,5-diethoxycarbonylphenylphosphonic acid and the like.
As these compounds, commercially available products can be preferably used as they are.

As the metal forming the metal salt of the phenylphosphonic acid compound, monovalent, divalent, and trivalent metals can be used. It is also possible to use a mixture of two or more kinds of metals.
Specific examples of the metal forming the metal salt include lithium, sodium, potassium, magnesium, calcium, barium, manganese, iron, cobalt, nickel, copper, zinc, silver, aluminum, tin and the like. Among the metal salts formed from these metals, calcium salts, manganese salts, zinc salts and tin salts are preferable. Among them, the manganese salt is particularly preferable because it can increase the crystallization rate of the PA resin and obtain a PA resin composition having excellent molding processability.

The method for producing the metal salt of the phenylphosphonic acid compound is not particularly limited, but in general, the phenylphosphonic acid compound, the chloride, sulfate, or nitrate of the metal and an alkali such as sodium hydroxide are mixed in water. The metal salt of the phenylphosphonic acid compound is precipitated, filtered, and dried to obtain a crystalline powder. Further, the phenylphosphonic acid compound and the oxide, hydroxide, carbonate, or organic acid salt of the metal are mixed and reacted in water or in an organic solvent, and then the solvent is filtered, distilled off, and dried. It can also be obtained by.
The form of the obtained powder is usually granular crystals, plate-like crystals, rod-like crystals, needle-like crystals, or the like, and may be a form in which these crystals are laminated.
When these compounds (crystalline powder) are commercially available, commercially available products can be used.
In the formation of the metal salt of the phenylphosphonic acid compound, the chemical quantitative ratio of the phenylphosphonic acid compound and the metal is not particularly limited, but generally, the chemical quantitative ratio of the phenylphosphonic acid compound / metal is 1/2 to 2 /. It is preferable to use in the range of 1. It is preferable that the metal salt of the phenylphosphonic acid compound does not contain a free phenylphosphonic acid compound or metal that does not form a salt.

The average particle size of the metal salt of the phenylphosphonic acid compound is preferably 10 μm or less, more preferably 5 μm or less. Here, the average particle diameter (μm) is a 50% volume diameter (median diameter) obtained by measuring by a laser diffraction / scattering method based on the Mie theory. The smaller the average particle size, the faster the crystallization rate tends to be, which is preferable.
In order to reduce the average particle size of the metal salt of the phenylphosphonic acid compound to 10 μm or less, the crystalline powder obtained by the above method is subjected to the shearing force of a homomixer, a Henschel mixer, a Ladyge mixer or the like, if necessary. It can be made into fine powder by a mixer having the above, or a dry crusher such as a ball mill, a pin disc mill, a palberizer, an inomizer, or a counter jet mill. Further, it can be made into fine powder by a wet pulverizer such as a ball mill, a bead mill, a sand grinder, or an attritor using water, an organic solvent that can be mixed with water, and a mixed solution thereof.

The amount of the metal salt added to the phenylphosphonic acid compound is 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the PA resin. Is. By setting the addition amount to 0.001 part by mass or more, a sufficient crystallization rate can be obtained. Further, even if it exceeds 10 parts by mass, the crystallization rate is not further increased, so that it is economically advantageous to use it in an amount of 10 parts by mass or less.

[Other additives]
A known inorganic filler may be added to the PA resin composition of the present invention as long as the effects of the present invention are not impaired. Examples of the inorganic filler include glass fiber, carbon fiber, talc, mica, silica, kaolin, clay, wolastonite, glass beads, glass flakes, potassium titanate, calcium carbonate, magnesium sulfate, titanium oxide and the like. .. The shape of these inorganic fillers may be fibrous, granular, plate-like, needle-like, spherical, or powder. These inorganic fillers can be used within 300 parts by mass with respect to 100 parts by mass of PA resin.

A known flame retardant may be added to the PA resin composition of the present invention as long as the effects of the present invention are not impaired. Examples of the flame retardant include halogen-based flame retardants such as bromine and chlorine; anti-mon flame retardants such as antimon trioxide and antimon pentoxide; and inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide and silicone compounds. ; Phosphorus flame retardants such as red phosphorus, phosphate esters, ammonium polyphosphate, phosphazene; melamine, melam, melem, melon, melamine cyanurate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine polyphosphate / melam -Melamine-based flame retardants such as melem compound salt, melamine alkylphosphonate, melamine phenylphosphonate, melamine sulfate, and melamine methanesulfonate; fluororesins such as PTFE can be mentioned. These flame retardants can be used within 200 parts by mass with respect to 100 parts by mass of PA resin.

Further, additives generally added to the PA resin composition of the present invention as needed, such as end-capping agents, hydrolysis inhibitors, heat stabilizers, as long as the effects of the present invention are not impaired. Light stabilizers, heat ray absorbers, ultraviolet absorbers, antioxidants, impact improvers, plasticizers, compatibilizers, various coupling agents such as silane, titanium, and aluminum, foaming agents, antistatic agents, and release agents. Molds, lubricants, antibacterial antifungal agents, pigments, dyes, fragrances, various other fillers, other crystal nucleating agents, other thermoplastic resins and the like may be appropriately blended.

[Manufacturing method of polyamide resin composition]
The PA resin composition of the present invention can be produced by mixing the PA resin and a crystal nucleating agent composed of a metal salt of the phenylphosphonic acid compound. The method for mixing the crystal nucleating agent is not particularly limited. For example, a method of mixing the crystal nucleating agent with a PA resin or a composition containing a PA resin and another additive before molding, or a PA resin or PA resin at the time of molding. Examples thereof include a method of mixing a crystal nucleating agent with a composition containing the above and other additives (for example, side feed). Further, when producing a PA resin, it is also possible to produce a PA resin composition by mixing a crystal nucleating agent with a monomer of diamine and a dicarboxylic acid or an activator thereof.

The PA resin composition of the present invention preferably has a temperature-lowering crystallization temperature (temperature at which the resin crystallizes in the process of cooling the molten resin composition) Tcc of 188 ° C. or higher, preferably 191 ° C. or higher. Some are more preferred.

<Polyamide resin molded product>
The PA resin molded product of the present invention is composed of a crystal nucleating agent composed of the crystallized PA resin and a metal salt of the phenylphosphonic acid compound. The spherulite diameter of the PA resin molded product of the present invention is preferably 30 μm or less, more preferably 20 μm or less. By setting the spherulite diameter to 30 μm or less, a PA resin molded product having a smoother surface can be obtained.
Such a PA resin molded product can be obtained, for example, by using the PA resin composition of the present invention and crystallizing the PA resin contained therein. The method for crystallizing the PA resin is not particularly limited. For example, in the process of molding the PA resin composition into a predetermined shape, the PA resin composition may be heated to a crystallization temperature or higher and then cooled. Further, in the above process, the PA resin composition is heated to a crystallization temperature or higher, and then rapidly cooled to form a molded product in an amorphous state, which can also be heated to crystallize.
The PA resin molded product of the present invention has excellent mechanical strength and heat resistance.

When molding the PA resin composition of the present invention, various molded products can be easily manufactured by using conventional molding methods such as general injection molding, blow molding, vacuum forming, and compression molding.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
In the examples, the devices and conditions used for sample preparation and analysis of physical properties are as follows.

(1) Differential scanning calorimetry (DSC)
Equipment: Diamond DSC manufactured by PerkinElmer Japan Co., Ltd.

The abbreviations have the following meanings.
PA610: Polyamide 610 [Vestamide®, Terra HS16 Natural, manufactured by Daicel Evonik Industries, Ltd.]
PPA: Phenylphosphonic acid [manufactured by Nissan Chemical Industries, Ltd.]
PPA-Zn: Zinc Phenylphosphonate [Eco-Promote (registered trademark) manufactured by Nissan Chemical Industries, Ltd.]
HFIPA: 1,1,1,3,3,3-hexafluoro-2-propanol

[Production Example 1] Production of calcium phenylphosphonate (PPA-Ca) In a reaction vessel equipped with a stirrer, calcium chloride dihydrate [manufactured by Wako Pure Chemical Industries, Ltd.] 7.4 g (50 mmol) and 100 g of water. Was charged and stirred to obtain a uniform solution. Next, a solution prepared by dissolving 7.8 g (50 mmol) of PPA and 4.2 g (105 mmol) of sodium hydroxide in 68 g of water was added to this solution stirred at room temperature (approximately 23 ° C.), and the mixture was further stirred for 1 hour. .. The produced solid was collected by filtration under reduced pressure and washed with water. The obtained wet product was dried at 200 ° C. for 6 hours to obtain the desired calcium phenylphosphonate (PPA-Ca) as a white powder.

[Production Example 2] Manganese phenylphosphonate (PPA-Mn) Manganese chloride tetrahydrate [manufactured by Wako Pure Chemical Industries, Ltd.] 9.9 g (50 mmol) is used instead of calcium chloride dihydrate. The operation was carried out in the same manner as in Production Example 1 to obtain the desired manganese phenylphosphonate (PPA-Mn) as a light pink powder.
The obtained manganese phenylphosphonate was anhydrous immediately after drying, but became a monohydrate at room temperature (about 23 ° C.) under an air atmosphere.

[Production Example 3] Production of tin phenylphosphonate (PPA-Sn) 9.5 g (50 mmol) of tin (II) chloride [manufactured by Wako Pure Chemical Industries, Ltd.] was used instead of calcium chloride dihydrate. Except for the above, the same procedure as in Production Example 1 was carried out to obtain the desired tin phenylphosphonate (PPA-Sn) as an ivory-colored powder.

[Examples 1 to 4]
To 100 parts by mass of PA610, 0.5 parts by mass of the compound shown in Table 1 and 900 parts by mass of HFIPA were added as crystal nucleating agents, and using an ultrasonic cleaner (output 150 W) at room temperature (about 23 ° C.) for 30 minutes. A polyamide resin composition was obtained by irradiating with ultrasonic waves.
This resin composition was dropped onto a hot plate at 60 ° C. to evaporate the solvent to obtain a polyamide resin film-like molded product in an amorphous state containing a crystal nucleating agent.
The temperature-decreasing crystallization temperature (Tcc) and the semi-crystallization time (t _1/2 ) of the obtained amorphous film-shaped molded product were measured according to the following procedure. The results are also shown in Table 1.

[Low temperature crystallization temperature (Tcc)]
Approximately 2 mg was cut out from the amorphous film-like molded product. For the crystallization of polyamide, which is observed when this film piece is heated to 250 ° C. at 100 ° C./min using DSC, held as it is at 250 ° C. for 1 minute, and then cooled at 20 ° C./min. The temperature at the peak of the resulting exothermic (crystallization enthalpy ΔHc) peak was measured as the cooling crystallization temperature (Tcc). The larger the Tcc value, the faster the crystallization rate under the same conditions, indicating that the crystal nucleating agent has an excellent effect.

[Semi-crystallization time (t _1/2 )]
Approximately 2 mg was cut out from the amorphous film-like molded product. When this film piece was heated to 250 ° C. at 100 ° C./min using DSC, held at 250 ° C. for 1 minute, then cooled to 150 ° C. at 100 ° C./min, and held at 150 ° C. as it was. The time from when the temperature reached 150 ° C. until the exotherm (crystallization enthalpy ΔHc) derived from the crystallization of the polyamide reached its peak was measured as the _{semi-crystallization time (t 1/2).} The _{smaller the value of t 1/2,} the faster the crystallization rate under the same conditions, indicating that the crystal nucleating agent has an excellent effect.

[Comparative Example 1]
The operation and evaluation were carried out in the same manner as in Example 1 except that the crystal nucleating agent was not added. The results are also shown in Table 1.

[Reference example]
The operation and evaluation were carried out in the same manner as in Example 1 except that the crystal nucleating agent was changed to talc [Microace P-8 manufactured by Nippon Talc Co., Ltd.]. The results are also shown in Table 1.

From the results in Table 1, those using a metal salt of a specific phenylphosphonic acid compound as the crystal nucleating agent (Examples 1 to 4) are higher than those without adding the crystal nucleating agent (Comparative Example 1). It showed Tcc and fast t _1/2 , and was confirmed to have a crystallization promoting effect. _{In particular, the one using manganese phenylphosphonate shows high Tcc and fast t 1/2} even when compared with the one using conventionally used talc (reference example), and has an extremely excellent crystallization promoting effect. Was confirmed to have.
That is, by adding a metal salt of a specific phenylphosphonic acid compound as a crystal nucleating agent to the polyamide resin, the crystallization rate of the polyamide resin is increased, and a polyamide resin composition having excellent heat resistance and molding processability is provided. Is now possible.

Claims (5)

A polyamide resin composition containing a polyamide resin and a crystal nucleating agent composed of a manganese salt of a phenylphosphonic acid compound represented by the formula [1].

(In the formula, R ¹ and R ² independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxycarbonyl group having 2 to 11 carbon atoms.) The content of the crystal nucleating agent is 0.001 to 10 parts by weight with respect to the polyamide resin 100 parts by weight of the polyamide resin composition according to claim 1. The polyamide resin is polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 1212, polyamide 4T, polyamide M5T, polyamide 6T, polyamide 6I, polyamide 9T, polyamide 10T, The polyamide resin composition according to claim 1 or 2 , wherein the polyamide resin composition comprises at least one selected from the group consisting of and polyamide MXD6. The polyamide resin composition according to claim 3 , wherein the polyamide resin contains at least polyamide 610. A polyamide resin molded product obtained by crystallizing the polyamide resin composition according to any one of claims 1 to 4.